CN1894177A - Method for producing propylene - Google Patents
Method for producing propylene Download PDFInfo
- Publication number
- CN1894177A CN1894177A CN 200480037104 CN200480037104A CN1894177A CN 1894177 A CN1894177 A CN 1894177A CN 200480037104 CN200480037104 CN 200480037104 CN 200480037104 A CN200480037104 A CN 200480037104A CN 1894177 A CN1894177 A CN 1894177A
- Authority
- CN
- China
- Prior art keywords
- ethene
- propylene
- reaction system
- reaction
- dme
- 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.)
- Granted
Links
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 125
- 238000004519 manufacturing process Methods 0.000 title claims description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 328
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 200
- 238000000034 method Methods 0.000 claims abstract description 165
- 238000006243 chemical reaction Methods 0.000 claims abstract description 139
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000011541 reaction mixture Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 71
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 66
- 238000002360 preparation method Methods 0.000 claims description 61
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 56
- 229910052751 metal Inorganic materials 0.000 claims description 53
- 239000010457 zeolite Substances 0.000 claims description 49
- 229910021536 Zeolite Inorganic materials 0.000 claims description 48
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 47
- 150000001336 alkenes Chemical class 0.000 claims description 45
- 229910052782 aluminium Inorganic materials 0.000 claims description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 42
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 32
- 239000002994 raw material Substances 0.000 claims description 26
- 230000004048 modification Effects 0.000 claims description 24
- 238000012986 modification Methods 0.000 claims description 24
- 239000003208 petroleum Substances 0.000 claims description 22
- 239000004411 aluminium Substances 0.000 claims description 20
- 239000011973 solid acid Substances 0.000 claims description 18
- 238000001149 thermolysis Methods 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 7
- 238000004230 steam cracking Methods 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 abstract description 83
- 230000008569 process Effects 0.000 abstract description 47
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000203 mixture Substances 0.000 description 77
- 239000000047 product Substances 0.000 description 44
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 35
- 239000000463 material Substances 0.000 description 32
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 30
- 239000007789 gas Substances 0.000 description 26
- 238000001354 calcination Methods 0.000 description 24
- 229930195733 hydrocarbon Natural products 0.000 description 24
- 150000002430 hydrocarbons Chemical class 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 22
- -1 carbon atoms hydro carbons Chemical class 0.000 description 21
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 20
- 229910004298 SiO 2 Inorganic materials 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 239000002243 precursor Substances 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000006227 byproduct Substances 0.000 description 15
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 229910052791 calcium Inorganic materials 0.000 description 11
- 239000011575 calcium Substances 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 230000008859 change Effects 0.000 description 10
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 239000001294 propane Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 229910000323 aluminium silicate Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 230000008676 import Effects 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 229960001866 silicon dioxide Drugs 0.000 description 7
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 7
- 239000013543 active substance Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 230000036571 hydration Effects 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 6
- 229910052712 strontium Inorganic materials 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 101100112997 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) MCM22 gene Proteins 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 230000031709 bromination Effects 0.000 description 5
- 238000005893 bromination reaction Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 229910052914 metal silicate Inorganic materials 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000004645 aluminates Chemical class 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910000018 strontium carbonate Inorganic materials 0.000 description 4
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 3
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 229960004217 benzyl alcohol Drugs 0.000 description 3
- 235000013844 butane Nutrition 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000002075 main ingredient Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- 238000002525 ultrasonication Methods 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical class [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 235000011285 magnesium acetate Nutrition 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910021426 porous silicon Inorganic materials 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000011800 void material Substances 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
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 101150086923 ERB1 gene Proteins 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 101100095760 Schizosaccharomyces pombe (strain 972 / ATCC 24843) psh3 gene Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000000475 acetylene derivatives Chemical class 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
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- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 229910052663 cancrinite Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000011284 combination treatment Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 230000009849 deactivation Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical compound CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- LGPMBEHDKBYMNU-UHFFFAOYSA-N ethane;ethene Chemical group CC.C=C LGPMBEHDKBYMNU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000011905 homologation Methods 0.000 description 1
- 238000007163 homologation reaction Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- HDJUVFZHZGPHCQ-UHFFFAOYSA-L manganese(2+);oxalate;dihydrate Chemical compound O.O.[Mn+2].[O-]C(=O)C([O-])=O HDJUVFZHZGPHCQ-UHFFFAOYSA-L 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- ULSIYEODSMZIPX-UHFFFAOYSA-N phenylethanolamine Chemical compound NCC(O)C1=CC=CC=C1 ULSIYEODSMZIPX-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
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- JTXAHXNXKFGXIT-UHFFFAOYSA-N propane;prop-1-ene Chemical group CCC.CC=C JTXAHXNXKFGXIT-UHFFFAOYSA-N 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for efficiently producing propylene from ethylene and methanol and/or dimethyl ether. The process comprises bringing ethylene into contact with methanol and/or dimethyl ether in the presence of a catalyst to produce propylene, and is characterized in that the amount of the ethylene contained in a reaction mixture which is being discharged from the reaction system is reduced as compared with the amount of the ethylene which is being fed to the reaction system, and that propylene is obtained in a yield of 40 mol% or higher based on the sum of the number of moles of the methanol and two times the number of moles of the dimethyl ether which are being fed to the reaction system.
Description
Technical field
The present invention relates to a kind of method by ethene and methyl alcohol and/or dimethyl ether production propylene.
Background technology
As the method for preparing paraffinic hydrocarbons, alkene and aromatic hydrocarbon, after deliberation several different methods, the method that wherein not only comprises petroleum cracking, also comprise the method that adopts new forms of energy, in the method that adopts new forms of energy, obtain hydrogen/CO mixed gas by the Sweet natural gas modification, with the methyl alcohol that obtains by this mixed gas and dme as raw material.Especially, compare, in a kind of method in back, do not have sulfocompound in the product substantially with the resulting product of preceding a kind of method, thereby, be considered to the petrochemical material of environmental protection.
These adopt methyl alcohol and dme to name according to its primary product type usually as the method for feedstock production paraffinic hydrocarbons, alkene and aromatic hydrocarbon, promptly, to obtain gasoline is that the method for main ingredient is called the MTG method, to obtain light alkene is that the method for main ingredient is called the MTO method, is that the method for main ingredient is called the MTP method to obtain in the light alkene propylene particularly.
But under the situation that is made propylene by methyl alcohol (referring to for example patent documentation 1～3), theoretically, 3 molecule methyl alcohol form 1 molecule propylene, thereby, be that the productive rate maximum of benchmark only is 33% with the material benzenemethanol mole number.In addition, the weight of the water that generates as by product is big.So,, can not think that this method is preferred commercial run from the efficient aspect of for example equipment cost.
On the other hand, as an embodiment of MTP method, know that also having a kind of is the method that is made propylene (non-patent literature 1) by ethene and methyl alcohol.But, adopt this method, be that the productivity of propylene of benchmark is no more than 40 moles of % with the material benzenemethanol, this also is inadequate.
Patent documentation 1:JP-A-59-222329
Patent documentation 2:JP-A-4-217928
Patent documentation 3:US-A-2003-139635
Non-patent literature 1:Applied Catalysis A:General 218 (2001), 241-250.
Summary of the invention
Purpose of the present invention
In the prior art, be that the productive rate of propylene of benchmark is lower with the material benzenemethanol mole number, be not enough to as industrial process.
The objective of the invention is, preparing under the situation of propylene, provide a kind of productivity ratio traditional method the high method for preparing propylene by ethene and methyl alcohol.
Realize the means of the object of the invention
For achieving the above object, the inventor has carried out deep research, found that, under the reaction conditions of specified range, makes the reaction of ethene and methyl alcohol and/or dme obtain propylene by high productivity, thereby has finished the present invention.That is to say, purport of the present invention is a kind of method for preparing propylene, this method is included in the step that under the existence of catalyzer ethene is contacted with methyl alcohol and/or dme, the method is characterized in that, with respect to the amount of the ethene that adds reaction system, the ethene amount from the reaction mixture that reaction system is discharged is reduced, and, with the moles of methanol of adding reaction system and two times of mole number sums of dme is benchmark, and the productive rate of propylene is at least 40 moles of %.
In the method for the invention, in order to improve the productive rate that makes ethylene reaction obtain propylene, preferably reaction pressure is transferred at least 0.1kPa to the scope that is less than 2MPa, and, with the moles of methanol of adding reaction system and two times of mole number sums of dme is benchmark, and the amount that adds the ethene of reaction system is transferred at least 1 to maximum 20 mol ratio.And, preferably the methyl alcohol that is added is adjusted to 0.01hr at least with the weight hourly space velocity of the per unit catalyst activity composition weight of the dme that is scaled methyl alcohol
-1(hour
-1) to maximum 70hr
-1
The invention effect
According to the present invention, adopting ethene and methyl alcohol and/or dme is raw material, can make propylene with the productive rate high than traditional method.
Embodiment
Now, will describe typical embodiment of the present invention in detail.
(1) response matrix (raw material)
The method of the invention adopts the gas-phase reaction mode, so raw material of the present invention is made up of the mixed gas that contains ethene and methyl alcohol and/or dme.Except gasiform ethene and methyl alcohol and/or dme, this mixed gas can also comprise the gas to this reaction non-activity, for example hydro carbons, aromatic compound or their mixtures such as helium, argon, nitrogen, carbon monoxide, carbonic acid gas, hydrogen, water, paraffinic hydrocarbons, methane, their shared concentration in described mixed gas can be arbitrarily, for example is the amount of 1 mole of %～99 mole %.In above-mentioned gas, preferably there is water (being water vapor) at least simultaneously to this reaction non-activity.
And, do not limit for the form that adds the mixed gas in the reactor is special, as long as this mixed gas is sneaked into when reaction is carried out.Ethene and methyl alcohol and/or dme (also having other gas to the reaction non-activity when needing) can add in the reactor respectively, or they are made in the mixed gas adding reactor in advance.
(1)-a ethene
There is no particular limitation for the used ethene of the present invention, can adopt the ethene that is made by multiple known method arbitrarily, for example, and the ethene that the raw material of being originated by oil makes by for example catalystic pyrolysis or steam splitting process; Hydrogen/the Co mixed gas that adopts the coal gasification gained is the ethene that raw material makes through FT (Fischer-Tropsch) reaction; The ethene that makes through ethane dehydrogenation method or oxidative dehydrogenation of ethane method; Transposition (methathesis) reaction and homologization (homologation) through propylene react the ethene that makes; The ethene that makes through the catalyzed reaction of solid acid catalyst of oxidized material such as methyl alcohol and/or dme for example; Or the ethene that makes through the dehydrogenation reaction of corresponding alcohol (ethanol).In this case, can directly adopt the product that generates by various preparation methods, be mixed with the compound except that ethene in this product, or adopt purified ethene.
Wherein, the raw material that preferably adopts oil source by for example catalystic pyrolysis or the prepared ethene of steam splitting process as raw material.More preferably following ethene, promptly the hydro carbons that contains at least two carbon atoms with for example ethane, propane, butane/butene mixture, petroleum naphtha, lightweight NGL (liquify natural gas), heavy NGL or kerosene light oil etc. is a raw material, the boiling point of this class hydrocarbon is smaller or equal to 300 ℃, and handle by desulfurization and to have reduced sulphur content, be under 760 ℃～900 ℃ the condition in the temperature out of pyrolyzer, the ethene that makes by catalytic pyrolysis or steam cracking.
As ethene, the preferred employing utilized the ethene of olefines production unit by the thermolysis gained of petroleum naphtha, because like this, in this olefines production unit, can change the productive rate balance of ethene and propylene, thereby significantly increase the propylene/ethylene ratio.
And the preferred ethene that utilizes light alkene class production unit to be made by methyl alcohol and/or dme that adopts is because like this, in this light alkene class production unit, can change the productive rate balance of ethene and propylene, thereby significantly increase the propylene/ethylene ratio.
Further, the preferred ethene that utilizes ethylene production equipment to make through the steam splitting process of ethane that adopts because like this, can mainly separate the ethane that obtains from Sweet natural gas and prepare propylene as raw material by adopting.
But, as the method that is used as preparation example such as olefines such as ethene and propylene usually, the olefines of petroleum naphtha thermal decomposition method gained contains ethene, the propylene of about 17 weight % and the butylene/divinyl of about 11 weight % of average about 28 weight % usually, thereby, according to ethene and the required balance of propylene, there is the limit in both productive rate balances.In this respect, after deliberation multiple thermolysis process, but in these methods, all be difficult to significantly change the productive rate balance.At for example above-mentioned patent documentation 3 or 4 disclosed by methyl alcohol and/or dimethyl ether production for example in the method for light alkenes such as ethene, propylene or butylene, for example in patent documentation 3, the performance that shows is, ethene with respect to about 10 weight %, propylene is about 50 weight % and butylene is about 20 weight %'s, it is attracted attention as optionally preparing the method for light alkene, but it still is difficult to significantly change the productive rate balance.Preparing in the method for ethene through ethane steam cracking by ethylene production equipment, forming differently because of raw material, mainly obtaining ethene, and be difficult to obtain propylene although contain the composition of the product of ethene.
In these cases, the invention provides a kind of useful method for preparing propylene by ethene efficiently.That is to say that the method for preparing propylene of the present invention is the important technology that a kind of productive rate balance that can make ethene and propylene in above-mentioned olefin production plant changes.Olefin production plant (i), (ii) and (iii) below will be described.
(i) prepare the equipment of alkene by the petroleum naphtha thermolysis
Prepare the equipment of alkene as of the present invention by the petroleum naphtha thermolysis, its summary flow process is described with reference to steam splitting process.Steam splitting process is usually as the method for preparing alkene such as ethene, propylene, and typical example has the tubular oven method.In front end demethanizing process as its a kind of method, petroleum naphtha is imported in the thermal degradation stove together with steam, under about 760 ℃～900 ℃ temperature, carry out thermal degradation, make the hydro carbons quenching of gained, then described hydro carbons is imported rectifying tower, obtain tar from tower bottom, obtain gas and oil, from overhead fraction, obtain hydro carbons from this tower sidepiece.Make hydro carbons quenching, with the water and the mixture that is mainly the hydro carbons of maximum 6 carbon atoms of isolating the hydro carbons that is mainly maximum 5 carbon atoms and being derived from steam with cat head.With described moisture and be mainly maximum 6 carbon atoms hydro carbons mixture separation Cheng Shui and be mainly the hydro carbons of maximum 6 carbon atoms.And the isolated water in this place imports the thermal degradation stove by vapour generator and is reused.But this separating obtained water contains non-volatile hydro carbons, thus remove portion water removing these non-volatile hydro carbons, and add fresh water to replenish the water that is removed.
Compressor compresses is removed sulfide then by the hydro carbons that is mainly maximum 5 carbon atoms of the aforementioned overhead fraction gained of quenching in the alkali cleaning district, behind drying zone, this degradation production is imported demethanizing tower, thereby methane and hydrogen are reclaimed as overhead fraction.Simultaneously, described tower bottom distillate is imported deethanizing column, thereby will change into ethane/ethylene by hydrogenator as the acetylene in the ethane-ethylene mixture of overhead fraction, this ethane/ethylene will be imported into ethylene rectification tower, simultaneously, tower bottom distillate is imported depropanizing tower.To change into propane/propylene by hydrogenator as propine in the propane-propylene mixtures of overhead fraction and propadiene, this propane/propylene will be imported propylene rectification tower, simultaneously, tower bottom distillate be imported debutanizing tower.In ethylene rectification tower, reclaim ethylene product from the tower sidepiece, ethane is circulated to decomposing furnace as tower bottom distillate, in propylene rectification tower, reclaims propylene product from the tower sidepiece, and simultaneously, propane is circulated to decomposing furnace as tower bottom distillate.By this individual system, the high-purity ethylene of separable recovery about 99.95% and about 99.0% high-purity propylene.
And, in process as the front end depropanizing of another method, as previously mentioned, degradation production is imported into depropanizing tower after by above-mentioned drying zone, thereby will be converted into ethane/ethylene and propane/propylene as ethane/ethylene and the acetylene in the propane/propylene mixtures, propine and the propadiene of overhead fraction by hydrogenator, described ethane/ethylene and propane/propylene are imported demethanizing tower, meanwhile, tower bottom distillate is imported debutanizing tower.In described demethanizing tower, methane and hydrogen are reclaimed as overhead fraction, simultaneously, tower bottom distillate is imported deethanizing column, thereby will import ethylene rectification tower as the ethane/ethylene of the overhead fraction of deethanizing column, simultaneously, tower bottom distillate is imported propylene rectification tower.In ethylene rectification tower, reclaim ethylene product from the tower sidepiece, simultaneously, ethane is circulated to decomposing furnace as tower bottom distillate.And, in propylene rectification tower, reclaim propylene product from the tower sidepiece, simultaneously, propane is circulated to decomposing furnace as tower bottom distillate.
And other versions as above-mentioned front end depropanizing process have a kind of method to be, with the overhead fraction importing deethanizing column of depropanizing tower, rather than import demethanizing tower.In the overhead fraction of depropanizing tower, contain acetylene and propine, under the big situation of propine content, can make this overhead fraction, and then it is imported deethanizing column in the same manner as described above by hydrogenator.And, under the little situation of propine content, can be without hydrogenator and this overhead fraction is imported deethanizing column, then will be as the acetylene in methane, hydrogen and the ethane/ethylene mixture of the overhead fraction of deethanizing column by hydrogenator, and be converted into ethane/ethylene.Can be with the overhead fraction of deethanizing column by being connected on the hydrogen separator after the hydrogenator as required, and then import demethanizing tower, meanwhile, tower bottom distillate is imported propylene rectification tower.In demethanizing tower, methane is recovered as overhead fraction, and simultaneously, ethane/ethylene is imported into ethylene rectification tower as tower bottom distillate.In propylene rectification tower, reclaim propylene product from the tower sidepiece, simultaneously, propane is circulated to decomposing furnace as tower bottom distillate.In ethylene rectification tower, reclaim ethylene product from the tower sidepiece, simultaneously, ethane is circulated to decomposing furnace as tower bottom distillate.
And, as another kind of method, as previously mentioned, can also carry out front end deethanizing process, wherein, will import deethanizing column by the degradation production behind the above-mentioned drying zone.
In the present invention, preferably, make through the petroleum naphtha thermolysis to prepare propylene, simultaneously, adopt the water that forms as by product to produce the source as the steam in the petroleum naphtha thermolysis with the ethene of the equipment gained of aforementioned preparation alkene and the gas reaction that contains methyl alcohol and/or dme.Can reduce the steam consumption in the petroleum naphtha thermolysis when the petroleum naphtha thermolysis prepares alkene thus.
As mentioned above, the thermal decomposition furnace that is used for the petroleum naphtha thermal decomposition process adopts the diluent gas of water as petroleum naphtha, but when utilizing, requires to remove a part of recycle-water again.And according to the operational condition of thermal decomposition furnace, water may be not enough.Yet by ethene and methyl alcohol and/or dimethyl ether production propylene the time, every mole, of methanol and/or dme will produce 1 mol of by-products water, by this water as by product, can replenish the deficiency of water in the steam generation source.
And, can utilize a part of water that preparation forms as by product during propylene as the reaction of this preparation propylene in ethene and contain the thinner of the gas of methyl alcohol and/or dme, and adopt such method of utilizing, remainder water is offered steam generating equipment in the petroleum naphtha thermolysis.Can be used as ethene and methyl alcohol and/or dme reaction ethene and the thinner that contains the gas of methyl alcohol and/or dme from the water that is used for petroleum naphtha pyrolysated vapor recovery.
At this, about using the ethene for preparing the equipment gained of alkene by the petroleum naphtha thermolysis, its meaning is the ethene that not only comprises in above-mentioned front end demethanizing process, front end depropanizing process and the front end deethanizing process through the ethylene rectification tower gained, also comprise: adopt hydrogenator, will be in above-mentioned front end demethanizing process, become ethane/ethylene mixture after the ethane/ethylene as the acetylene conversion in the ethane/ethylene mixture of deethanizer overhead cut; In above-mentioned front end depropanizing process as the ethane/ethylene mixture of the overhead fraction of deethanizing column; If desired, adopt hydrogenator, will above-mentioned front end depropanizing process, other versions in, be the mixture that contains ethene after the ethane/ethylene as the acetylene conversion in methane, hydrogen and the ethane/ethylene mixture of deethanizer overhead cut; And, adopt hydrogenator, will be in above-mentioned front end deethanizing process, be the mixture that contains ethene after the ethane/ethylene as the acetylene conversion in methane, hydrogen and the ethane/ethylene mixture of deethanizer overhead cut.And if desired, in other versions and above-mentioned front end deethanizing process of above-mentioned front end depropanizing process, the mixture that contains ethene can also be the mixture to small part hydrogen and/or the ethane that is contained in this mixture through isolating.
Wherein, as through the ethene of petroleum naphtha thermolysis, preferably adopt ethane/ethylene mixed gas from above-mentioned deethanizer overhead cut gained with the equipment gained of aforementioned preparation alkene.Compare with the situation of the raw material ethene of methyl alcohol and/or dme reaction with adopting ethylene product conduct, can reduce the load of ethylene rectification tower like this from the recovery of ethylene distillation Tata sidepiece.Simultaneously, the ethane that accounts for ethane/ethylene mixed gas 10%～20% will be as the carrier in reacting with methyl alcohol and/or dme, so do not need to provide carrier substance from the outside, the reaction of ethene and methyl alcohol and/or dme can be carried out very effectively.
At this, be meant from the ethane/ethylene mixed gas of deethanizer overhead cut gained: above-mentioned front end demethanizing process, will be as the material of acetylene after hydrogenator changes into ethane/ethylene in the ethane/ethylene mixture of overhead fraction; In above-mentioned front end depropanizing process as the ethane/ethylene of overhead fraction; If desired, adopting hydrogenator, in other versions of above-mentioned front end depropanizing process, will be the material after the ethane/ethylene as the acetylene conversion in methane, hydrogen and the ethane/ethylene mixture of overhead fraction; Or in above-mentioned front end deethanizing process, will be as the material of acetylene after hydrogenator changes into ethane/ethylene in methane, hydrogen and the ethane/ethylene mixture of overhead fraction.
And, in other versions and above-mentioned front end deethanizing process of above-mentioned various front end depropanizing processes,, the hydrogen that contains in this mixture and/or at least a portion of methane can be separated when needing for the mixture that contains ethene.For example, after the separation of hydrogen,, can adopt the method for in this process, extracting out from the tower sidepiece of demethanizing tower in order to be separated to small part methane.At this, when being separated to small part methane,, not only can alleviate the load of above-mentioned ethylene rectification tower by staying part methane, can also alleviate the load of demethanizing tower.Meanwhile, be not only ethane contained in the ethane/ethylene mixed gas, and methane also will as with the reaction of methyl alcohol and/or dme in carrier, therefore help effectively the carrying out of reaction of ethene and methyl alcohol and/or dme.
(ii) by the method for methyl alcohol and/or dimethyl ether production light alkene
By the method for methyl alcohol and/or dimethyl ether production light alkene is by the traditional method known to the above-mentioned patent documentation 1～4 for example, this method is at 200 ℃～600 ℃, under 10kPa～600kPa pressure, under the situation of existence such as solid acid catalyst, if desired, can there be water to exist, reacts light alkenes such as preparation example such as ethene, propylene, butylene by methyl alcohol and/or dme.
At this, the ratio of methyl alcohol and/or dme and water preferred 1: 0～2.As the preferred siliceous compound of the solid acid catalyst of catalyzer.Described siliceous compound can be a silicon-dioxide for example, but more preferably crystallinity aluminosilicate, metal silicate (metallosilicate) or crystallinity aluminum phosphate class, special preferred zeolite.And, preferred 300 ℃～600 ℃ of temperature, the preferred 20kPa～1MPa of pressure.
So for example, methyl alcohol and/or dme react under these conditions, with the cooling of this reactant gases, partial concentration, and be separated into three-phase by separator.Then, extract the liquid phase contain higher fatty acid and aromatic compound, in washing tower, wash with water remaining water is gentle, extract from this washing tower top and contain C
2-C
4The gaseous mixture of alkene, and be separated into C by known method
2, C
3And C
4, then, carry out purifying, to obtain ethene, propylene and butylene product.In addition, extract from its bottom and to contain unreacted methanol and unreacted dme and, and isolate methyl alcohol and/or dme, be recycled to then in the reactor, simultaneously, water is removed from this aqueous phase as the water of the dme of intermediate product.
The C that contains as this moment
2-C
4Separation of gaseous mixture/the purification system of alkene, described gaseous mixture is successively by for example taking off ethylene/ethane tower, eparating methanol tower, take off the propylene tower and taking off the butenes/butanes tower, if desired, for as taking off the ethylene/ethane mixture of ethylene/ethane column overhead cut, available hydrogenator is an ethylene/ethane with the acetylene conversion in this mixture.Then, this mixture is imported ethylene rectification tower by eparating methanol tower, simultaneously, the propylene tower is taken off in the tower bottom distillate importing, if desired, for as taking off the propylene mixture of propylene column overhead cut, available hydrogenator is converted into propylene with propine in this mixture and propadiene.Subsequently, this mixture is delivered to propylene rectification tower, simultaneously, tower bottom distillate is imported the butenes/butanes tower.In ethylene rectification tower, reclaim ethylene product from top of tower, and at the bottom of tower, separate ethane.And, in described propylene rectification tower, reclaim propylene product from top of tower, and at the bottom of the tower separating propane.
At this, not only can be following ethylene product by the ethene of the aforementioned device gained of methyl alcohol and/or dimethyl ether production light alkene, can also be mixture.Described ethylene product for example is, to handling as the ethylene/ethane mixture that takes off ethylene/ethane column overhead cut, adopting hydrogenator when needing is ethylene/ethane with the acetylene conversion in this mixture, then this ethylene/ethane is imported ethylene rectification tower by eparating methanol tower, from the ethylene product of ethylene rectification tower recovered overhead; Described mixture is, as the ethylene/ethane mixture that takes off ethylene/ethane column overhead cut, or to adopt hydrogenator when needing be ethylene/ethane mixture after the ethylene/ethane with the acetylene conversion in this mixture.
The equipment that (iii) prepares ethene by ethane steam cracking
Ethane steam cracking is a kind of like this reaction, promptly at 500 ℃～900 ℃ with to low normal atmosphere, the paraffins mixture that mainly contains ethane is carried out dehydrogenation reaction, and what obtain mainly is alkene and part diolefine or alkynes class.As separation/purification system, for example, at first in the deethanizing column of front terminal type, isolate than C to the gained reaction mixture
3Heavy cut is from the recovered overhead hydrocarbon mixture.Then, if desired, remove acetylene in this mixture with hydrogenator, and with this acetylene through being converted into ethylene/ethane.After this, import ethylene rectification tower, reclaim ethene from this top of tower by demethanizing tower.At this, being used for equipment reaction of the present invention, that adopt preparation ethene not only can be the ethylene product that reclaims from ethylene rectification tower through the ethene of ethane steam cracking gained, it can also be mixture as the ethylene/ethane/methane/hydrogen of demethanizer tops, perhaps, can also be that front end deethanizer overhead fraction mixture is handled, when needing with hydrogenator with the mixture of the acetylene in this mixture after being converted into ethylene/ethane.
(1)-b methyl alcohol and dme
Having no particular limits as the methyl alcohol of raw material and the source of dme, for example can be coal or Sweet natural gas.Perhaps, they can be by product in the system ironworker industry derive hydrogen/Co mixed gas of obtaining through the material of hydrogenation reaction gained, alcohols that plant derivation obtains through the material of modified-reaction gained, with the material of fermentation method gained or from reclaiming the resulting materials of organic substance such as plastics or Municipal waste.
Wherein, preferred hydrogen/Co mixed gas obtains the method for above-mentioned methyl alcohol and dme through hydrogenation reaction.
(2) catalyzer
Catalyzer used among the present invention has no particular limits, and gets final product so long as contain the solid catalyst of Bronsted (Bronsted) acid position.Can adopt known catalyzer such as following solid acid catalyst arbitrarily: for example, clay pits such as kaolin; On carriers such as clay pit, contain or carry on a shoulder pole the catalyzer of holding acid such as for example sulfuric acid or phosphoric acid etc.; Acidic ion exchange resin; Phosphalugel; Mesopore sial such as Al-MCM41 for example; Zeolite; Or layered zeolite such as ITQ-2 for example.
As solid acid catalyst, preferred surface is amassed big catalyzer, and the catalyzer that has a lot of acid position.The suitable BET specific surface area of used solid acid catalyst is at least 100m usually
2/ g, preferably 200m at least
2/ g, more preferably 300m at least
2/ g mostly is 1 most usually, 000m
2/ g preferably mostly is most 800m
2/ g more preferably mostly is most 700m
2/ g.And void content is 0.01cc/g at least usually, preferred 0.05cc/g at least, and more preferably 0.1cc/g at least mostly is most 0.8cc/g usually, preferably mostly is most 0.6cc/g, more preferably mostly is most 0.5cc/g.
In these solid acid catalysts, the catalyzer that preferred acid intensity is not too high.That for example can mention has mesoporous silicon, zeolite or a layered zeolite.
(i) zeolite
The structure of zeolite can represent with the code of International Zeolite Association (IZA) regulation, for example AEI, AET, AEL, AFI, AFO, AFS, AST, ATN, BEA, CAN, CHA, DDR, EMT, ERI, EUO, FAU, FER, LEV, LTL, MAZ, MEL, MFI, MOR, MTT, MTW, MWW, OFF, PAU, RHO, STT, TON etc.
Wherein, preferably has the zeolite that the aperture is the micropore of 3 ～9 .
In zeolite, preferred crystallinity porous silicate or crystallinity porous aluminum phosphoric acid salt, more preferably the crystallinity porous silicate of the metallic element modification beyond silica removal and the aluminium element or in periodictable the 1st～14 family through the crystallinity porous aluminum phosphoric acid salt of similar modification.
(i)-a crystallinity porous silicate
The crystallinity porous silicate can be: for example crystallinity porous silicate, aluminosilicate, aluminium silicophosphate, borosilicate and aluminoborosilicate etc., and the part element silicon in them is replaced by aluminium element and/or phosphoric and/or boron; Or the metal silicate that replaced by other elements of part element silicon.Wherein, preferred silicate, aluminosilicate, aluminium silicophosphate and the crystallinity aluminosilicate that is replaced by aluminoborosilicate, or below the crystallinity porous silicate of the modification mentioned.And, preferred SiO
2/ Al
2O
3Mol ratio greater than 10 aluminosilicate.
The structure of crystallinity porous silicate can be represented with the code that is used for zeolite of International Zeolite Association (IZA) regulation, AEI for example, AET, AEL, AFI, AFO, AFS, AST, ATN, BEA, CAN, CHA, DDR, EMT, ERI, EUO, FAU, FER, LEV, LTL, MAZ, MEL, MFI, MOR, MTT, MTW, MWW, OFF, PAU, RHO, STT, TON etc., preferred AFI, BEA, CAN, CHA, DDR, EMT, ERI, EUO, FAU, FER, LEV, LTL, MAZ, MEL, MFI, MOR, MTT, MTW, MWW, OFF, PAU, RHO, STT and TON.That specifically, can mention has SSZ-24 with AFI structure etc., has the β of BEA structure etc., has the cancrinite of CAN structure etc., chabazite with CHA structure, SSZ-13 etc., has the σ-1 of DDR structure etc., has the EMC-2 of EMT structure etc., has the erionite of ERI structure etc., has the EU-1 of EUO structure etc., has the USY of FAU structure etc., ferrierite with FER structure, ZSM35 etc., has the levyne of LEV structure etc., has the zeolite L of LTL structure etc., has the mazzite of MAZ structure etc., has the ZSM5 of MFI structure etc., has the ZSM11 of MEL structure etc., has the mordenite of MOR structure etc., has the ZSM23 of MTT structure etc., has the ZSM12 of MTW structure etc., has the MCM22 of MWW structure etc., has the Offrrtite of OFF structure etc., has the ECR18 of PAU structure etc., has the Rho of RHO structure etc., has the SSZ23 of STT structure etc., has the ZSM22 of TON structure etc.Wherein, preferably have the crystallinity porous silicate of AEI structure, BEA structure, CHA structure, MFI structure, more preferably have the crystallinity porous silicate of BEA structure and MFI structure.Specifically, can mention for example β and ZSM5 etc.
These crystallinity porous silicates can be various commercially available prod.In addition, can adopt by those crystallinity porous silicates of currently known methods synthetic, these methods are for example disclosed method in " synthetic (the Verified Syntheses Of Zeolitic Materials) of the zeolitic material of checking and approving " (the 2nd revised edition of 2001Elsevier) that IZA publishes.
And, in above-mentioned crystallinity porous silicate, the crystallinity porous aluminum silicate that contains aluminium element can be, by steam or acid treatment, remove the part aluminium of forming the crystallinity porous silicate that contains aluminium element, to reach high silica/alumina ratio.Preferred especially SiO
2/ Al
2O
3Mol ratio be at least 30 crystallinity porous aluminum silicate, more preferably be at least 50, further preferably be at least 100, especially preferably be at least 200.On the other hand, as the upper limit of this ratio, SiO
2/ Al
2O
3Mol ratio mostly be 1,000 most usually, more preferably mostly be most 750, preferably mostly be most 500 especially.For ZSM5 etc., not only can regulate its aluminum content by aforesaid method, also can regulate its aluminum content by control aluminium amount when it is synthetic.
The preferred BET specific surface area of described crystallinity porous aluminum silicate is 200m
2/ g～700m
2/ g, void content are the crystallinity porous aluminum silicate of 0.1cc/g～0.5cc/g.
(i)-b crystallinity porous aluminum phosphoric acid salt
Crystallinity porous aluminum phosphoric acid salt can be aluminium element and the phosphoric crystallinity porous aluminum phosphoric acid salt that can partly be replaced by element silicon and/or boron that constitutes it, for example crystallinity porous aluminate or phosphate, aluminosilicophosphate or boron aluminate or phosphate further can be the crystallinity porous aluminum phosphoric acid salt that can be replaced or pass through following modification by other atoms metals.
The phosphatic structure of this crystallinity porous aluminum can represent with the code that is used for zeolite of above-mentioned IZA regulation, for example, and AEI, AEL, AFI, AFO, AST, CHA, ERI or FAU.Preferred CHA.
The preferred crystallinity porous silicon of above-mentioned crystallinity porous aluminum phosphoric acid salt aluminate or phosphate.Specifically, can mention SAPO18 with AEI structure etc. is arranged, have SAPO5 of AFI structure etc., have SAPO41 of AFO structure etc., have SAPO11 of AEL structure etc., have SAPO16 of AST structure etc., have the CHA structure SAPO34, SAPO44 etc., have the SAPO17 etc. of ERI structure or have SAPO37 of FAU structure etc.The crystallinity porous silicon aluminate or phosphate that preferably has the CHA structure, preferred especially SAPO34.
These crystallinity porous aluminum phosphoric acid salt can be various commercially available prod, maybe can adopt by those crystallinity porous aluminum phosphoric acid salt of currently known methods synthetic, these methods are for example disclosed method in " synthetic (the Verified Syntheses Of Zeolitic Materials) of the zeolitic material of checking and approving " (the 2nd revised edition of 2001Elsevier) that IZA publishes.
＜modification solid acid catalyst 〉
In the solid acid catalyst of the present invention, above-mentioned crystallinity porous silicate and above-mentioned crystallinity porous aluminum phosphoric acid salt is the crystallinity porous silicate and the crystallinity porous aluminum phosphoric acid salt of the metallic element modification beyond silica removal and the aluminium element in periodictable the 1st～14 family preferably.
In the present invention, as being used for phosphatic periodictable the 1st～14 family's silica removal of above-mentioned crystallinity porous silicate of modification and above-mentioned crystallinity porous aluminum and aluminium element metallic element in addition, the metallic element in preferred the 1st～4 family and the 7th～13 family.In the metallic element of the 1st～4 family, the metallic element of preferred the 1st～3 family, the more preferably metallic element of the 1st～2 family.And, in the metallic element of the 7th～13 family, the metallic element of preferred the 7th family.
And, in the metallic element of periodictable the 1st～14 family, for the 1st～2 family, the metallic element in 3～5 cycles of preferred cycle table the, the more preferably metallic element in the 4th～5 cycle, the metallic element in preferred especially the 4th cycle.And, for the 3rd～14 family, the metallic element in the 4th～5 cycle in the preferred cycle table, the more preferably metallic element in the 4th cycle.Specifically, the example of these preferred metallic elements can be Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, lanthanon, Mn and Ni etc.Wherein as the metallic element of modification crystallinity porous silicate, specifically the metallic element of preferred the 1st～4 family, has Na, K, Rb, Cs, Mg, Ca, Sr and Ba, more preferably Na, K, Mg, Ca, Sr and Ba.And as the phosphatic metallic element of modification crystallinity porous aluminum, specifically the metallic element of preferred the 7th～13 family, has Mn and Ni, more preferably Mn.
And, for zeolite, preferably by the zeolite of the metallic element modification of the periodic table of elements the 2nd family by the structure of the coded representation such as BEA, ERI, FAU, MFI, MOR, MWW or OFF of above-mentioned IZA regulation.
＜method of modifying 〉
In the present invention, as above-mentioned crystallinity porous silicate of above-mentioned metallic element modification and the phosphatic method of crystallinity porous aluminum with periodictable the 1st～14 family, can adopt one of following method: (A) method, wherein in above-mentioned crystallinity porous silicate of preparation or the phosphatic process of crystallinity porous aluminum, under the situation of the compound of the above-mentioned metallic element that has periodictable the 1st～14 family, preparation crystallinity porous silicate or crystallinity porous aluminum phosphoric acid salt; (B) method wherein adopts the compound of the above-mentioned metallic element of periodictable the 1st～14 family to handle above-mentioned crystallinity porous silicate or crystallinity porous aluminum phosphoric acid salt, also can unite employing (A) and method (B).
The compound of above-mentioned metallic element as periodictable the 1st～14 family of the modification that is used for this moment for example, can adopt salt, oxide compound or the oxyhydroxide of the above-mentioned metal of periodictable the 1st～14 family.As salt, can adopt for example inorganic salt such as nitrate, phosphoric acid salt or muriate, or organic salt such as carboxylate salt such as acetate or carbonate.
And, as above-mentioned (A) method, promptly in above-mentioned crystallinity porous silicate of preparation or the phosphatic process of crystallinity porous aluminum, under the situation of the compound of the above-mentioned metallic element that has periodictable the 1st～14 family, preparation crystallinity porous silicate or crystallinity porous aluminum phosphoric acid salt, specifically, for example according to the method for JP-A-59-97523 and JP-A-3-101628 record, in preparation crystallinity porous silicate or the phosphatic raw material of crystallinity porous aluminum, exist under the situation of compound of metallic element of periodictable the 1st～14 family, in lattice, introduce described metallic element, thereby obtain crystallinity porous silicate by this metallic element modification, i.e. metal silicate for example, metallic aluminium silicon silicate (metalloaluminosilicosilicate), metallic aluminium silicophosphate (metallophosphosilicate), so-called crystallinity metal silicates such as inclined to one side borosilicate (metaborosilicate) or metallic aluminium borosilicate, or the crystallinity porous aluminum phosphoric acid salt of same modification, for example metallic aluminium phosphoric acid salt, so-called crystallinity metallic aluminium phosphoric acid salt such as Pure Silicon Metal aluminate or phosphate or metal boron aluminate or phosphate.
And, as above-mentioned (B) method, promptly adopt the compound of the above-mentioned metallic element of periodictable the 1st～14 family to handle above-mentioned crystallinity porous silicate or crystallinity porous aluminum phosphoric acid salt, specifically, can adopt following method (B-1), (B-2), (B-3).
(B-1): according to ordinary method, the solution of the compound of the above-mentioned metallic element by containing periodictable the 1st～14 family, above-mentioned crystallinity porous silicate and above-mentioned crystallinity porous aluminum phosphoric acid salt are carried out ion-exchange, the metallic element of periodictable the 1st～14 family is introduced lattice, thereby obtain crystallinity porous silicate by this metallic element modification, be above-mentioned crystallinity metal silicate, or the crystallinity porous calcium phosphate salt of same modification, the promptly above-mentioned crystallinity metallic aluminium phosphoric acid salt of mentioning.
(B-2): according to ordinary method, come above-mentioned crystallinity porous silicate or crystallinity metallic aluminium phosphoric acid salt are carried out surface treatment by for example pickling process or osmose process, can obtain crystallinity porous silicate or crystallinity porous aluminum phosphoric acid salt by the metallic element modification of periodictable the 1st～14 family.In described pickling process, above-mentioned crystallinity porous silicate or crystallinity metallic aluminium phosphoric acid salt are immersed the solution of the compound of the metallic element that contains periodictable the 1st～14 family, then, filter or separate by for example centrifugation; In described osmose process, above-mentioned crystallinity porous silicate or crystallinity metallic aluminium phosphoric acid salt are immersed in the solution of the compound that contains above-mentioned metallic element, then evaporate to dryness solution.
In this case, the solvent in the solution of the compound that contains above-mentioned metallic element is not particularly limited, can adopts water or alcohol, preferably water.And the concentration of solution is generally minimum 0.01 weight %, and solution reaches capacity at most.In described pickling process, need to consider described crystallinity porous silicate or the phosphatic water regain of crystallinity porous aluminum, but the preferred solution that adopts high density, thus described metallic element can be introduced effectively.And, in process the crystallinity porous silicate or crystallinity porous aluminum phosphoric acid salt of modification, the amount of the compound of contained periodictable the 1st～14 family's metallic element and the weight ratio of silicate or aluminate or phosphate are at least 0.001 usually, preferably at least 0.01, more preferably at least 0.1, mostly be 1,000 most usually, preferred maximum 100, more preferably maximum 10.
(B-3): according to ordinary method, the compound of above-mentioned crystallinity porous silicate or crystallinity porous aluminum phosphoric acid salt and periodictable the 1st～14 family's metallic element is carried out physical mixed, thereby can obtain crystallinity porous silicate or crystallinity porous aluminum phosphoric acid salt by the metallic element modification of periodictable the 1st～14 family.
In this physical mixed, consider the stability of compound under this admixture of the metallic element of periodictable the 1st～14 family, preferably adopt oxide compound and carbonate.And the compound preferable particle size of above-mentioned crystallinity porous silicate or crystallinity porous aluminum phosphoric acid salt and periodictable the 1st～14 family's metallic element is at least 0.01mm usually, mostly is the particle of 5mm most.Yet in order to carry out effective combination treatment, the particle diameter of metallic compound is the smaller the better.The blending ratio of the compound of crystallinity porous silicate or crystallinity porous aluminum phosphoric acid salt and periodictable the 1st～14 family's metallic element is, weight ratio in atoms metal and the crystallinity porous silicate or the aluminate or phosphate of metallic element, usually at least 0.001, preferably at least 0.01, more preferably at least 0.1, usually maximum 100, preferred maximum 10, more preferably maximum 5.And the mixing equipment of this moment is restriction especially not, can adopt common whipping device to mix.Consider that from the angle of efficient preferred employing can be pulverized and the blended device simultaneously.Can change mixing time according to the amount of handling, but be at least usually 1 second, preferably at least 1 minute, mostly be 10 hours usually most, preferred maximum 1 hour, more preferably maximum 30 minutes.
In above-mentioned method of modifying, material by above-mentioned (A) method gained has the initial performance as catalyzer, specifically, it is the high solid acid catalyst of a kind of propylene selectivity, and will be a kind of selectivity and all high solid acid catalyst of catalytic activity by the material of above-mentioned (B) method gained.
(ii) layered zeolite
Layered zeolite of the present invention is the zeolite that the layer of lamellar precursor is stripped from, as the record of " zeolite scientific and engineering (Science and Engineering of Zeolite) " the 10th page (talk society, 2000).Layered zeolite is the aluminosilicate that strength of acid is equal to zeolite, is a kind of material with mesopore.It has short-period rather than macrocyclic compound with regular structure.
Layered zeolite is generally aluminosilicate, and wherein, the mol ratio of Si/Al is at least 5, preferably is at least 7.5, more preferably is at least 10, mostly is 10,000 most, more preferably mostly is most 5,000, further preferably mostly is most 1,000.It can be the material that part or all of aluminium is replaced by the atom of periodictable the 2nd～14 family.The atom that is used to replace preferably can be B, Ti, V, Fe, Zn, Ga, Ge, Zr or Sn etc.
The BET specific surface area of layered zeolite is at least 300m usually
2/ g, preferably 400m at least
2/ g, more preferably 500m at least
2/ g mostly is 2 most usually, 000m
2/ g preferably mostly is most 1,800m
2/ g more preferably mostly is most 1,500m
2/ g.And in whole BET specific surface area, the ratio of the specific surface area in 1.7nm～30nm hole is at least 0.4 usually, preferably at least 0.5, more preferably at least 0.6.In XRD, when the K α line that adopts Cu is measured, there is not maximum peak every the d place at the interplanar of at least 17 , at 3～4.5 places the peak is arranged.
The volume in hole is at least 0.3cc/g usually, and preferably 0.5cc/g at least mostly is most 3cc/g usually, preferably mostly is most 2cc/g.
As the object lesson of layered zeolite, can mention for example ITQ-2, YNU-1 or ITQ-6, preferred ITQ-2.
＜prepare the method for layered zeolite 〉
General method as the preparation layered zeolite can adopt known method, " catalyzer magazine (Journal of Catalysis) " 186 for example, 57-63, (1999) or J.Am.Chem.Soc.122,2804-2809, (2000) disclosed method.Below will describe this method in detail, but should be appreciated that preparation is not limited only to this as the method for the layered zeolite of catalyzer of the present invention.
At first, silicon source, aluminium source, water and template (template) are mixed, if desired, also be mixed with mineralizer, this mixture is carried out hydro-thermal synthesize.As described silicon source, can adopt water glass, silicon sol, fine particle silica or alkyl silicate such as tetraethyl silicate for example.As the aluminium source, can adopt organic acid salt, oxyhydroxide, oxide compound, pseudobochmite, alkoxide or sodium aluminates etc. such as the inorganic acid salt such as nitrate, vitriol or muriate of aluminium for example or acetate.As template, can adopt for example alkyl quaternary ammonium salts, alkylamine, diamines, hydramine, alcohol, ether, acid amides, alkyl urea or cyano group alkane, preferred alkyl quaternary ammonium salt or amine.
As mineralizer, can adopt oxyhydroxide, supercarbonate or the carbonate etc. of basic metal for example or alkaline-earth metal.
For the ratio in silicon source and aluminium source, SiO
2/ Al
2O
3Usually be at least 1, preferably be at least 5, more preferably be at least 10, mostly be 1,000 most usually, preferably mostly be most 500, more preferably mostly be most 300.
The mol ratio in water and silicon source is H
2O/SiO
2Usually be at least 1, preferably be at least 2, more preferably be at least 3, mostly be 200 most usually, preferably mostly be most 150, more preferably mostly be most 120.
The ratio in mineralizer and silicon source is atoms metal and SiO in the mineralizer
2Mol ratio be at least 0.0001 usually, preferably be at least 0.001, more preferably be at least 0.01, mostly be 20 most usually, preferably mostly be most 10, more preferably mostly be most 8.
The ratio in template and silicon source is template and SiO
2Mol ratio be at least 0.01 usually, preferably be at least 0.02, more preferably be at least 0.05, mostly be 20 most usually, preferably mostly be most 10, more preferably mostly be most 6.
The aqueous mixture that makes like this is overheated, reach at least 80 ℃ usually, preferably at least 90 ℃, mostly be 260 ℃ most, preferably mostly be most 220 ℃, and, have hydro-thermal stirring or that do not have stirring synthetic at natural pressure or more under the high pressure.
The synthetic required time of this hydro-thermal was at least 1 hour usually, preferably at least 5 hours, mostly was 30 days usually most.
The lamellar precursor that separation such as filtration by hydro-thermal for example after synthetic are formed thus.
For supersiliceous zeolite, in the hydro-thermal building-up process, adopt the organic substance that is commonly referred to template, the at first synthetic precursor that contains the state (as-made) of template, and calcine this precursor, thus dehydrating condensation between genetic horizon forms zeolite.In this zeolite, be lamellar precursor through the synthetic prepared zeolite of hydro-thermal.As one of this product of decision index of whether being lamellar precursor is that the state of gained (as-made) is different from the structure after template is removed in calcining.For example this can be confirmed by XRD analysis.
Lamellar precursor for example can be the precursor of MWW type zeolite, this precursor can become MCM22, SSZ25, ITQ1, ERB1 or PSH3 by calcining, can be the so-called PREFER precursor that becomes FER through calcining, can be layered silicates such as PLS-1, RUB-15, RUB-18 for example.
Obtained by lamellar precursor under the situation of layered zeolite, usually, the interlamellar spacing that can widen this lamellar precursor by tensio-active agent is removed organic substance then, thereby layer is peeled off, and obtains layered zeolite.
For widening interlamellar spacing, handle lamellar precursor with the aqueous solution that contains tensio-active agent and quaternary ammonium salt.As tensio-active agent, adopt the water-soluble long-chain organic compound usually, specifically adopt the oxyhydroxide or the halogenide of octyl group trimethyl ammonium, dodecyl trimethyl ammonium or cetyltrimethyl ammonium, halogenide is preferably for example muriate or bromide etc.
Can adopt the alkylammonium of alkyl, for example tetrapropyl ammonium as quaternary ammonium salt with maximum 8 carbon atoms.
The ratio of mixture of quaternary ammonium salt and tensio-active agent (quaternary ammonium salt/tensio-active agent) is at least 0.1 usually, and preferably at least 0.2, more preferably at least 0.3, mostly be 10 most usually, preferably mostly be most 5, more preferably mostly be most 3.
The concentration of the aqueous solution is that the sum of tensio-active agent mole number and quaternary ammonium salt mole number is at least 0.1mol/L usually, preferred 0.2mol/L at least, more preferably 0.3mol/L at least mostly is most 10mol/L usually, preferably mostly be most 5mol/L, more preferably mostly be most 3mol/L.
The amount of this aqueous solution is that the weight ratio of the layered precursor and the aqueous solution is at least 2 usually, preferably at least 4, more preferably at least 10, mostly be 200 most usually, and preferably mostly be most 100, more preferably mostly be most 50.
Treatment temp is at least 20 ℃ usually, and preferably at least 40 ℃, more preferably at least 80 ℃, mostly be 120 ℃ usually most, preferably mostly be most 110 ℃, more preferably mostly be most 100 ℃.Treatment time was at least 1 hour usually, and preferably at least 7 hours, mostly be 40 hours usually most, preferably mostly be most 25 hours.
After the processing, described product is directly washed with water or will wash with water after the product filtration once, form slurry with water once more, carry out peeling off of layer then.Layer peel off for example known stripping meanss such as vigorous stirring, ultrasonication or spraying drying of common employing.Under the situation of vigorous stirring or ultrasonication, splitting time was at least 0.5 hour usually, and preferably at least 1 hour, mostly be 100 hours usually most, preferably mostly be most 20 hours.
After layer is peeled off, layered zeolite is separated.Can adopt filtration or centrifugation to separate.But, under the little situation of layered zeolite size, can add for example acid such as hydrochloric acid or sulfuric acid usually and produce throwing out, to improve organic efficiency.
To obtain containing the layered zeolite of template thus.But,, will carry out drying and calcining to obtain layered zeolite in order to remove template.
Drying temperature is at least 80 ℃ usually, mostly is 150 ℃ most, and drying was carried out 10 minutes usually at least, and preferably at least 30 minutes, maximum 24 hours usually, preferred maximum 12 hours.Calcining temperature is at least 300 ℃ usually, and preferably at least 400 ℃, mostly be 800 ℃ usually most, preferably mostly be most 600 ℃, calcining was carried out 10 minutes usually at least, and preferably at least 30 minutes, maximum 24 hours usually, preferred maximum 12 hours.
As by the above synthetic layered zeolite, that can mention has the ITQ-2 that for example is derived from MWW type zeolite precursor, an ITQ-6 that is derived from YUN-1 or PREFER.
The layered zeolite that makes like this has the short period compound with regular structure, therefore has the isoreactivity position, for example acid position as common zeolite, but than the more apparent stratiform of common zeolite, thereby have big outer surface.In view of these features, be beneficial to dispersion etc. in the present invention, and be catalyzer with good selectivity and weather resistance.
Above-mentioned catalyzer can be directly used in reaction, maybe can adopt material or tamanori to reactionlessness to carry out granulating and forming, is used for reaction then.As material or the tamanori to reactionlessness, that can mention has aluminum oxide or aluminium colloidal sol, silicon-dioxide, silica gel, quartz or their mixture.By mix the cost that can reduce whole catalyzer effectively with these materials, auxiliary adiabatic heat absorption function also is of value to the densification of catalyzer and the increase of catalyst strength in addition when being of value to the performance catalyst regeneration.
(3) reaction conditions of the present invention
The reactive mode of manufacture method of the present invention is not particularly limited, as long as the raw material of supplying with in conversion zone is a gas phase, can adopt the known gas phase reaction process that is undertaken by fluidized-bed reactor, moving-burden bed reactor or fixed-bed reactor.And, can react with batch-type, semi continuous or continous way, but preferably adopt continous way to carry out this reaction.This method can be to adopt the method for single reaction vessel, or adopts the method for a plurality of reactors of serial or parallel connection configuration.
According to the present invention, