US20050029194A1 - Method for removal of guanidine compound from aqueous media - Google Patents
Method for removal of guanidine compound from aqueous media Download PDFInfo
- Publication number
- US20050029194A1 US20050029194A1 US10/743,239 US74323903A US2005029194A1 US 20050029194 A1 US20050029194 A1 US 20050029194A1 US 74323903 A US74323903 A US 74323903A US 2005029194 A1 US2005029194 A1 US 2005029194A1
- Authority
- US
- United States
- Prior art keywords
- guanidine compound
- aqueous media
- adsorbent
- alkali metal
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- -1 guanidine compound Chemical class 0.000 title claims abstract description 125
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 title claims abstract description 121
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000012736 aqueous medium Substances 0.000 title claims abstract description 106
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 87
- 239000003463 adsorbent Substances 0.000 claims abstract description 83
- 239000004927 clay Substances 0.000 claims abstract description 40
- 239000012528 membrane Substances 0.000 claims abstract description 33
- 238000001728 nano-filtration Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001179 sorption measurement Methods 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 230000007935 neutral effect Effects 0.000 claims abstract description 17
- 229910001508 alkali metal halide Inorganic materials 0.000 claims abstract description 15
- 150000008045 alkali metal halides Chemical class 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 63
- LYWKAJZTPLXHEM-UHFFFAOYSA-M bis(diethylamino)methylidene-diethylazanium;chloride Chemical compound [Cl-].CCN(CC)C(N(CC)CC)=[N+](CC)CC LYWKAJZTPLXHEM-UHFFFAOYSA-M 0.000 claims description 60
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 20
- HHJJPFYGIRKQOM-UHFFFAOYSA-N sodium;oxido-oxo-phenylphosphanium Chemical group [Na+].[O-][P+](=O)C1=CC=CC=C1 HHJJPFYGIRKQOM-UHFFFAOYSA-N 0.000 claims description 16
- 239000011780 sodium chloride Substances 0.000 claims description 15
- BKFXSOCDAQACQM-UHFFFAOYSA-N 3-chlorophthalic acid Chemical group OC(=O)C1=CC=CC(Cl)=C1C(O)=O BKFXSOCDAQACQM-UHFFFAOYSA-N 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 238000000197 pyrolysis Methods 0.000 claims description 8
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- NRGWEQLAXOTOPB-UHFFFAOYSA-N 1,1,2,3,3-pentaethylguanidine Chemical compound CCN=C(N(CC)CC)N(CC)CC NRGWEQLAXOTOPB-UHFFFAOYSA-N 0.000 claims description 5
- 150000001450 anions Chemical group 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 229910000275 saponite Inorganic materials 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910001594 brammallite Inorganic materials 0.000 claims description 2
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001596 celadonite Inorganic materials 0.000 claims description 2
- 229910001649 dickite Inorganic materials 0.000 claims description 2
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000271 hectorite Inorganic materials 0.000 claims description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 229940094522 laponite Drugs 0.000 claims description 2
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 claims description 2
- 229910052627 muscovite Inorganic materials 0.000 claims description 2
- 229910000273 nontronite Inorganic materials 0.000 claims description 2
- 229910000276 sauconite Inorganic materials 0.000 claims description 2
- 229910021647 smectite Inorganic materials 0.000 claims description 2
- 229910052902 vermiculite Inorganic materials 0.000 claims description 2
- 239000010455 vermiculite Substances 0.000 claims description 2
- 235000019354 vermiculite Nutrition 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims 1
- 229910052618 mica group Inorganic materials 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 description 51
- 239000002351 wastewater Substances 0.000 description 26
- 150000003839 salts Chemical class 0.000 description 19
- 239000011148 porous material Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 14
- 150000002357 guanidines Chemical class 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 11
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 11
- 229910021385 hard carbon Inorganic materials 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 241000894007 species Species 0.000 description 9
- 239000012466 permeate Substances 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000002952 polymeric resin Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229920003002 synthetic resin Polymers 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000012465 retentate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 0 [1*]n([2*])c(n([3*])[4*])n([5*])[6*] Chemical compound [1*]n([2*])c(n([3*])[4*])n([5*])[6*] 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229920001429 chelating resin Polymers 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920001601 polyetherimide Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920001059 synthetic polymer Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000013213 extrapolation Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000004255 ion exchange chromatography Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- APOAEMIYHVGWEZ-UHFFFAOYSA-N 4-chloroisoindole-1,3-dione Chemical class ClC1=CC=CC2=C1C(=O)NC2=O APOAEMIYHVGWEZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- RYTLGWCJESCDMY-UHFFFAOYSA-N carbamimidoyl chloride Chemical class NC(Cl)=N RYTLGWCJESCDMY-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000011549 displacement method Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- JBCHWGTZAAZJKG-UHFFFAOYSA-N 2-methyl-5-nitroisoindole-1,3-dione Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(C)C(=O)C2=C1 JBCHWGTZAAZJKG-UHFFFAOYSA-N 0.000 description 1
- BYJQAPYDPPKJGH-UHFFFAOYSA-N 3-(2-carboxyethyl)-1h-indole-2-carboxylic acid Chemical compound C1=CC=C2C(CCC(=O)O)=C(C(O)=O)NC2=C1 BYJQAPYDPPKJGH-UHFFFAOYSA-N 0.000 description 1
- DCFSQEWFDPNDPQ-UHFFFAOYSA-N 5-chloro-2-methylisoindole-1,3-dione Chemical compound C1=C(Cl)C=C2C(=O)N(C)C(=O)C2=C1 DCFSQEWFDPNDPQ-UHFFFAOYSA-N 0.000 description 1
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- HZOVEAKQSNCUCB-UHFFFAOYSA-N [diethylamino(ethylamino)methylidene]-diethylazanium;chloride Chemical compound [Cl-].CCNC(N(CC)CC)=[N+](CC)CC HZOVEAKQSNCUCB-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000003973 alkyl amines Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- AXQUONJGMAVWJA-UHFFFAOYSA-O dibutyl-[butylamino-(dibutylamino)methylidene]azanium Chemical compound CCCCNC(N(CCCC)CCCC)=[N+](CCCC)CCCC AXQUONJGMAVWJA-UHFFFAOYSA-O 0.000 description 1
- WGMBWDBRVAKMOO-UHFFFAOYSA-L disodium;4-[2-(4-oxidophenyl)propan-2-yl]phenolate Chemical compound [Na+].[Na+].C=1C=C([O-])C=CC=1C(C)(C)C1=CC=C([O-])C=C1 WGMBWDBRVAKMOO-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical group [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/06—Purification or separation of guanidine
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Definitions
- the present invention relates a method for removing a guanidine compound from aqueous media. More particularly, it relates a method for removing an ionic or a neutral, or both an ionic and a neutral guanidine compound from aqueous media.
- Guanidine compounds are frequently used as catalysts in chemical reactions, for example because of their basic properties in the case of neutral guanidine compounds or because of their phase transfer catalytic properties in the case of ionic guanidine compounds (also know as guanidinium salts).
- U.S. Pat. No. 5,229,482 discloses a displacement method for the preparation of polyetherimides from bis(chlorophthalimides) and alkali metal salts of dihydroxy-substituted aromatic hydrocarbons using a solvent of low polarity such as o-dichlorobenzene in the presence of a thermally stable phase transfer catalyst such as a hexaalkylguanidinium halide.
- a thermally stable phase transfer catalyst such as a hexaalkylguanidinium halide.
- 5,830,974 discloses a similar method using a monoalkoxybenzene such as anisole as solvent. Isolation of product from organic media comprising a guanidine compound often involves washing the organic media with water. In these cases all or at least a portion of guanidine compound may transfer to the aqueous phase. For proper disposal of the wash water and for recovery and reuse of valuable guanidine compounds, a method is needed to remove a guanidine compound from the aqueous media.
- U.S. Pat. No. 5,759,406 teaches removal of adsorbates such as guanidinium salts from brine solution using a non-ion-exchangeable adsorbent polymeric resin.
- adsorbates such as guanidinium salts from brine solution
- a non-ion-exchangeable adsorbent polymeric resin show limited adsorption capacity and must be used in relatively large amounts for efficient removal of the target adsorbates.
- U.S. Pat. No. 6,214,235 teaches purification of brine solution for electrolysis by removal of organic salts using carbonaceous adsorbents.
- the method requires brine solutions with concentration of salt greater than 5 weight percent and makes no suggestion for recovery of organic salts.
- the present inventors have discovered a method for removing guanidine compounds from aqueous media.
- the method is efficient and is also applicable to a wide variety of aqueous media.
- the method works surprisingly well for removing a guanidine compound from aqueous media quite low in ionic strength as measured by concentration of salt.
- the present invention comprises a method for removing a neutral or an ionic guanidine compound from an aqueous media comprising less than 4 wt. % of an alkali metal halide, wherein the method is selected from the group consisting of (a) adsorption onto a carbonaceous adsorbent, (b) adsorption onto a clay adsorbent, (c) filtration through a nanofiltration membrane, and (d) removal of water and calcination.
- the present invention comprises a method for removing a guanidine compound selected from the group consisting of hexaethylguanidinium chloride, pentaethylguanidine, and mixtures thereof, from an aqueous media optionally comprising an alkali metal halide, wherein the method is selected from the group consisting of (b) adsorption onto a clay adsorbent, (c) filtration through a nanofiltration membrane having a molecular weight cut-off sufficient to retain from about 80% to about 100% of the guanidine compound, and (d) removal of water and calcination at a temperature in a range of between about 500° C.
- concentration of guanidine compound present initially in the aqueous media ranges from about 1 part per million to about 20,000 parts per million, and wherein the concentration of guanidine compound following removal is less than 20% of the initial concentration.
- guanidine compound as used in the present invention describes a composition comprising either an ionic guanidinium salt or a neutral guanidine compound, or both.
- guanidine compounds comprise ionic guanidinium species of the formula (I):
- the alkyl radicals suitable as R 1-6 in formulas (I) and (II) comprise primary alkyl radicals, generally containing about 1-12 carbon atoms.
- R 1 is usually an alkyl radical of the same structure or a C 2-12 alkylene radical in which the terminal carbons are primary; most preferably, it is C 2-6 alkyl or C 4-8 straight chain alkylene.
- any combination of R 1-6 and the corresponding nitrogen atom(s) may form a heterocyclic radical including, but not limited to, piperidino, pyrrolo or morpholino.
- the positive charge in the guanidinium salt is delocalized over one carbon and three nitrogen atoms. This is believed to contribute to the salts stability under the relatively high temperature conditions encountered by the salts in some applications. As a result, decomposition of the guanidinium salt does not occur or occurs only to a very minor extent. The results include suppression of by-product formation and potential for continued use of the salts via recycle.
- Guanidinium salts include those disclosed in U.S. Pat. Nos. 5,116,975, 5,132,423 and 5,229,482.
- Hexaalkylguanidinium salts may be prepared by the reaction of a corresponding urea (e.g., a tetraalkylurea) with phosgene or phosphorus oxychloride, or by the reaction of a similar thiourea with an N,N-dialkylcarbamoyl halide, to yield a chloroformamidinium salt, frequently referred to as a “Vilsmeier salt”, followed by reaction of said salt with a corresponding amine (e.g., a dialkylamine).
- a corresponding amine e.g., a dialkylamine
- alpha,omega-Bis(pentaalkylguanidinium)alkane salts may be similarly prepared by reaction of the chloroformamidinium salt with a monoalkylamine, followed by reaction of the resulting pentaalkylguanidinium salt with an alkylene dihalide.
- the alpha,omega-bis(pentaalkylguanidinium)alkane salts defined when R 1 is alkylene and n is 2 are disclosed, for example, in U.S. Pat. No. 5,081,298.
- the concentration of guanidine compound initially in aqueous media ranges from about 0.5 parts per million (ppm) to 100,000 ppm (10%), by weight of the aqueous media, and preferably ranges from about 1 ppm to about 20,000 ppm (2%) by weight of the aqueous media. In particularly preferred embodiments the concentration of guanidine compound initially in aqueous media ranges from about 1 ppm to about 1000 ppm, or from about 1 ppm to about 500 ppm.
- Aqueous media in the present invention comprises any aqueous media comprising water and at least one ionic or neutral guanidine compound, or both of at least one ionic and at least one neutral guanidine compound.
- aqueous media may also comprise any additional components which are water-soluble or at least partially water-soluble and which arise from or are present initially in chemical reactions in which a guanidine compound is present in the capacity of reaction product, reaction byproduct, decomposition product, reactant or catalyst, or in more than one capacity.
- aqueous media comprises at least one guanidine compound which was added as a catalyst in a displacement reaction, illustrative examples of which include polymerization reactions.
- aqueous media comprises both at least one guanidine compound added as a catalyst in a polymerization reaction and at least one guanidine compound decomposition product derived from an initial guanidine compound.
- Guanidine compounds which may be employed as catalysts in displacement reactions comprise guanidinium salts, illustrative examples of which include hexaalkylguanidinium salts and alpha,omega-bis(pentaalkylguanidinium)alkane salts.
- hexaalkylguanidinium salts and alpha,omega-bis(pentaalkylguanidinium)alkane salts comprise halogen salts, particularly bromides and chlorides.
- a hexaalkylguanidinium salt employed as a catalyst is hexaethylguanidinium chloride.
- an alpha,omega-bis(pentaalkylguanidinium)alkane salt employed as a catalyst is 1,6-bis(penta-n-butylguanidinium)hexane dibromide.
- guanidinium salts are employed as catalysts in displacement reactions of bisphenol salts such as bisphenol A disodium salt with nitro- or halo-substituted imides such as 4-nitro-N-methylphthalimide, 4-chloro-N-methylphthalimide or 1,3-bis(N-(4-chlorophthalimido))benzene also known as 2,2′-(1,3-phenylene)bis(5-chloro-1H-isoindole-1,3(2H-dione)), to produce bisimides or polyetherimides.
- U.S. Pat. No. 5,229,482 discloses a displacement method for the preparation of polyetherimides from bis(chlorophthalimides) and alkali metal salts of dihydroxy-substituted aromatic hydrocarbons using a solvent of low polarity such as o-dichlorobenzene in the presence of a thermally stable phase transfer catalyst such as a hexaalkylguanidinium halide.
- a thermally stable phase transfer catalyst such as a hexaalkylguanidinium halide.
- U.S. Pat. No. 5,830,974 discloses a similar method using a monoalkoxybenzene such as anisole as solvent.
- an aqueous medium comprising at least one guanidine compound is formed when a reaction mixture comprising an organic solvent and at least one guanidine compound is washed with water.
- an aqueous medium comprising at least one guanidine compound may optionally comprise less than about 5 wt. % of an organic solvent and any other water-soluble or partially water-soluble species present in said reaction mixture.
- said organic solvent has a boiling point above about 150° C.
- said organic solvent forms an azeotrope with water.
- an aqueous medium comprising at least one guanidine compound may optionally comprise an alkali metal salt, and in particular, sodium chloride or potassium chloride.
- an alkali metal salt is typically present in the aqueous media, it is typically present at a level in a range of between about 0.01 wt. % and about 10 wt. %, based on the total weight of the aqueous media. In other embodiments when an alkali metal salt is present in the aqueous media, it is typically present at less than 5 wt.%, or less than 4 wt.
- an alkali metal salt is present in the aqueous media at a level of between about 0.01 wt. % and about 4 wt. % or at a level of between about 0.01 wt. % and about 3.5 wt. %, based on the total weight of the aqueous media.
- a hexaalkylguanidinium salt may undergo some dealkylation to form the corresponding pentaalkylguanidine, for example under displacement reaction conditions.
- an aqueous medium comprises a first guanidinium salt and one or both of a neutral guanidine compound and its corresponding protonated analog (that is, a second guanidinium compound which is the protonated decomposition product a first guanidinium compound).
- a aqueous medium comprises hexaethylguanidinium chloride and one or both of pentaethylguanidine and pentaethylguanidinium chloride (the protonated decomposition product of hexaethylguanidinium chloride).
- displacement reaction mixtures may optionally comprise still other inorganic or organic components in addition to at least one guanidine compound. Washing said reaction mixture with water may result in an aqueous medium comprising at least one guanidine compound and additional components which may be at least partially water-soluble. Said additional inorganic or organic components may be removed along with a guanidine compound from aqueous media by methods of the present invention. Therefore, it is to be understood that, although removal of a guanidine compound is referred to, additional organic or inorganic components may also be present in the aqueous media and may also be removed using the teachings herein. In a particular embodiment an aqueous medium may optionally comprise an imidization catalyst used in a displacement reaction.
- Suitable imidization catalysts are known in the art; they include salts of organophosphorus acids, particularly phosphinates such as sodium phenylphosphinate and heterocyclic amines such as 4-diaminopyridine.
- a preferred catalyst is sodium phenylphosphinate also known as phenyl phosphinic acid, sodium salt.
- Imidization catalyst levels in the aqueous media can vary widely, for example from about 10 ppm to about 5000 ppm.
- an aqueous medium may optionally comprise an organic component of a polymerization reaction, such as a monomer or end-capping agent or a reaction product thereof.
- chlorophthalic acid may be present in aqueous media obtained by washing a polymerization reaction mixture used to prepare a polyetherimide.
- Chlorophthalic acid levels in the aqueous media can vary widely, for example from about 1 ppm to about 20,000 ppm. In some particular embodiments chlorophthalic acid levels in the aqueous media can vary from about 1 ppm to about 5,000 ppm, or from about 1 ppm to about 2,000 ppm.
- aqueous media is contacted with a carbon adsorbent to remove a guanidine compound.
- Suitable carbon adsorbents may be activated carbons.
- Activated carbons can be produced by pyrolyzing organic materials such as coal, peat, or coconut shells under high temperatures in a nonoxidizing environment.
- the raw carbonaceous material can also be mixed with a binding agent to form a granular material.
- the pyrolyzed carbonaceous material can then be activated by steaming to create a high capacity, high surface area adsorbent.
- Raw materials with low metals content are sometimes preferred as they produce more pure activated carbons with a final lower metals content although an acid wash step can be used leach some of the residual metals from the as produced activated carbon.
- the carbon is acid washed to prevent leaching of components from the adsorbent into an acidic solution to be treated.
- One suitable activated carbon material that is commercially available is Type CPG Granular Carbon with particle size between 12 mesh and 40 mesh (i.e. mesh size 12 ⁇ 40), available from Calgon Carbon Corporation. Other factors useful in selecting activated carbons include base exchange capacity and particle size. Optimum activated carbons for treating a particular guanidine compound-comprising aqueous media may be determined without undue experimentation by those skilled in the art.
- a suitable carbon adsorbent may be derived from the pyrolysis of a synthetic resinous polymer.
- hard carbon adsorbents such adsorbents and their method of preparation are described, for example, in U.S. Pat. Nos. 4,040,990 and 4,957,897.
- these carbons are partially pyrolyzed particles preferably in the form of hard beads or spheres and having multimodal pore size, including micro and macro pores. They are produced by the controlled decomposition of a synthetic polymer.
- the pyrolysis as described in U.S. Pat. No.
- 4,040,990 is generally conducted in an inert atmosphere comprised of, for example, helium, argon, or nitrogen.
- Any of the many synthetic polymers disclosed in U.S. Pat. No. 4,040,990 can be employed in preparing the hard carbon adsorbent for the process of this invention.
- suitable polymers are those derived from aliphatic and aromatic materials which are ethylenically unsaturated.
- the polymer is cross-linked, because cross-linking often stabilizes the polymer thermally and leads to greater carbon yields.
- the polymer contains a carbon-fixing moiety, such as a cation, anion, strong base, weak base, sulfonic acid, carboxylic acid, halogen, or alkylamine moiety.
- a carbon-fixing moiety such as a cation, anion, strong base, weak base, sulfonic acid, carboxylic acid, halogen, or alkylamine moiety.
- suitable polymers include polylvinylidene chloride, and macroreticular ion-exchange resins derived from aliphatic and aromatic materials which are ethylenically unsaturated.
- the synthetic polymer is a polystyrene-divinylbenzene sulfonic acid ion-exchange resin.
- Suitable hard carbon adsorbents include, but are not limited to, those commercially available under the name AMBERSORB, available from Rohm and Haas Co.
- the hard carbon adsorbents are highly stable, chemically, thermally and physically. In general they have a surface area of about 100-2000 m 2 /g, usually about 500-1200 m 2 /g and can be used, for example, in the form of approximately spherical particles having a mean particle size of, for example, from about 0.2 to 1.5 mm, preferably from about 0.3 to 1.0 mm.
- hard carbon adsorbents which are prepared by the pyrolysis of a synthetic resinous polymer, typically contain at least three distinct sets of pores of differing average size.
- One set comprises large pores or macropores, which typically range in size of at least 500 Angstroms in average diameter.
- the second set comprises intermediate pores or mesopores, which typically range in size from about 20 Angstroms to about 500 Angstroms.
- the third set and smallest pores or micropores are typically less than about 20 Angstroms in average diameter; however, the exact size depends on the temperature of pyrolysis of the synthetic polymer.
- the pyrolysis temperature also controls total pore volumes. Generally, as the pyrolysis temperature increases, the micropore volume increases.
- the macropore volume of hard carbon adsorbents useful for this invention are typically at least 0.10 ml/g; preferably in the range from about 0.10 ml/g to about 0.35 ml/g; more preferably in the range from about 0.15 ml/g to about 0.30 ml/g; and most preferably in the range from about 0.20 ml/g to about 0.25 ml/g.
- the mesopore volume of hard carbon adsorbents useful for this invention are typically in the range from about 0.05 ml/g to about 0.30 ml/g; preferably in the range from about 0.10 ml/g to about 0.25 ml/g; and most preferably in the range from about 0.12 ml/g to about 0.20 ml/g.
- the micropore volume of hard carbon adsorbents useful for this invention are at least about 0.10 ml/g; more preferably, in the range from about 0.20 ml/g to about 0.50 ml/g; and most preferably in the range from about 0.30 ml/g to about 0.45 ml/g.
- the process for removal of a guanidine compound from aqueous media using a carbonaceous adsorbent can be implemented in accordance with conventional methods for adsorption processes, for example as illustrated in U.S. Pat. Nos. 5,094,754 and 5,104,530.
- said process comprises bringing said aqueous media into contact with said carbonaceous adsorbent for a time sufficient to allow a guanidine compound to be adsorbed from said aqueous media onto said carbonaceous adsorbent; and separating said aqueous media from said carbonaceous adsorbent containing said absorbed guanidine compound.
- the carbonaceous adsorbents may be used in the form of a slurry or contained in a column or filter bed.
- the optimum particle size of the carbon may depend upon such factors as the particular mode of operation, e.g. slurrying the carbon with the aqueous media or passing the aqueous media through a column of activated carbon, and may be determined without undue experimentation by those skilled in the art.
- the carbonaceous adsorbent bed When in the form of a column or filter bed, the carbonaceous adsorbent bed may operated in an up flow process or a down flow process. In other embodiments two or more carbonaceous adsorbent beds may be connected in series.
- the process for removal of a guanidine compound from aqueous media using a carbonaceous adsorbent may be operated in continuous, semi-continuous or batch mode.
- the pH of the aqueous media may be in any convenient range, typically between about 1 and about 13. In some particular embodiments the pH of the aqueous media is greater than about 7. In other particular embodiments the pH of the aqueous media is in a range of between about 8 and about 13 or in a range of between about 9 and about 11.
- aqueous media is contacted with a clay adsorbent to remove a guanidine compound.
- Suitable clays typically comprise layered clays, usually silicate clays.
- layered clays usually silicate clays.
- layered clays that may be employed in this invention other than that they are capable of decreasing the concentration of guanidine compounds in an aqueous media.
- Illustrative of such layered clays that may be employed in this invention include, for instance, smectite and those of the kaolinite group such as kaolinite, halloysite, dickite, nacrite and the like.
- the layered clays are preferably natural or synthetic phyllosilicates, particularly smectic clays.
- Illustrative examples include, for instance, halloysite, montmorillonite, nontronite, beidellite, saponite, volkonskoite, laponite, sauconite, magadite, kenyaite, bentonite, stevensite, and the like. It is also within the scope of the invention to employ clays comprising minerals of the illite group, including hydromicas, phengite, brammallite, glaucomite, celadonite and the like.
- the preferred layered minerals include those often referred to as 2:1 layered silicate minerals, including muscovite, vermiculite, saponite, hectorite and montmorillonite, the latter often being most preferred.
- the clays may be synthetically produced, but most often they comprise naturally occurring minerals and are commercially available. Mixtures containing at least one of the clays as described herein are also suitable.
- Other suitable clay adsorbents include those described in U.S. Pat. No. 5,530,052.
- Preferred layered clays comprise particles containing a plurality of silicate platelets having a thickness of about 7-15 angstroms bound together at interlayer spacings of about 4 angstroms or less, and containing exchangeable cations such as Na + , Ca +2 , K + , Al +3 , and/or Mg +2 present at the interlayer surfaces.
- the clays typically have a cation exchange capacity of about 50-200 milliequivalents per 100 grams on a dry basis.
- the clay adsorbents are employed when predominantly in their alkali metal ion forms and particularly in their sodium ion forms. Generally, the clays are swollen with an aqueous solution prior to use to increase their adsorption capacity.
- the process for removal of a guanidine compound from aqueous media using a clay adsorbent can be implemented in accordance with conventional methods for adsorption processes.
- said process comprises bringing said aqueous media into contact with said clay adsorbent for a time sufficient to allow a guanidine compound to be adsorbed from said aqueous media onto said clay adsorbent; and separating said aqueous media from said clay adsorbent containing said absorbed guanidine compound.
- Illustrative methods of contacting the clay with the aqueous media comprising at least one guanidine compound include flow through columns and batch methods. The column method involves passing the aqueous media through a packed column of clay.
- Another method is to contact the clay with the aqueous media in a fluidized bed manner, for example an upflow of the aqueous media through a bed of clay. Additionally, stirred beds of clay may be contacted with the aqueous media.
- the clay is added to the aqueous media as a finely divided powder and after a sufficient amount of time is removed by well-known methods, illustrative examples of which comprise filtration, flocculation, flotation or centrifugation.
- the guanidine compound is sorbed on the clay and removed from the aqueous media when the clay is physically removed.
- aqueous media is contacted with a nanofiltration membrane to remove a guanidine compound.
- Nanofiltration is a known operation in which a solution or dispersion of a material to be treated is passed over a nanofiltration separation membrane at a pressure which is generally in the range of from about 1 to about 5 megapascals (depending upon the strength of the membrane) to cause the lower molecular weight materials to pass through the membrane along with the water to form a permeate and an aqueous phase which does not pass through the membrane, which is known as a retentate.
- An increase in pressure usually increases the rate of permeate formation.
- the pressure which can be utilized may be determined by such factors as the temperature, nature of the particular nanofiltration membrane and the particular design of the nanofiltration apparatus and may be readily determined without undue experimentation by those skilled in the art.
- the permeate Upon passage through the nanofiltration module, the permeate has a lower concentration of the guanidine compound than the retentate or the initial aqueous media.
- a suitable nanofiltration membrane has a molecular weight cut-off (MWCO) which is often related to membrane pore size, and which retains the guanidine compounds while allowing water to pass through the membrane.
- the desired MWCO is generally less than the molecular weight of a guanidine compound in the aqueous media.
- Nanofiltration membranes generally have a nominal MWCO of between about 100 Daltons (Da) and about 5 kilodaltons (kDa), or between about 100 Da and about 3 kDa, or between about 100 Da and about 1 kDa, or between about 100 Da and about 600 Da, or between about 150 Da and about 600 Da.
- a suitable nanofiltration membrane has an MWCO sufficient to retain from about 40% to about 100% of the guanidine compound, preferably from about 70% to about 100% of the guanidine compound, and more preferably from about 80% to about 100% of the guanidine compound.
- the process for removal of a guanidine compound from aqueous media using a nanofiltration membrane may be operated in continuous, semi-continuous or batch mode.
- Suitable nanofiltration membranes comprise sintered metal, ceramics or polymeric materials.
- Suitable polymeric nanofiltration membranes may be made, for example, of cellulose, cellulose acetate, polyamide, aramid, polyether, polysulfone, polyethersulfone, polyvinylpyrrolidone, polytetrafluoroethylene, or polyvinylidene fluoride; and are commercially available from several manufacturers, including Desalination Membrane Products (Escondido, Calif.), Dow/Film Tec Corporation (Minneapolis, Minn.), Osmonics (Minnetonka, Minn.), and Membrane Products Kiryat Weizman Ltd. (Rehovot, Israel).
- the type of membrane which is selected may be dependent upon such factors as the pH of the aqueous media to be treated with the nanofiltration unit, the molecular weight cut-off required, and the temperature and pressure at which the nanofiltration is to be carried out.
- aqueous media is subjected to removal of water and calcination to remove a guanidine compound.
- Water may be removed from the aqueous media by any convenient method. In a particular embodiment water is removed by evaporation. Evaporation may be conducted at any convenient pressure, typically at or below atmospheric pressure. Removal of water typically leaves less than 5 wt. % of the original amount of water remaining.
- the substantially solid residue is subjected to calcination at a temperature of greater than 400° C. or greater than 450° C. or greater than 500° C. In one embodiment calcination is performed at a temperature in a range of between about 500° C. and about 600° C.
- the time of calcination is typically such that substantially all organic residue comprising a guanidine compound is burned off. Removal of substantially all organic residue typically leaves less than 5 wt. % of the original organic residue remaining. In a particular embodiment removal of substantially all organic residue typically leaves less than 5 wt. % or less than 2 wt. % of the initial amount of guanidine compound, based on the weight of guanidine compound initially present in aqueous media. In some particular embodiments removal of substantially all organic residue results in no detectable guanidine compound remaining, and less than 1000 ppm, or less than 500 ppm, or less than 200 ppm total organic carbon remaining. There are no particular limitations on the apparatus or protocol for performing calcination. Calcination may be performed under air or under an inert atmosphere. Removal of water and calcination may be performed in continuous, semi-continuous or batch mode. Following calcination any solid residue may be disposed of in an appropriate manner such as land-filling.
- the concentration of guanidine compound in aqueous media is less than 50% of the initial concentration, or less than 30% of the initial concentration, or less than 25% of the initial concentration, or less than 20% of the initial concentration, or less than 15% of the initial concentration, or less than 10% of the initial concentration.
- the final concentrations of guanidine compound refer to that part of the aqueous medium which has passed through the membrane.
- the final concentrations of guanidine compound refers to weight percent based on the weight initially present in the aqueous medium.
- more than one step or a combination of steps selected from the group consisting of adsorption onto a carbonaceous adsorbent, adsorption onto a clay adsorbent, filtration through a nanofiltration membrane, and removal of water and calcination may be employed for removal of a guanidine compound from aqueous media.
- an additional inorganic or organic component which may optionally be present and which may be concurrently removed by methods of the present invention along with the guanidine compound may remain at a concentration in aqueous media of less than 50% of its initial concentration, or less than 30% of its initial concentration, or less than 25% of its initial concentration, or less than 20% of its initial concentration, or less than 15% of its initial concentration, or less than 10% of its initial concentration, depending upon such factors as the identity of the additional component, the type of treatment method, and the amount of adsorption agent.
- a guanidine compound may optionally be recovered from the adsorption media. Any known means may be used for recovery.
- a guanidine compound may be at least partially recovered from a carbonaceous adsorbent by treating the adsorbent with a boiling aqueous solution.
- a surfactant may be present in the aqueous solution to aid in recovery of the guanidine compound.
- a guanidine compound may be at least partially recovered from a carbonaceous or clay adsorbent by treating the adsorbent with an acidic media, particularly an aqueous acidic solution, optionally at elevated temperature and optionally containing a surfactant.
- Acidic solutions may be derived from either organic or inorganic acids.
- a guanidine compound may be recovered from an aqueous media in which the guanidine compound has previously been concentrated through contact of the aqueous media with a nanofiltration membrane.
- Illustrative methods for recovering a guanidine compound from aqueous media include removal of water or adsorption of the guanidine compound on an adsorbent. Recovered guanidine compounds may be recycled and reused in chemical processes, illustrative examples of which include those described herein above.
- a guanidine compound may be reactivated before reuse, such as by neutralization in the case of a protonated guanidine compound or by alkylation in the case of a dealkylated guanidine compound or by ion exchange in the case of a guanidinium compound.
- the carbonaceous and clay adsorbents and the nanofiltration membranes themselves may optionally be regenerated and optionally reused.
- the method of the invention is also applicable for treatment of waste water comprising said inorganic or organic components in the absence of at least one guanidine compound.
- the method of the invention may be used to remove an imidization catalyst such as sodium phenylphosphinate or an organic component of a polymerization reaction, such as a monomer or end-capping agent or a reaction product thereof, illustrative examples of which include chlorophthalic acid.
- the method of the invention may be used to remove both an imidization catalyst such as sodium phenylphosphinate and an organic component of a polymerization reaction, such as a monomer or end-capping agent or a reaction product thereof, illustrative examples of which include chlorophthalic acid.
- an imidization catalyst such as sodium phenylphosphinate
- an organic component of a polymerization reaction such as a monomer or end-capping agent or a reaction product thereof, illustrative examples of which include chlorophthalic acid.
- Calgon CPG acid-washed granular carbon was pulverized using a cryo-grinder.
- the pulverized carbon was sieved and particles of less than 325 mesh were collected and dried at 150° C. for 4 hours for use in isotherm experiments. Said carbon is referred to hereinafter as sieved Calgon CPG carbon.
- the pH of the waste water samples was generally in a range of between about 3 and 5.
- a waste water sample comprised 3.2 wt. % sodium chloride, 348 milligrams per liter (mg/L) of HEGCl and 72 mg/L of PEG.
- Six waste water samples (10 milliliters (ml) each) were individually treated with 50 mg. sieved Calgon CPG carbon and agitated for various periods of time at room temperature in a mechanical shaker. The samples were filtered and the filtrates were analyzed for concentration of HEGCl and PEG versus time. Values are given in Table 1. The data show the equilibrium is reached very quickly (less than about 5 minutes). TABLE 1 Time (minutes) conc.
- PEG (mg/ml) 0 0.35 0.07 5 0.04 0.01 10 0.04 0.01 30 0.04 0.01 60 0.05 0.01 90 0.04 0.01
- a waste water sample comprised 3.2 wt. % sodium chloride, 237 milligrams per liter (mg/L) of HEGCl and 46 mg/L of PEG.
- Samples of the waste water (10 ml. each) were treated with 50 mg. unpulverized Calgon CPG carbon.
- the pH of each mixture was adjusted to some value by the optional addition of either concentrated aqueous hydrochloric acid or 50% aqueous sodium hydroxide solution.
- Each mixture was agitated for 1 hour at room temperature in a mechanical shaker. The samples were filtered and the filtrates were analyzed for concentration of HEGCl and PEG. Values are given in Table 3.
- a waste water sample comprised 237 milligrams per liter (mg/L) of HEGCl and 46 mg/L of PEG. Samples of the waste water (10 ml. each) were treated with 50 mg. unpulverized Calgon CPG carbon. Varying amounts of sodium chloride were dissolved in each mixture. Each mixture was agitated for 1 hour at room temperature in a mechanical shaker. The samples were filtered and the filtrates were analyzed for concentration of HEGCl and PEG. Values are given in Table 4.
- a waste water sample with composition similar to that described above except comprising 6.4 wt. % sodium chloride was adjusted to pH 13 with 50% aqueous sodium hydroxide, treated with varying amounts of sieved Calgon CPG carbon and agitated for 1 hour at room temperature in a mechanical shaker.
- the sample was filtered and the filtrates was analyzed for concentration of HEGCl and PEG. Values are given in Table 5. From linear extrapolation the adsorptive capacity of the carbon adsorbent under these specified conditions was found to be approximately 139 mg HEGCl per gram of carbon adsorbent when equilibrium had been established. TABLE 5 Wt. of Concentration mg. mg. HEGCl Concentration mg.
- PEG carbon of HEGCl in HEGCl adsorbed per of PEG in mg PEG adsorbed per (g/L) solution (mg/L) adsorbed gram of carbon solution (mg/L) adsorbed gram of carbon 0 361 — — 68 — — 0.6 285 76 127 44 24 40 1.2 225 136 113 24 44 37 2.3 93 268 116 6 62 27 3.7 17 344 93 1 67 18 5.8 4 357 62 0 68 12
- AMBERSORB 572 a carbonaceous adsorbent with surface area of about 1100 square meters per gram (m2/g), was obtained from Rohm and Haas in mesh size of 20-50, and was used as received.
- a waste water sample comprised 3.2 wt. % sodium chloride, 348 mg/L of HEGCl and 78 mg/L of PEG.
- AMBERSORB 572 carbon was dried at 150° C. for 4 hours and then added in varying amounts in grams per liter (g/L) to individual waste water samples as described in Example 1. The samples were agitated for 15 minutes at room temperature in a mechanical shaker. The samples were filtered and the filtrates were analyzed to provide amount of HEGCl and PEG adsorbed per unit weight of adsorbent versus concentration of adsorbent in the mixture. Values are given in Table 6.
- AMBERSORB 572 (“A”); Calgon CPG (“B”); AMBERSORB 563 (“C”), a carbonaceous adsorbent with BET surface area of about 550 m 2 /g and about 62% of its pore volume associated with pores less than 2 nanometers (nm) and about 38% of its pore volume associated with pores of diameter greater than 2 nm and less than 30 nm.
- AMBERLITE XAD-2 (“D”) a non-ion-exchangeable adsorbent polymeric resin comprising structural units derived from styrene cross-linked with divinylbenzene
- AMBERLITE XAD-4 (“E”) a non-ion-exchangeable adsorbent polymeric resin comprising structural units derived from styrene cross-linked with divinylbenzene and having a surface area of about 750 m 2 /g and an average pore diameter of about 100 angstroms ( ⁇ ); AMBERL
- aqueous solution comprising HEGCl and PEG was subjected to filtration through a nanofiltration membrane comprising polytetrafluoroethylene (Osmonics type DK-5).
- the membrane pore size was such that it rejects 98% magnesium sulfate.
- the experimental protocol employed a standard membrane test cell (SEPA-CF test apparatus) in which wastewater at pH 1 was pumped in a crossflow manner across the surface of the membrane in a continuous fashion at a pressure of 276-310 kilopascals and flow rate of 2 liters per minute with 2 hour cycle time. Permeate flux was measured volumetrically and HEGCl/PEG concentrations in permeate and retentate were measured via ion chromatography. Data are shown in Table 8.
- Sodium montmorillonite (type KUNIPIA-F; sometimes referred to herein after as “clay”) was obtained from Kunimine Industries, Japan, and had a cation exchange capacity of 119 milliequivalents of sodium per 100 grams of clay on a basis of 90% dry weight of clay. Simulated waste water solutions were prepared by dissolving various amounts of HEGCl in deionized water. Varying equivalent amounts of sodium montmorillonite were suspended in water in a high-speed blender and the HEGCl solution was added thereto under various conditions with agitation at room temperature. The mixtures were filtered and the filtrates were analyzed by ion chromatography for amount of HEGCl remaining. Values are given in Table 9.
- Sodium montmorillonite was used as in Examples 10-18. Individual waste water samples comprising 366 mg/L of HEGCl; 73 mg/L of PEG and optionally 3.2 wt. % sodium chloride as noted were treated with 2 equivalents clay (based on HEGCI) and agitated under different conditions. The mixtures were filtered and the filtrates were analyzed by ion chromatography for amount of HEGCl and PEG remaining. Values are given in Table 10. The abbreviation “rt” means “room temperature”. TABLE 10 Con- Conc. of centration HEGCl % of PEG remaining HEGCl remaining % PEG Ex. (mg/L) removal (mg/L) removal Conditions 19 51 86 11 85 10 min.
- Waste water samples comprised HEGCl, PEG and sodium phenylphosphinate (SPP).
- Samples of the waste water (20 ml. each) were adjusted to either pH 1.9 or pH 13.9 with hydrochloric acid or aqueous sodium hydroxide, and treated with various amounts of pulverized Calgon CPG carbon. Each mixture was agitated for 1 hour at room temperature in a mechanical shaker. The samples were filtered and the filtrates were analyzed for concentration of HEGCI, PEG and SPP. Values are given in Table 11 compared to the initial concentration of the measured components. The data in Table 11 show that, as the pH is increased, the amounts of both ionic and neutral guanidine species and of SPP adsorbed by the carbon adsorbent increases.
- a 2.1 liter waste water sample comprising 1000 ppm total HEGCl and PEG, 253 ppm SPP, and 2404 ppm total organic carbon was evaporated to dryness by distillation to yield 170 g residue and 1.8 liters distillate. Analysis of the distillate showed no detectable HEGCl, PEG, or SPP.
- a 70 g sample of solid residue was heated in a stationary furnace under flowing nitrogen at a heating rate of 50° C. per minute to a temperature of 600° C. and held at 600° C. for 6 hours. Analysis showed that the residue weighed 67.92 g and had 100 ppm total organic carbon with no detectable HEGCl, PEG, or SPP.
Abstract
Description
- The present invention relates a method for removing a guanidine compound from aqueous media. More particularly, it relates a method for removing an ionic or a neutral, or both an ionic and a neutral guanidine compound from aqueous media.
- Guanidine compounds are frequently used as catalysts in chemical reactions, for example because of their basic properties in the case of neutral guanidine compounds or because of their phase transfer catalytic properties in the case of ionic guanidine compounds (also know as guanidinium salts). In particular examples U.S. Pat. No. 5,229,482 discloses a displacement method for the preparation of polyetherimides from bis(chlorophthalimides) and alkali metal salts of dihydroxy-substituted aromatic hydrocarbons using a solvent of low polarity such as o-dichlorobenzene in the presence of a thermally stable phase transfer catalyst such as a hexaalkylguanidinium halide. U.S. Pat. No. 5,830,974 discloses a similar method using a monoalkoxybenzene such as anisole as solvent. Isolation of product from organic media comprising a guanidine compound often involves washing the organic media with water. In these cases all or at least a portion of guanidine compound may transfer to the aqueous phase. For proper disposal of the wash water and for recovery and reuse of valuable guanidine compounds, a method is needed to remove a guanidine compound from the aqueous media.
- U.S. Pat. No. 5,759,406 teaches removal of adsorbates such as guanidinium salts from brine solution using a non-ion-exchangeable adsorbent polymeric resin. However, the polymeric resins show limited adsorption capacity and must be used in relatively large amounts for efficient removal of the target adsorbates.
- U.S. Pat. No. 6,214,235 teaches purification of brine solution for electrolysis by removal of organic salts using carbonaceous adsorbents. However, the method requires brine solutions with concentration of salt greater than 5 weight percent and makes no suggestion for recovery of organic salts. There is a continuing need for a method to remove guanidine compounds from aqueous media, particularly for waste water treatment and disposal, and for recovery of guanidine compounds for further use.
- The present inventors have discovered a method for removing guanidine compounds from aqueous media. The method is efficient and is also applicable to a wide variety of aqueous media. In one embodiment the method works surprisingly well for removing a guanidine compound from aqueous media quite low in ionic strength as measured by concentration of salt.
- In one of its embodiments the present invention comprises a method for removing a neutral or an ionic guanidine compound from an aqueous media comprising less than 4 wt. % of an alkali metal halide, wherein the method is selected from the group consisting of (a) adsorption onto a carbonaceous adsorbent, (b) adsorption onto a clay adsorbent, (c) filtration through a nanofiltration membrane, and (d) removal of water and calcination.
- In another of its embodiments the present invention comprises a method for removing a guanidine compound selected from the group consisting of hexaethylguanidinium chloride, pentaethylguanidine, and mixtures thereof, from an aqueous media optionally comprising an alkali metal halide, wherein the method is selected from the group consisting of (b) adsorption onto a clay adsorbent, (c) filtration through a nanofiltration membrane having a molecular weight cut-off sufficient to retain from about 80% to about 100% of the guanidine compound, and (d) removal of water and calcination at a temperature in a range of between about 500° C. and about 600° C.; wherein the concentration of guanidine compound present initially in the aqueous media ranges from about 1 part per million to about 20,000 parts per million, and wherein the concentration of guanidine compound following removal is less than 20% of the initial concentration.
- Various other features, aspects, and advantages of the present invention will become more apparent with reference to the following description, examples, and appended claims.
- In the following specification and the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings. The singular forms “a”, “an” and “the” include plural referents unless the context clearly dictates otherwise. “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not. The phrase “waste water” is sometimes used to refer to aqueous media comprising at least one guanidine compound. However, it should be understood that the present invention encompasses methods to treat any aqueous media comprising at least one guanidine compound.
-
-
- wherein each of R2, R3, R4, R5 and R6 is independently a primary alkyl radical and R1 a primary alkyl or bis(primary alkylene) radical, or at least one of R2, R3, R4, R5 and R6 is hydrogen, or at least one of the R1-R2, R3-R4 or R5-R6 combinations with the connecting nitrogen atom forms a heterocyclic radical; the moiety X is an anion; and the value of the parameter n is 1 or 2. The moiety X in formula (I) may be any anion and is preferably an anion of a strong acid, illustrative examples of which comprise chloride, bromide and methanesulfonate. Chloride and bromide ions are usually preferred. The value of n will be 1 or 2 depending upon whether R1 is alkyl or alkylene, respectively.
- wherein each of R2, R3, R4 and R5 is independently a primary alkyl radical and R1 is a primary alkyl or bis(primary alkylene) radical, or at least one of the R1-R2 or R3-R4 combinations with the connecting nitrogen atom forms a heterocyclic radical; and the value of the parameter n is 1 or 2.
- wherein each of R2, R3, R4, R5 and R6 is independently a primary alkyl radical and R1 a primary alkyl or bis(primary alkylene) radical, or at least one of R2, R3, R4, R5 and R6 is hydrogen, or at least one of the R1-R2, R3-R4 or R5-R6 combinations with the connecting nitrogen atom forms a heterocyclic radical; the moiety X is an anion; and the value of the parameter n is 1 or 2. The moiety X in formula (I) may be any anion and is preferably an anion of a strong acid, illustrative examples of which comprise chloride, bromide and methanesulfonate. Chloride and bromide ions are usually preferred. The value of n will be 1 or 2 depending upon whether R1 is alkyl or alkylene, respectively.
- The alkyl radicals suitable as R1-6 in formulas (I) and (II) comprise primary alkyl radicals, generally containing about 1-12 carbon atoms. R1 is usually an alkyl radical of the same structure or a C2-12 alkylene radical in which the terminal carbons are primary; most preferably, it is C2-6 alkyl or C4-8 straight chain alkylene. Alternatively, any combination of R1-6 and the corresponding nitrogen atom(s) may form a heterocyclic radical including, but not limited to, piperidino, pyrrolo or morpholino.
- As indicated by the dotted bonds in formula (I), the positive charge in the guanidinium salt is delocalized over one carbon and three nitrogen atoms. This is believed to contribute to the salts stability under the relatively high temperature conditions encountered by the salts in some applications. As a result, decomposition of the guanidinium salt does not occur or occurs only to a very minor extent. The results include suppression of by-product formation and potential for continued use of the salts via recycle.
- Guanidinium salts include those disclosed in U.S. Pat. Nos. 5,116,975, 5,132,423 and 5,229,482. Hexaalkylguanidinium salts may be prepared by the reaction of a corresponding urea (e.g., a tetraalkylurea) with phosgene or phosphorus oxychloride, or by the reaction of a similar thiourea with an N,N-dialkylcarbamoyl halide, to yield a chloroformamidinium salt, frequently referred to as a “Vilsmeier salt”, followed by reaction of said salt with a corresponding amine (e.g., a dialkylamine). Reference is made to Kantlehner et al., Liebigs Ann. Chem., 1984, pp. 108-126, and Pruszynski, Can. J. Chem., vol. 65, pp. 626-629 (1987). alpha,omega-Bis(pentaalkylguanidinium)alkane salts may be similarly prepared by reaction of the chloroformamidinium salt with a monoalkylamine, followed by reaction of the resulting pentaalkylguanidinium salt with an alkylene dihalide. The alpha,omega-bis(pentaalkylguanidinium)alkane salts defined when R1 is alkylene and n is 2 are disclosed, for example, in U.S. Pat. No. 5,081,298.
- The concentration of guanidine compound initially in aqueous media ranges from about 0.5 parts per million (ppm) to 100,000 ppm (10%), by weight of the aqueous media, and preferably ranges from about 1 ppm to about 20,000 ppm (2%) by weight of the aqueous media. In particularly preferred embodiments the concentration of guanidine compound initially in aqueous media ranges from about 1 ppm to about 1000 ppm, or from about 1 ppm to about 500 ppm.
- Aqueous media in the present invention comprises any aqueous media comprising water and at least one ionic or neutral guanidine compound, or both of at least one ionic and at least one neutral guanidine compound. In various embodiments aqueous media may also comprise any additional components which are water-soluble or at least partially water-soluble and which arise from or are present initially in chemical reactions in which a guanidine compound is present in the capacity of reaction product, reaction byproduct, decomposition product, reactant or catalyst, or in more than one capacity. In some particular embodiments aqueous media comprises at least one guanidine compound which was added as a catalyst in a displacement reaction, illustrative examples of which include polymerization reactions. In one particular embodiment aqueous media comprises both at least one guanidine compound added as a catalyst in a polymerization reaction and at least one guanidine compound decomposition product derived from an initial guanidine compound.
- Guanidine compounds which may be employed as catalysts in displacement reactions comprise guanidinium salts, illustrative examples of which include hexaalkylguanidinium salts and alpha,omega-bis(pentaalkylguanidinium)alkane salts. In particular embodiments hexaalkylguanidinium salts and alpha,omega-bis(pentaalkylguanidinium)alkane salts comprise halogen salts, particularly bromides and chlorides. In one particular embodiment a hexaalkylguanidinium salt employed as a catalyst is hexaethylguanidinium chloride. In another particular embodiment an alpha,omega-bis(pentaalkylguanidinium)alkane salt employed as a catalyst is 1,6-bis(penta-n-butylguanidinium)hexane dibromide. In other particular embodiments guanidinium salts are employed as catalysts in displacement reactions of bisphenol salts such as bisphenol A disodium salt with nitro- or halo-substituted imides such as 4-nitro-N-methylphthalimide, 4-chloro-N-methylphthalimide or 1,3-bis(N-(4-chlorophthalimido))benzene also known as 2,2′-(1,3-phenylene)bis(5-chloro-1H-isoindole-1,3(2H-dione)), to produce bisimides or polyetherimides. In particular examples U.S. Pat. No. 5,229,482 discloses a displacement method for the preparation of polyetherimides from bis(chlorophthalimides) and alkali metal salts of dihydroxy-substituted aromatic hydrocarbons using a solvent of low polarity such as o-dichlorobenzene in the presence of a thermally stable phase transfer catalyst such as a hexaalkylguanidinium halide. U.S. Pat. No. 5,830,974 discloses a similar method using a monoalkoxybenzene such as anisole as solvent.
- In some embodiments an aqueous medium comprising at least one guanidine compound is formed when a reaction mixture comprising an organic solvent and at least one guanidine compound is washed with water. Thus, in some embodiments an aqueous medium comprising at least one guanidine compound may optionally comprise less than about 5 wt. % of an organic solvent and any other water-soluble or partially water-soluble species present in said reaction mixture. In various embodiments said organic solvent has a boiling point above about 150° C. and includes as illustrative examples ortho-dichlorobenzene, para-dichlorobenzene, dichlorotoluene, 1,2,4-trichlorobenzene, diphenyl sulfone, phenetole, anisole and veratrole, and mixtures thereof. In some embodiments said organic solvent forms an azeotrope with water.
- In certain types of reactions such as displacement reactions a salt by-product such as an alkali metal salt may be formed as a side-product. Thus, in some embodiments an aqueous medium comprising at least one guanidine compound may optionally comprise an alkali metal salt, and in particular, sodium chloride or potassium chloride. When an alkali metal salt is present in the aqueous media, it is typically present at a level in a range of between about 0.01 wt. % and about 10 wt. %, based on the total weight of the aqueous media. In other embodiments when an alkali metal salt is present in the aqueous media, it is typically present at less than 5 wt.%, or less than 4 wt. %, or less than 3 wt. %, based on the total weight of the aqueous media. In some particular embodiments an alkali metal salt is present in the aqueous media at a level of between about 0.01 wt. % and about 4 wt. % or at a level of between about 0.01 wt. % and about 3.5 wt. %, based on the total weight of the aqueous media. A hexaalkylguanidinium salt may undergo some dealkylation to form the corresponding pentaalkylguanidine, for example under displacement reaction conditions. Thus, in another embodiment an aqueous medium comprises a first guanidinium salt and one or both of a neutral guanidine compound and its corresponding protonated analog (that is, a second guanidinium compound which is the protonated decomposition product a first guanidinium compound). In another particular embodiment an aqueous medium comprises hexaethylguanidinium chloride and one or both of pentaethylguanidine and pentaethylguanidinium chloride (the protonated decomposition product of hexaethylguanidinium chloride).
- In other embodiments displacement reaction mixtures may optionally comprise still other inorganic or organic components in addition to at least one guanidine compound. Washing said reaction mixture with water may result in an aqueous medium comprising at least one guanidine compound and additional components which may be at least partially water-soluble. Said additional inorganic or organic components may be removed along with a guanidine compound from aqueous media by methods of the present invention. Therefore, it is to be understood that, although removal of a guanidine compound is referred to, additional organic or inorganic components may also be present in the aqueous media and may also be removed using the teachings herein. In a particular embodiment an aqueous medium may optionally comprise an imidization catalyst used in a displacement reaction. Suitable imidization catalysts are known in the art; they include salts of organophosphorus acids, particularly phosphinates such as sodium phenylphosphinate and heterocyclic amines such as 4-diaminopyridine. A preferred catalyst is sodium phenylphosphinate also known as phenyl phosphinic acid, sodium salt. Imidization catalyst levels in the aqueous media can vary widely, for example from about 10 ppm to about 5000 ppm. In another particular embodiment an aqueous medium may optionally comprise an organic component of a polymerization reaction, such as a monomer or end-capping agent or a reaction product thereof. In an illustrative example chlorophthalic acid may be present in aqueous media obtained by washing a polymerization reaction mixture used to prepare a polyetherimide. Chlorophthalic acid levels in the aqueous media can vary widely, for example from about 1 ppm to about 20,000 ppm. In some particular embodiments chlorophthalic acid levels in the aqueous media can vary from about 1 ppm to about 5,000 ppm, or from about 1 ppm to about 2,000 ppm.
- In one embodiment of the invention aqueous media is contacted with a carbon adsorbent to remove a guanidine compound. Suitable carbon adsorbents may be activated carbons. Activated carbons can be produced by pyrolyzing organic materials such as coal, peat, or coconut shells under high temperatures in a nonoxidizing environment. The raw carbonaceous material can also be mixed with a binding agent to form a granular material. The pyrolyzed carbonaceous material can then be activated by steaming to create a high capacity, high surface area adsorbent. Raw materials with low metals content are sometimes preferred as they produce more pure activated carbons with a final lower metals content although an acid wash step can be used leach some of the residual metals from the as produced activated carbon. In many embodiments the carbon is acid washed to prevent leaching of components from the adsorbent into an acidic solution to be treated. One suitable activated carbon material that is commercially available is Type CPG Granular Carbon with particle size between 12 mesh and 40 mesh (i.e. mesh size 12×40), available from Calgon Carbon Corporation. Other factors useful in selecting activated carbons include base exchange capacity and particle size. Optimum activated carbons for treating a particular guanidine compound-comprising aqueous media may be determined without undue experimentation by those skilled in the art.
- In another embodiment of the invention a suitable carbon adsorbent may be derived from the pyrolysis of a synthetic resinous polymer. Sometimes referred to as hard carbon adsorbents, such adsorbents and their method of preparation are described, for example, in U.S. Pat. Nos. 4,040,990 and 4,957,897. As described therein, these carbons are partially pyrolyzed particles preferably in the form of hard beads or spheres and having multimodal pore size, including micro and macro pores. They are produced by the controlled decomposition of a synthetic polymer. The pyrolysis, as described in U.S. Pat. No. 4,040,990, is generally conducted in an inert atmosphere comprised of, for example, helium, argon, or nitrogen. Any of the many synthetic polymers disclosed in U.S. Pat. No. 4,040,990 can be employed in preparing the hard carbon adsorbent for the process of this invention. In some embodiments suitable polymers are those derived from aliphatic and aromatic materials which are ethylenically unsaturated. In other embodiments the polymer is cross-linked, because cross-linking often stabilizes the polymer thermally and leads to greater carbon yields. In still other embodiments the polymer contains a carbon-fixing moiety, such as a cation, anion, strong base, weak base, sulfonic acid, carboxylic acid, halogen, or alkylamine moiety. Particular examples of suitable polymers include polylvinylidene chloride, and macroreticular ion-exchange resins derived from aliphatic and aromatic materials which are ethylenically unsaturated. In one particular embodiment the synthetic polymer is a polystyrene-divinylbenzene sulfonic acid ion-exchange resin. In addition to the polymers disclosed above, any of the polysulfonated polymers disclosed in U.S. Pat. No. 4,839,331 can be employed in preparing a hard carbon adsorbent for processes of the invention. Suitable hard carbon adsorbents include, but are not limited to, those commercially available under the name AMBERSORB, available from Rohm and Haas Co.
- Typically the hard carbon adsorbents are highly stable, chemically, thermally and physically. In general they have a surface area of about 100-2000 m2/g, usually about 500-1200 m2/g and can be used, for example, in the form of approximately spherical particles having a mean particle size of, for example, from about 0.2 to 1.5 mm, preferably from about 0.3 to 1.0 mm.
- In particular embodiments hard carbon adsorbents, which are prepared by the pyrolysis of a synthetic resinous polymer, typically contain at least three distinct sets of pores of differing average size. One set comprises large pores or macropores, which typically range in size of at least 500 Angstroms in average diameter. The second set comprises intermediate pores or mesopores, which typically range in size from about 20 Angstroms to about 500 Angstroms. The third set and smallest pores or micropores are typically less than about 20 Angstroms in average diameter; however, the exact size depends on the temperature of pyrolysis of the synthetic polymer. In addition to pore size, the pyrolysis temperature also controls total pore volumes. Generally, as the pyrolysis temperature increases, the micropore volume increases.
- The macropore volume of hard carbon adsorbents useful for this invention are typically at least 0.10 ml/g; preferably in the range from about 0.10 ml/g to about 0.35 ml/g; more preferably in the range from about 0.15 ml/g to about 0.30 ml/g; and most preferably in the range from about 0.20 ml/g to about 0.25 ml/g. The mesopore volume of hard carbon adsorbents useful for this invention are typically in the range from about 0.05 ml/g to about 0.30 ml/g; preferably in the range from about 0.10 ml/g to about 0.25 ml/g; and most preferably in the range from about 0.12 ml/g to about 0.20 ml/g. The micropore volume of hard carbon adsorbents useful for this invention are at least about 0.10 ml/g; more preferably, in the range from about 0.20 ml/g to about 0.50 ml/g; and most preferably in the range from about 0.30 ml/g to about 0.45 ml/g.
- The process for removal of a guanidine compound from aqueous media using a carbonaceous adsorbent (either activated carbon or hard carbon adsorbent) can be implemented in accordance with conventional methods for adsorption processes, for example as illustrated in U.S. Pat. Nos. 5,094,754 and 5,104,530. In some particular embodiments said process comprises bringing said aqueous media into contact with said carbonaceous adsorbent for a time sufficient to allow a guanidine compound to be adsorbed from said aqueous media onto said carbonaceous adsorbent; and separating said aqueous media from said carbonaceous adsorbent containing said absorbed guanidine compound. In some embodiments the carbonaceous adsorbents may be used in the form of a slurry or contained in a column or filter bed. The optimum particle size of the carbon may depend upon such factors as the particular mode of operation, e.g. slurrying the carbon with the aqueous media or passing the aqueous media through a column of activated carbon, and may be determined without undue experimentation by those skilled in the art. When in the form of a column or filter bed, the carbonaceous adsorbent bed may operated in an up flow process or a down flow process. In other embodiments two or more carbonaceous adsorbent beds may be connected in series. The process for removal of a guanidine compound from aqueous media using a carbonaceous adsorbent may be operated in continuous, semi-continuous or batch mode.
- When a carbon adsorbent is used to remove at least one guanidine compound from aqueous media, then the pH of the aqueous media may be in any convenient range, typically between about 1 and about 13. In some particular embodiments the pH of the aqueous media is greater than about 7. In other particular embodiments the pH of the aqueous media is in a range of between about 8 and about 13 or in a range of between about 9 and about 11.
- In another embodiment of the invention aqueous media is contacted with a clay adsorbent to remove a guanidine compound. Suitable clays typically comprise layered clays, usually silicate clays. There is no particular limitation with respect to the layered clays that may be employed in this invention other than that they are capable of decreasing the concentration of guanidine compounds in an aqueous media. Illustrative of such layered clays that may be employed in this invention include, for instance, smectite and those of the kaolinite group such as kaolinite, halloysite, dickite, nacrite and the like.
- The layered clays are preferably natural or synthetic phyllosilicates, particularly smectic clays. Illustrative examples include, for instance, halloysite, montmorillonite, nontronite, beidellite, saponite, volkonskoite, laponite, sauconite, magadite, kenyaite, bentonite, stevensite, and the like. It is also within the scope of the invention to employ clays comprising minerals of the illite group, including hydromicas, phengite, brammallite, glaucomite, celadonite and the like. Often, the preferred layered minerals include those often referred to as 2:1 layered silicate minerals, including muscovite, vermiculite, saponite, hectorite and montmorillonite, the latter often being most preferred. The clays may be synthetically produced, but most often they comprise naturally occurring minerals and are commercially available. Mixtures containing at least one of the clays as described herein are also suitable. Other suitable clay adsorbents include those described in U.S. Pat. No. 5,530,052. Preferred layered clays comprise particles containing a plurality of silicate platelets having a thickness of about 7-15 angstroms bound together at interlayer spacings of about 4 angstroms or less, and containing exchangeable cations such as Na+, Ca+2, K+, Al+3, and/or Mg+2 present at the interlayer surfaces. The clays typically have a cation exchange capacity of about 50-200 milliequivalents per 100 grams on a dry basis. In various embodiments of the invention the clay adsorbents are employed when predominantly in their alkali metal ion forms and particularly in their sodium ion forms. Generally, the clays are swollen with an aqueous solution prior to use to increase their adsorption capacity.
- The process for removal of a guanidine compound from aqueous media using a clay adsorbent can be implemented in accordance with conventional methods for adsorption processes. In some particular embodiments said process comprises bringing said aqueous media into contact with said clay adsorbent for a time sufficient to allow a guanidine compound to be adsorbed from said aqueous media onto said clay adsorbent; and separating said aqueous media from said clay adsorbent containing said absorbed guanidine compound. Illustrative methods of contacting the clay with the aqueous media comprising at least one guanidine compound include flow through columns and batch methods. The column method involves passing the aqueous media through a packed column of clay. Another method is to contact the clay with the aqueous media in a fluidized bed manner, for example an upflow of the aqueous media through a bed of clay. Additionally, stirred beds of clay may be contacted with the aqueous media. In a batch method of contacting the clay with the aqueous media, the clay is added to the aqueous media as a finely divided powder and after a sufficient amount of time is removed by well-known methods, illustrative examples of which comprise filtration, flocculation, flotation or centrifugation. In this mode of operation, the guanidine compound is sorbed on the clay and removed from the aqueous media when the clay is physically removed.
- In yet another embodiment of the invention aqueous media is contacted with a nanofiltration membrane to remove a guanidine compound. Nanofiltration is a known operation in which a solution or dispersion of a material to be treated is passed over a nanofiltration separation membrane at a pressure which is generally in the range of from about 1 to about 5 megapascals (depending upon the strength of the membrane) to cause the lower molecular weight materials to pass through the membrane along with the water to form a permeate and an aqueous phase which does not pass through the membrane, which is known as a retentate. An increase in pressure usually increases the rate of permeate formation. However, the pressure which can be utilized may be determined by such factors as the temperature, nature of the particular nanofiltration membrane and the particular design of the nanofiltration apparatus and may be readily determined without undue experimentation by those skilled in the art. Upon passage through the nanofiltration module, the permeate has a lower concentration of the guanidine compound than the retentate or the initial aqueous media.
- A suitable nanofiltration membrane has a molecular weight cut-off (MWCO) which is often related to membrane pore size, and which retains the guanidine compounds while allowing water to pass through the membrane. The desired MWCO is generally less than the molecular weight of a guanidine compound in the aqueous media. Nanofiltration membranes generally have a nominal MWCO of between about 100 Daltons (Da) and about 5 kilodaltons (kDa), or between about 100 Da and about 3 kDa, or between about 100 Da and about 1 kDa, or between about 100 Da and about 600 Da, or between about 150 Da and about 600 Da. In some embodiments a suitable nanofiltration membrane has an MWCO sufficient to retain from about 40% to about 100% of the guanidine compound, preferably from about 70% to about 100% of the guanidine compound, and more preferably from about 80% to about 100% of the guanidine compound. The process for removal of a guanidine compound from aqueous media using a nanofiltration membrane may be operated in continuous, semi-continuous or batch mode.
- Suitable nanofiltration membranes comprise sintered metal, ceramics or polymeric materials. Suitable polymeric nanofiltration membranes may be made, for example, of cellulose, cellulose acetate, polyamide, aramid, polyether, polysulfone, polyethersulfone, polyvinylpyrrolidone, polytetrafluoroethylene, or polyvinylidene fluoride; and are commercially available from several manufacturers, including Desalination Membrane Products (Escondido, Calif.), Dow/Film Tec Corporation (Minneapolis, Minn.), Osmonics (Minnetonka, Minn.), and Membrane Products Kiryat Weizman Ltd. (Rehovot, Israel). The type of membrane which is selected may be dependent upon such factors as the pH of the aqueous media to be treated with the nanofiltration unit, the molecular weight cut-off required, and the temperature and pressure at which the nanofiltration is to be carried out.
- In yet another embodiment of the invention aqueous media is subjected to removal of water and calcination to remove a guanidine compound. Water may be removed from the aqueous media by any convenient method. In a particular embodiment water is removed by evaporation. Evaporation may be conducted at any convenient pressure, typically at or below atmospheric pressure. Removal of water typically leaves less than 5 wt. % of the original amount of water remaining. Following removal of water the substantially solid residue is subjected to calcination at a temperature of greater than 400° C. or greater than 450° C. or greater than 500° C. In one embodiment calcination is performed at a temperature in a range of between about 500° C. and about 600° C. The time of calcination is typically such that substantially all organic residue comprising a guanidine compound is burned off. Removal of substantially all organic residue typically leaves less than 5 wt. % of the original organic residue remaining. In a particular embodiment removal of substantially all organic residue typically leaves less than 5 wt. % or less than 2 wt. % of the initial amount of guanidine compound, based on the weight of guanidine compound initially present in aqueous media. In some particular embodiments removal of substantially all organic residue results in no detectable guanidine compound remaining, and less than 1000 ppm, or less than 500 ppm, or less than 200 ppm total organic carbon remaining. There are no particular limitations on the apparatus or protocol for performing calcination. Calcination may be performed under air or under an inert atmosphere. Removal of water and calcination may be performed in continuous, semi-continuous or batch mode. Following calcination any solid residue may be disposed of in an appropriate manner such as land-filling.
- Following treatment of aqueous media to remove a guanidine compound using the method of the invention the concentration of guanidine compound in aqueous media is less than 50% of the initial concentration, or less than 30% of the initial concentration, or less than 25% of the initial concentration, or less than 20% of the initial concentration, or less than 15% of the initial concentration, or less than 10% of the initial concentration. In the case of an aqueous medium treated using a nanofiltration membrane the final concentrations of guanidine compound refer to that part of the aqueous medium which has passed through the membrane. In the case of an aqueous medium treated by removal of water and calcination of the residue, the final concentrations of guanidine compound refers to weight percent based on the weight initially present in the aqueous medium. If so desired, more than one step or a combination of steps selected from the group consisting of adsorption onto a carbonaceous adsorbent, adsorption onto a clay adsorbent, filtration through a nanofiltration membrane, and removal of water and calcination may be employed for removal of a guanidine compound from aqueous media.
- Furthermore, following treatment of aqueous media to remove a guanidine compound, an additional inorganic or organic component which may optionally be present and which may be concurrently removed by methods of the present invention along with the guanidine compound may remain at a concentration in aqueous media of less than 50% of its initial concentration, or less than 30% of its initial concentration, or less than 25% of its initial concentration, or less than 20% of its initial concentration, or less than 15% of its initial concentration, or less than 10% of its initial concentration, depending upon such factors as the identity of the additional component, the type of treatment method, and the amount of adsorption agent.
- In some embodiments of the invention a guanidine compound may optionally be recovered from the adsorption media. Any known means may be used for recovery. In some embodiments a guanidine compound may be at least partially recovered from a carbonaceous adsorbent by treating the adsorbent with a boiling aqueous solution. Optionally, a surfactant may be present in the aqueous solution to aid in recovery of the guanidine compound. In other embodiments a guanidine compound may be at least partially recovered from a carbonaceous or clay adsorbent by treating the adsorbent with an acidic media, particularly an aqueous acidic solution, optionally at elevated temperature and optionally containing a surfactant. Acidic solutions may be derived from either organic or inorganic acids.
- In yet another embodiment a guanidine compound may be recovered from an aqueous media in which the guanidine compound has previously been concentrated through contact of the aqueous media with a nanofiltration membrane. Illustrative methods for recovering a guanidine compound from aqueous media include removal of water or adsorption of the guanidine compound on an adsorbent. Recovered guanidine compounds may be recycled and reused in chemical processes, illustrative examples of which include those described herein above. If necessary, a guanidine compound may be reactivated before reuse, such as by neutralization in the case of a protonated guanidine compound or by alkylation in the case of a dealkylated guanidine compound or by ion exchange in the case of a guanidinium compound. The carbonaceous and clay adsorbents and the nanofiltration membranes themselves may optionally be regenerated and optionally reused.
- Although the invention is illustrated by treatment of waste water comprising at least one guanidine compound and optionally additional inorganic or organic components which may be at least partially water-soluble, it is to be understood that the method of the invention is also applicable for treatment of waste water comprising said inorganic or organic components in the absence of at least one guanidine compound. In particular embodiments the method of the invention may be used to remove an imidization catalyst such as sodium phenylphosphinate or an organic component of a polymerization reaction, such as a monomer or end-capping agent or a reaction product thereof, illustrative examples of which include chlorophthalic acid. In other particular embodiments the method of the invention may be used to remove both an imidization catalyst such as sodium phenylphosphinate and an organic component of a polymerization reaction, such as a monomer or end-capping agent or a reaction product thereof, illustrative examples of which include chlorophthalic acid.
- Without further elaboration, it is believed that one skilled in the art can, using the description herein, utilize the present invention to its fullest extent. The following examples are included to provide additional guidance to those skilled in the art in practicing the claimed invention. The examples provided are merely representative of the work that contributes to the teaching of the present application. Accordingly, these examples are not intended to limit the invention, as defined in the appended claims, in any manner. In the following examples HEGCl is an abbreviation for hexaethylguanidinium chloride and PEG is an abbreviation for pentaethylguanidine.
- In the following examples Calgon CPG acid-washed granular carbon was pulverized using a cryo-grinder. The pulverized carbon was sieved and particles of less than 325 mesh were collected and dried at 150° C. for 4 hours for use in isotherm experiments. Said carbon is referred to hereinafter as sieved Calgon CPG carbon. Unless adjusted by the addition of acid or base, the pH of the waste water samples was generally in a range of between about 3 and 5.
- A waste water sample comprised 3.2 wt. % sodium chloride, 348 milligrams per liter (mg/L) of HEGCl and 72 mg/L of PEG. Six waste water samples (10 milliliters (ml) each) were individually treated with 50 mg. sieved Calgon CPG carbon and agitated for various periods of time at room temperature in a mechanical shaker. The samples were filtered and the filtrates were analyzed for concentration of HEGCl and PEG versus time. Values are given in Table 1. The data show the equilibrium is reached very quickly (less than about 5 minutes).
TABLE 1 Time (minutes) conc. HEGCl (mg/ml) conc. PEG (mg/ml) 0 0.35 0.07 5 0.04 0.01 10 0.04 0.01 30 0.04 0.01 60 0.05 0.01 90 0.04 0.01 - For determination of adsorption isotherms sieved Calgon CPG carbon was dried at 150° C. for 4 hours and then added in varying amounts in grams per liter (g/L) to waste water samples as described in Example 1. The samples were agitated for 15 minutes at room temperature in a mechanical shaker. The samples were filtered and the filtrates were analyzed to provide amount of HEGCl and PEG adsorbed per unit weight to adsorbent versus concentration of adsorbent in the mixture. Values are given in table 2.
- Some conclusions may be drawn from the data in Table 2. From linear extrapolation the adsorptive capacity of the carbon adsorbent was found to be approximately 78 mg. HEGCl per gram Calgon CPG adsorbent when equilibrium had been established under the specified conditions. Somewhere between about 65 mg. and about 100 mg. of carbon removed essentially all traces of HEGCl and PEG from 10 ml. waste water containing these particular concentrations of waste water components.
TABLE 2 Wt. of Concentration mg. mg. HEGCl Concentration mg. PEG carbon of HEGCl in HEGCl adsorbed per of PEG in mg. PEG adsorbed per (g/L) solution (mg/L) adsorbed gram of carbon solution (mg/L) adsorbed gram of carbon 0 347.7 — — 72 — — 0.51 303.5 44.2 86.7 65.4 6.6 12.9 1.01 280.2 67.5 66.8 59.7 12.3 12.2 2.05 200 147.7 72.0 40.7 31.3 15.2 3.54 107.54 240.2 67.8 21.4 50.6 14.3 5.03 55.2 292.5 58.2 11.5 60.5 12.0 6.54 15 332.7 50.9 3.8 68.2 10.4 10.03 0 347.7 34.7 0 72 7.2 24.93 0 347.7 13.9 0 72 2.9 50.1 0 347.7 6.9 0 72 1.4 100 0 347.7 3.5 0 72 0.7 - A waste water sample comprised 3.2 wt. % sodium chloride, 237 milligrams per liter (mg/L) of HEGCl and 46 mg/L of PEG. Samples of the waste water (10 ml. each) were treated with 50 mg. unpulverized Calgon CPG carbon. The pH of each mixture was adjusted to some value by the optional addition of either concentrated aqueous hydrochloric acid or 50% aqueous sodium hydroxide solution. Each mixture was agitated for 1 hour at room temperature in a mechanical shaker. The samples were filtered and the filtrates were analyzed for concentration of HEGCl and PEG. Values are given in Table 3. The data in Table 3 show that, as the pH is increased, the amounts of both ionic and neutral guanidine species adsorbed by the carbon adsorbent increases.
TABLE 3 mg. HEGCl adsorbed mg. PEG adsorbed pH per gram of carbon per gram of carbon 1 40 9 3.5 46 10 13 62 14 - A waste water sample comprised 237 milligrams per liter (mg/L) of HEGCl and 46 mg/L of PEG. Samples of the waste water (10 ml. each) were treated with 50 mg. unpulverized Calgon CPG carbon. Varying amounts of sodium chloride were dissolved in each mixture. Each mixture was agitated for 1 hour at room temperature in a mechanical shaker. The samples were filtered and the filtrates were analyzed for concentration of HEGCl and PEG. Values are given in Table 4. The data in Table 4 show that, as the polarity of the solution is increased through addition of increasing amounts of salt, the amounts of both ionic and neutral guanidine species adsorbed by the carbon adsorbent increases, although the % increase diminishes at higher salt level.
TABLE 4 Wt. % mg. HEGCl adsorbed mg. PEG adsorbed NaCl per gram of carbon per gram of carbon 0 33 8 3.2 47 10 6.4 52 11 - A waste water sample with composition similar to that described above except comprising 6.4 wt. % sodium chloride was adjusted to pH 13 with 50% aqueous sodium hydroxide, treated with varying amounts of sieved Calgon CPG carbon and agitated for 1 hour at room temperature in a mechanical shaker. The sample was filtered and the filtrates was analyzed for concentration of HEGCl and PEG. Values are given in Table 5. From linear extrapolation the adsorptive capacity of the carbon adsorbent under these specified conditions was found to be approximately 139 mg HEGCl per gram of carbon adsorbent when equilibrium had been established.
TABLE 5 Wt. of Concentration mg. mg. HEGCl Concentration mg. PEG carbon of HEGCl in HEGCl adsorbed per of PEG in mg. PEG adsorbed per (g/L) solution (mg/L) adsorbed gram of carbon solution (mg/L) adsorbed gram of carbon 0 361 — — 68 — — 0.6 285 76 127 44 24 40 1.2 225 136 113 24 44 37 2.3 93 268 116 6 62 27 3.7 17 344 93 1 67 18 5.8 4 357 62 0 68 12 - In the following examples AMBERSORB 572, a carbonaceous adsorbent with surface area of about 1100 square meters per gram (m2/g), was obtained from Rohm and Haas in mesh size of 20-50, and was used as received. A waste water sample comprised 3.2 wt. % sodium chloride, 348 mg/L of HEGCl and 78 mg/L of PEG. For determination of adsorption isotherms AMBERSORB 572 carbon was dried at 150° C. for 4 hours and then added in varying amounts in grams per liter (g/L) to individual waste water samples as described in Example 1. The samples were agitated for 15 minutes at room temperature in a mechanical shaker. The samples were filtered and the filtrates were analyzed to provide amount of HEGCl and PEG adsorbed per unit weight of adsorbent versus concentration of adsorbent in the mixture. Values are given in Table 6.
- Some conclusions may be drawn from the data in Table 6. From linear extrapolation the adsorptive capacity of the carbon adsorbent was found to be approximately 138 mg. HEGCl per gram of AMBERSORB 572 adsorbent when equilibrium had been established under the specified conditions. Somewhere between about 50 mg. and about 80 mg. of carbon removed essentially all traces of HEGCl and PEG from 10 ml. of waste water containing these particular concentrations of waste water components.
TABLE 6 Wt. of Concentration mg. mg. HEGCl Concentration mg. PEG carbon of HEGCl in HEGCl adsorbed per of PEG in mg. PEG adsorbed per (g/L) solution (mg/L) adsorbed gram of carbon solution (mg/L) adsorbed gram of carbon 0 366 — — 73 — — 0.5 281 85 170 49 24 48 0.9 248 118 131 41 32 35 2.1 165 201 96 23 50 23 3.4 83 283 83 7 66 19 5.7 6 360 63 0 73 12 7.8 0 366 47 0 73 9 - Individual waste water samples (30 ml. each) comprising 3.2 wt. % sodium chloride, 366 mg/L of HEGCl and 73 mg/L of PEG were stirred with 150 mg. of an adsorbent over 17 hours at ambient temperature. The samples were filtered and the filtrates were analyzed for amount of HEGCl and PEG in the mixture. Values are given in Table 7. Comparative Examples are designated “C.Ex.”. The following adsorbents were used: AMBERSORB 572 (“A”); Calgon CPG (“B”); AMBERSORB 563 (“C”), a carbonaceous adsorbent with BET surface area of about 550 m2/g and about 62% of its pore volume associated with pores less than 2 nanometers (nm) and about 38% of its pore volume associated with pores of diameter greater than 2 nm and less than 30 nm.; AMBERLITE XAD-2 (“D”) a non-ion-exchangeable adsorbent polymeric resin comprising structural units derived from styrene cross-linked with divinylbenzene; AMBERLITE XAD-4 (“E”) a non-ion-exchangeable adsorbent polymeric resin comprising structural units derived from styrene cross-linked with divinylbenzene and having a surface area of about 750 m 2/g and an average pore diameter of about 100 angstroms (Å); AMBERLITE XAD-7 (“F”) a non-ion-exchangeable adsorbent polymeric resin having methyl methacrylate units rather than styrene units and having a surface area of about 450 m2/g; and AMBERLITE XAD-16 (“G”) a non-ion-exchangeable adsorbent polymeric resin comprising structural units derived from styrene cross-linked with divinylbenzene and having a surface area of about 800 square meters per gram (m2/g) and an average pore diameter of about 150 angstroms (Å).
TABLE 7 mg/L HEGCl % HEGCl mg/L PEG % PEG Example Adsorbent remaining removed remaining removed Ex. 7 A 9 98 1 99 Ex. 8 B 55 85 11 85 C. Ex. 1 C 273 25 48 34 C. Ex. 2 D 166 55 30 59 C. Ex. 3 E 207 43 43 41 C. Ex. 4 F 346 5 68 7 C. Ex. 5 G 202 45 42 42 - The data in Table 7 show that the non-ion-exchangeable adsorbent polymeric resins (Comparative Examples 2-5) have less capacity for adsorption of guanidine species than do the carbonaceous adsorbents of Examples 7 and 8. In comparing Example 7 with Comparative Example 1 it is evident that the carbonaceous adsorbent with the higher surface area has a higher capacity for adsorption of guanidine species.
- An aqueous solution comprising HEGCl and PEG was subjected to filtration through a nanofiltration membrane comprising polytetrafluoroethylene (Osmonics type DK-5). The membrane pore size was such that it rejects 98% magnesium sulfate. The experimental protocol employed a standard membrane test cell (SEPA-CF test apparatus) in which wastewater at pH 1 was pumped in a crossflow manner across the surface of the membrane in a continuous fashion at a pressure of 276-310 kilopascals and flow rate of 2 liters per minute with 2 hour cycle time. Permeate flux was measured volumetrically and HEGCl/PEG concentrations in permeate and retentate were measured via ion chromatography. Data are shown in Table 8. The difference between “Feed” amount and the sum of “Retentate” and Permeate” represents experimental error. The data show that the concentration of guanidine species in the permeate is approximately 7-8 times lower than the initial concentration of said species in the feed.
TABLE 8 Sample Amount (grams) HEGCl (ppm) PEG (ppm) Feed 332 3021 931 Retentate 195 4300 1345 Permeate 149 384 120 - Sodium montmorillonite (type KUNIPIA-F; sometimes referred to herein after as “clay”) was obtained from Kunimine Industries, Japan, and had a cation exchange capacity of 119 milliequivalents of sodium per 100 grams of clay on a basis of 90% dry weight of clay. Simulated waste water solutions were prepared by dissolving various amounts of HEGCl in deionized water. Varying equivalent amounts of sodium montmorillonite were suspended in water in a high-speed blender and the HEGCl solution was added thereto under various conditions with agitation at room temperature. The mixtures were filtered and the filtrates were analyzed by ion chromatography for amount of HEGCl remaining. Values are given in Table 9. The abbreviation “equiv.” means “equivalents”. The column for “Conditions” includes the time of agitation.
TABLE 9 Con- Con- centration centration of HEGCl of HEGCl % initially remaining HEGCl Example (mg/L) (mg/L) removal Conditions 10 606 175 71 1 equiv. clay; 10 min. 11 556 25 96 2 equiv. clay; 15 min. 12 392 21 95 2 equivs. clay; 15 min.; clay mixture added to HEGCl soln. 13 392 21 95 Ex. 12 after 1 day aging 14 392 19 95 Ex.12 after 4 days aging 15 392 38 90 0.1 ml. HNO3 added to 100 ml. soln. after agitation 16 43 18 58 1 equiv. clay; 10 min. 17 40 5 88 2 equiv. clay; 10 min. 18 513 8 98 3 equiv. clay; 10 min. - The data in Table 9 shows that greater than 1 equivalent of clay is necessary for efficient removal of HEGCl from solution under the conditions of the experiment. Little increase in HEGCl adsorption is obtained upon prolonged standing of the sample with clay (Examples 13-14).
- Sodium montmorillonite was used as in Examples 10-18. Individual waste water samples comprising 366 mg/L of HEGCl; 73 mg/L of PEG and optionally 3.2 wt. % sodium chloride as noted were treated with 2 equivalents clay (based on HEGCI) and agitated under different conditions. The mixtures were filtered and the filtrates were analyzed by ion chromatography for amount of HEGCl and PEG remaining. Values are given in Table 10. The abbreviation “rt” means “room temperature”.
TABLE 10 Con- Conc. of centration HEGCl % of PEG remaining HEGCl remaining % PEG Ex. (mg/L) removal (mg/L) removal Conditions 19 51 86 11 85 10 min. in blender at rt 20 111 70 27 63 3.2 wt. % NaCl; shake overnight at rt 21 154 58 29 60 3.2 wt. % NaCl in blender for 10 min. at rt 22 100 73 36 51 3.2 wt. % NaCl in blender for 10 min. at 80° C. - Waste water samples comprised HEGCl, PEG and sodium phenylphosphinate (SPP). Samples of the waste water (20 ml. each) were adjusted to either pH 1.9 or pH 13.9 with hydrochloric acid or aqueous sodium hydroxide, and treated with various amounts of pulverized Calgon CPG carbon. Each mixture was agitated for 1 hour at room temperature in a mechanical shaker. The samples were filtered and the filtrates were analyzed for concentration of HEGCI, PEG and SPP. Values are given in Table 11 compared to the initial concentration of the measured components. The data in Table 11 show that, as the pH is increased, the amounts of both ionic and neutral guanidine species and of SPP adsorbed by the carbon adsorbent increases.
TABLE 11 Carbon weight, HEGCl, PEG, SPP, pH grams/20 ml. ppm ppm ppm 13.9 0 646 168 123 13.9 0.05 370 58 80 13.9 0.1 98 23 18 13.9 0.15 54 18 18 13.9 0.2 0 17 7 13.9 0.25 0 0 3 1.9 0 675 169 116 1.9 0.05 — — 85 1.9 0.1 512 92 53 1.9 0.15 96 21 22 1.9 0.2 71 17 16 1.9 0.25 31 4 4 1.9 0.3 0 0 2 - In the following examples a reactivated Chemviron carbon (grade F400) was pulverized using a cryo-grinder. Individual waste water samples (20 ml. each) comprising chlorophthalic acid (ClPA) were treated with various amounts of carbon at pH 4. Each mixture was agitated for 1.5 hour at room temperature in a mechanical shaker. The samples were filtered and the filtrates were analyzed for concentration of CIPA. Values are given in Table 12 compared to the initial concentration of the measured component.
TABLE 12 Carbon weight, g/L ClPA, mg/L 0 1007 0.5 863 1.5 565 2.5 373 5 60 7.5 13 10 0 12.5 0 15 0 - A 2.1 liter waste water sample comprising 1000 ppm total HEGCl and PEG, 253 ppm SPP, and 2404 ppm total organic carbon was evaporated to dryness by distillation to yield 170 g residue and 1.8 liters distillate. Analysis of the distillate showed no detectable HEGCl, PEG, or SPP. A 70 g sample of solid residue was heated in a stationary furnace under flowing nitrogen at a heating rate of 50° C. per minute to a temperature of 600° C. and held at 600° C. for 6 hours. Analysis showed that the residue weighed 67.92 g and had 100 ppm total organic carbon with no detectable HEGCl, PEG, or SPP.
- While the invention has been illustrated and described in typical embodiments, it is not intended to be limited to the details shown, since various modifications and substitutions can be made without departing in any way from the spirit of the present invention. As such, further modifications and equivalents of the invention herein disclosed may occur to persons skilled in the art using no more than routine experimentation, and all such modifications and equivalents are believed to be within the spirit and scope of the invention as defined by the following claims. All Patents cited herein are incorporated herein by reference.
Claims (38)
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/743,239 US20050029194A1 (en) | 2003-08-07 | 2003-12-22 | Method for removal of guanidine compound from aqueous media |
CN2013103644788A CN103420535A (en) | 2003-12-22 | 2004-11-19 | Method for removal of guanidine compound from aqueous media |
ES04817865T ES2363976T3 (en) | 2003-12-22 | 2004-11-19 | PROCEDURE FOR THE ELIMINATION OF A GUANIDINE COMPOUND FROM A WATER MEDIA. |
AT04817865T ATE506345T1 (en) | 2003-12-22 | 2004-11-19 | METHOD FOR REMOVAL OF A GUANIDINE COMPOUND FROM AQUEOUS MEDIA |
PCT/US2004/039048 WO2005066118A1 (en) | 2003-12-22 | 2004-11-19 | Method for removal of guanidine compound from aqueous media |
DE602004032383T DE602004032383D1 (en) | 2003-12-22 | 2004-11-19 | METHOD FOR REMOVING A GUANIDINE COMPOUND FROM AQUEOUS MEDIA |
KR1020067012315A KR101149850B1 (en) | 2003-12-22 | 2004-11-19 | Method for removal of guanidine compound from aqueous media |
EP04817865A EP1699754B1 (en) | 2003-12-22 | 2004-11-19 | Method for removal of guanidine compound from aqueous media |
CN2011100924078A CN102219713B (en) | 2003-12-22 | 2004-11-19 | Method for removal of guanidine compound from aqueous media |
CN2004800419255A CN1918115B (en) | 2003-12-22 | 2004-11-19 | Method for removal of guanidine compound from aqueous media |
US11/684,882 US7842188B2 (en) | 2003-12-22 | 2007-03-12 | Method for removal of guanidine compound from aqueous media |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US49358903P | 2003-08-07 | 2003-08-07 | |
US10/743,239 US20050029194A1 (en) | 2003-08-07 | 2003-12-22 | Method for removal of guanidine compound from aqueous media |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/684,882 Continuation-In-Part US7842188B2 (en) | 2003-12-22 | 2007-03-12 | Method for removal of guanidine compound from aqueous media |
Publications (1)
Publication Number | Publication Date |
---|---|
US20050029194A1 true US20050029194A1 (en) | 2005-02-10 |
Family
ID=34749209
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/743,239 Abandoned US20050029194A1 (en) | 2003-08-07 | 2003-12-22 | Method for removal of guanidine compound from aqueous media |
US11/684,882 Expired - Fee Related US7842188B2 (en) | 2003-12-22 | 2007-03-12 | Method for removal of guanidine compound from aqueous media |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/684,882 Expired - Fee Related US7842188B2 (en) | 2003-12-22 | 2007-03-12 | Method for removal of guanidine compound from aqueous media |
Country Status (8)
Country | Link |
---|---|
US (2) | US20050029194A1 (en) |
EP (1) | EP1699754B1 (en) |
KR (1) | KR101149850B1 (en) |
CN (3) | CN103420535A (en) |
AT (1) | ATE506345T1 (en) |
DE (1) | DE602004032383D1 (en) |
ES (1) | ES2363976T3 (en) |
WO (1) | WO2005066118A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006119967A1 (en) * | 2005-05-10 | 2006-11-16 | Süd-Chemie AG | Use of stevensite for mycotoxin adsorption |
US20120180660A1 (en) * | 2011-01-19 | 2012-07-19 | Advanced Technology Materials, Inc. | Pvdf pyrolyzate adsorbent and gas storage and dispensing system utilizing same |
WO2013041448A1 (en) * | 2011-09-19 | 2013-03-28 | Solvay Sa | Removal of low molecular weight organic compounds from inorganic halide solutions |
US8865826B2 (en) | 2010-12-22 | 2014-10-21 | Industrial Technology Research Institute | Organic/inorganic composite film and method for forming the same |
CN114671554A (en) * | 2020-12-24 | 2022-06-28 | 大连波美科技有限公司 | Zero-discharge sewage system containing guanidine salt and application method |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2175728B1 (en) * | 2007-07-13 | 2014-09-10 | Icagen, Inc. | Sodium channel inhibitors |
CA2766374C (en) | 2009-06-30 | 2017-10-03 | Monsanto Technology Llc | N-phosphonomethylglycine guanidine derivative salts |
US9127127B2 (en) | 2012-10-03 | 2015-09-08 | Sabic Global Technologies B.V. | Polyetherimide compositions, methods of manufacture, and articles formed therefrom |
CN103073164B (en) * | 2013-02-06 | 2014-03-12 | 大连佳瑞环保科技有限公司 | Treating system for sewage containing guanidine salt and treating method thereof |
US10676571B2 (en) | 2013-12-02 | 2020-06-09 | Sabic Global Technologies B.V. | Polyetherimides with improved melt stability |
CN112625816B (en) * | 2020-12-29 | 2021-09-24 | 武汉瑞法医疗器械有限公司 | Method for cleaning disinfectant containing guanidine compound on surface of medical equipment |
Citations (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US115169A (en) * | 1871-05-23 | Improvement in shoes | ||
US3952057A (en) * | 1972-07-14 | 1976-04-20 | Chemie Linz Ag | Process for the preparation of guanidine carbonate |
US4040990A (en) * | 1975-02-18 | 1977-08-09 | Rohm And Haas Company | Partially pyrolyzed macroporous polymer particles having multimodal pore distribution with macropores ranging from 50-100,000 angstroms |
US4157348A (en) * | 1977-04-05 | 1979-06-05 | Mitsui Toatsu Chemicals, Inc. | Process for preparing guanidine |
US4297220A (en) * | 1958-07-18 | 1981-10-27 | Rohm And Haas Company | Macroreticulated copolymer adsorption process |
US4729834A (en) * | 1984-05-07 | 1988-03-08 | Mitsui Toatsu Chemicals, Inc. | Method for adsorbing and desorbing |
US4839331A (en) * | 1988-01-29 | 1989-06-13 | Rohm And Haas Company | Carbonaceous adsorbents from pyrolyzed polysulfonated polymers |
US4914235A (en) * | 1988-03-16 | 1990-04-03 | Skw Trostberg Aktiengesellschaft | Process for obtaining guanidine hydrohalides from by-product mixtures obtained in the production of mercaptoalkylsilanes |
US4957897A (en) * | 1988-01-29 | 1990-09-18 | Rohm And Haas Company | Carbonaceous adsorbents from pyrolyzed polysulfonated polymers |
US5041662A (en) * | 1987-12-29 | 1991-08-20 | Skw Trostberg Aktiengesellschaft | Process for the production of guanidine nitrate from urea and ammonium nitrate |
US5081298A (en) * | 1990-12-12 | 1992-01-14 | General Electric Company | Bis(pentaalkylguanidinium) alkane salts as phase transfer catalysts |
US5094754A (en) * | 1988-01-29 | 1992-03-10 | Rohm And Haas Company | Carbonaceous adsorbents from pyrolyzed polysulfonated polymers |
US5104530A (en) * | 1988-01-29 | 1992-04-14 | Maroldo Stephen G | Chromatography column with carbonaceous adsorbents from pyrolyzed polysulfonated polymers |
US5116975A (en) * | 1990-12-12 | 1992-05-26 | General Electric Company | Bis(guanidinium)alkane salts as phase transfer catalysts |
US5123423A (en) * | 1989-12-26 | 1992-06-23 | Kas Products, Inc. | Defibrillator pad assembly and method for using same |
US5229482A (en) * | 1991-02-28 | 1993-07-20 | General Electric Company | Phase transfer catalyzed preparation of aromatic polyether polymers |
US5530052A (en) * | 1995-04-03 | 1996-06-25 | General Electric Company | Layered minerals and compositions comprising the same |
US5696290A (en) * | 1994-09-12 | 1997-12-09 | Monsanto Company | Synthesis of penta-substituted guanidines |
US5759406A (en) * | 1994-08-17 | 1998-06-02 | General Electric Company | Adsorption process for organic base recovery from aqueous brine solutions |
US5830974A (en) * | 1997-02-13 | 1998-11-03 | General Electric Company | Method for preparing aromatic polyether polymers |
US5892294A (en) * | 1994-07-08 | 1999-04-06 | Reid; Dennis | Modular automotive racing simulation apparatus |
US6214235B1 (en) * | 1998-04-06 | 2001-04-10 | General Electric Company | Process for removal of quaternary ammonium salt |
US6235934B1 (en) * | 1996-01-11 | 2001-05-22 | General Electric Company | Aqueous hexasubstituted guanidinium chlorides and methods for their preparation and use |
US6630568B1 (en) * | 1999-04-08 | 2003-10-07 | General Electric Company | Method for purification of aromatic polyethers |
US6790934B2 (en) * | 1999-09-20 | 2004-09-14 | General Electric Company | Method for purification of aromatic polyethers |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0380934A (en) * | 1989-08-25 | 1991-04-05 | Takeda Chem Ind Ltd | Adsorbent of lower aldehydes |
US5132423A (en) | 1990-02-05 | 1992-07-21 | General Electric Company | Method for conducting organic reactions using guanidinium salt as phase transfer catalyst |
US5165946A (en) * | 1990-03-07 | 1992-11-24 | Engelhard Corporation | Animal feed additive and method for inactivating mycotoxins present in animal feeds |
US5824239A (en) * | 1997-08-14 | 1998-10-20 | Buckman Laboratories International, Inc. | Method to remove biguanide from an aqueous source |
US7544354B2 (en) * | 2000-10-27 | 2009-06-09 | Novartis Vaccines And Diagnostics | Methods of protein purification and recovery |
US7904428B2 (en) | 2003-09-23 | 2011-03-08 | Symantec Corporation | Methods and apparatus for recording write requests directed to a data store |
-
2003
- 2003-12-22 US US10/743,239 patent/US20050029194A1/en not_active Abandoned
-
2004
- 2004-11-19 EP EP04817865A patent/EP1699754B1/en not_active Not-in-force
- 2004-11-19 WO PCT/US2004/039048 patent/WO2005066118A1/en active Application Filing
- 2004-11-19 AT AT04817865T patent/ATE506345T1/en not_active IP Right Cessation
- 2004-11-19 CN CN2013103644788A patent/CN103420535A/en active Pending
- 2004-11-19 KR KR1020067012315A patent/KR101149850B1/en not_active IP Right Cessation
- 2004-11-19 CN CN2011100924078A patent/CN102219713B/en not_active Expired - Fee Related
- 2004-11-19 ES ES04817865T patent/ES2363976T3/en active Active
- 2004-11-19 CN CN2004800419255A patent/CN1918115B/en not_active Expired - Fee Related
- 2004-11-19 DE DE602004032383T patent/DE602004032383D1/en active Active
-
2007
- 2007-03-12 US US11/684,882 patent/US7842188B2/en not_active Expired - Fee Related
Patent Citations (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US115169A (en) * | 1871-05-23 | Improvement in shoes | ||
US4297220A (en) * | 1958-07-18 | 1981-10-27 | Rohm And Haas Company | Macroreticulated copolymer adsorption process |
US3952057A (en) * | 1972-07-14 | 1976-04-20 | Chemie Linz Ag | Process for the preparation of guanidine carbonate |
US4040990A (en) * | 1975-02-18 | 1977-08-09 | Rohm And Haas Company | Partially pyrolyzed macroporous polymer particles having multimodal pore distribution with macropores ranging from 50-100,000 angstroms |
US4157348A (en) * | 1977-04-05 | 1979-06-05 | Mitsui Toatsu Chemicals, Inc. | Process for preparing guanidine |
US4729834A (en) * | 1984-05-07 | 1988-03-08 | Mitsui Toatsu Chemicals, Inc. | Method for adsorbing and desorbing |
US5041662A (en) * | 1987-12-29 | 1991-08-20 | Skw Trostberg Aktiengesellschaft | Process for the production of guanidine nitrate from urea and ammonium nitrate |
US5104530A (en) * | 1988-01-29 | 1992-04-14 | Maroldo Stephen G | Chromatography column with carbonaceous adsorbents from pyrolyzed polysulfonated polymers |
US4957897A (en) * | 1988-01-29 | 1990-09-18 | Rohm And Haas Company | Carbonaceous adsorbents from pyrolyzed polysulfonated polymers |
US5094754A (en) * | 1988-01-29 | 1992-03-10 | Rohm And Haas Company | Carbonaceous adsorbents from pyrolyzed polysulfonated polymers |
US4839331A (en) * | 1988-01-29 | 1989-06-13 | Rohm And Haas Company | Carbonaceous adsorbents from pyrolyzed polysulfonated polymers |
US4914235A (en) * | 1988-03-16 | 1990-04-03 | Skw Trostberg Aktiengesellschaft | Process for obtaining guanidine hydrohalides from by-product mixtures obtained in the production of mercaptoalkylsilanes |
US5123423A (en) * | 1989-12-26 | 1992-06-23 | Kas Products, Inc. | Defibrillator pad assembly and method for using same |
US5081298A (en) * | 1990-12-12 | 1992-01-14 | General Electric Company | Bis(pentaalkylguanidinium) alkane salts as phase transfer catalysts |
US5116975A (en) * | 1990-12-12 | 1992-05-26 | General Electric Company | Bis(guanidinium)alkane salts as phase transfer catalysts |
US5229482A (en) * | 1991-02-28 | 1993-07-20 | General Electric Company | Phase transfer catalyzed preparation of aromatic polyether polymers |
US5892294A (en) * | 1994-07-08 | 1999-04-06 | Reid; Dennis | Modular automotive racing simulation apparatus |
US5759406A (en) * | 1994-08-17 | 1998-06-02 | General Electric Company | Adsorption process for organic base recovery from aqueous brine solutions |
US5696290A (en) * | 1994-09-12 | 1997-12-09 | Monsanto Company | Synthesis of penta-substituted guanidines |
US5530052A (en) * | 1995-04-03 | 1996-06-25 | General Electric Company | Layered minerals and compositions comprising the same |
US6235934B1 (en) * | 1996-01-11 | 2001-05-22 | General Electric Company | Aqueous hexasubstituted guanidinium chlorides and methods for their preparation and use |
US6570038B1 (en) * | 1996-01-11 | 2003-05-27 | Joseph John Caringi | Aqueous hexasubstituted guanidinium chlorides and methods for their preparation and use |
US5830974A (en) * | 1997-02-13 | 1998-11-03 | General Electric Company | Method for preparing aromatic polyether polymers |
US6214235B1 (en) * | 1998-04-06 | 2001-04-10 | General Electric Company | Process for removal of quaternary ammonium salt |
US6630568B1 (en) * | 1999-04-08 | 2003-10-07 | General Electric Company | Method for purification of aromatic polyethers |
US6790934B2 (en) * | 1999-09-20 | 2004-09-14 | General Electric Company | Method for purification of aromatic polyethers |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006119967A1 (en) * | 2005-05-10 | 2006-11-16 | Süd-Chemie AG | Use of stevensite for mycotoxin adsorption |
US20080248155A1 (en) * | 2005-05-10 | 2008-10-09 | Sud-Chemie Ag | Use of Stevensite For Mycotoxin Adsorption |
US8221807B2 (en) | 2005-05-10 | 2012-07-17 | Sud-Chemie Ag | Use of stevensite for mycotoxin adsorption |
US8865826B2 (en) | 2010-12-22 | 2014-10-21 | Industrial Technology Research Institute | Organic/inorganic composite film and method for forming the same |
US20120180660A1 (en) * | 2011-01-19 | 2012-07-19 | Advanced Technology Materials, Inc. | Pvdf pyrolyzate adsorbent and gas storage and dispensing system utilizing same |
US8679231B2 (en) * | 2011-01-19 | 2014-03-25 | Advanced Technology Materials, Inc. | PVDF pyrolyzate adsorbent and gas storage and dispensing system utilizing same |
US9234628B2 (en) | 2011-01-19 | 2016-01-12 | Entegris, Inc. | PVDF pyrolyzate adsorbent and gas storage and dispensing system utilizing same |
US9468901B2 (en) | 2011-01-19 | 2016-10-18 | Entegris, Inc. | PVDF pyrolyzate adsorbent and gas storage and dispensing system utilizing same |
WO2013041448A1 (en) * | 2011-09-19 | 2013-03-28 | Solvay Sa | Removal of low molecular weight organic compounds from inorganic halide solutions |
CN114671554A (en) * | 2020-12-24 | 2022-06-28 | 大连波美科技有限公司 | Zero-discharge sewage system containing guanidine salt and application method |
Also Published As
Publication number | Publication date |
---|---|
EP1699754B1 (en) | 2011-04-20 |
KR20060129225A (en) | 2006-12-15 |
KR101149850B1 (en) | 2012-05-25 |
ES2363976T3 (en) | 2011-08-22 |
CN1918115B (en) | 2011-06-01 |
CN1918115A (en) | 2007-02-21 |
ATE506345T1 (en) | 2011-05-15 |
CN102219713B (en) | 2013-09-18 |
US20070161821A1 (en) | 2007-07-12 |
US7842188B2 (en) | 2010-11-30 |
CN103420535A (en) | 2013-12-04 |
DE602004032383D1 (en) | 2011-06-01 |
EP1699754A1 (en) | 2006-09-13 |
WO2005066118A1 (en) | 2005-07-21 |
CN102219713A (en) | 2011-10-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7842188B2 (en) | Method for removal of guanidine compound from aqueous media | |
Unuabonah et al. | Clay–polymer nanocomposites (CPNs): Adsorbents of the future for water treatment | |
EP0253287B1 (en) | Combined membrane and sorption process for selective ion removal | |
Armagan et al. | Adsorption of negatively charged azo dyes onto surfactant-modified sepiolite | |
Martucci et al. | Recent advances in clean-up strategies of waters polluted with sulfonamide antibiotics: a review of sorbents and related properties | |
Mahdavi Far et al. | A review of zeolite materials used in membranes for water purification: History, applications, challenges and future trends | |
JP2018533473A (en) | Method and system for treating wastewater, and method and system for producing molecular sieve | |
US8357300B2 (en) | Methods and materials for selective boron adsorption from aqueous solution | |
Qiu et al. | Adsorption desalination: Advances in porous adsorbents | |
TW201829296A (en) | Aqueous hydrogen peroxide purification method and purification device | |
Priyadarshini et al. | Zeolite Y-carbonaceous composite membrane with a pseudo solid foam structure assessed by nanofiltration of aqueous dye solutions | |
Dey et al. | Antimicrobial two-dimensional covalent organic nanosheets (2D-CONs) for the fast and highly efficient capture and recovery of phosphate ions from water | |
JP5584043B2 (en) | Pretreatment device for membrane separation and membrane separation method using the same | |
CN105080366A (en) | Reverse osmosis membrane and preparation method thereof | |
Shahadat et al. | Clay‐based adsorbents for the analysis of dye pollutants | |
CN1006638B (en) | Method of purifying l-ascorbic acid | |
US20050035060A1 (en) | Process for purifying glyphosate solutions by nanofiltration | |
JP4617476B2 (en) | Method for removing potassium ions | |
JP4793863B2 (en) | Method for producing interlayer cross-linked clay porous body | |
Dlamini et al. | Chemistry behind the performance of ceramic membranes and their future in membrane technology | |
US6066259A (en) | Method for the deionization of substances that are not stable at acidic pH | |
Abu-Obaid et al. | Adsorptive membranes for nutrient recovery from wastewater: A novel solution for water purification challenges | |
JPS6159199B2 (en) | ||
US20080242778A1 (en) | Method For Purification And Modification Of Mineral Clays In Non-Aqueous Solvents | |
BULAI et al. | Copper ions concentration using ion exchange resins |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: GENERAL ELECTRIC COMPANY, NEW YORK Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HALL, DAVID BRUCE;GUGGENHEIM, THOMAS LINK;SILVA, JAMES MANIO;AND OTHERS;REEL/FRAME:015229/0219;SIGNING DATES FROM 20040302 TO 20040413 |
|
AS | Assignment |
Owner name: GENERAL ELECTRIC COMPANY, NEW YORK Free format text: A CORRECTIVE ASSIGNMENT TO REMOVE A INCORRECT SERIAL NUMBER 09/743,239 ON REEL 015229 FRAME 0219;ASSIGNORS:HALL, DAVID BRUCE;GUGGENHEIM, THOMAS LINK;SILVA, JAMES MANIO;AND OTHERS;REEL/FRAME:015935/0077;SIGNING DATES FROM 20040302 TO 20040413 |
|
AS | Assignment |
Owner name: GENERAL ELECTRIC COMPANY, NEW YORK Free format text: CORRECTIVE ASSIGNMENT TO CORRECT THE ADDRESS OF THE ASSIGNEE, PREVIOUSLY RECORDED ON REEL 015935 FRAME 0077;ASSIGNORS:HALL, DAVID BRUCE;GUGGENHEIM, THOMAS LINK;SILVA, JAMES MANIO;AND OTHERS;REEL/FRAME:016021/0322;SIGNING DATES FROM 20040302 TO 20040413 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |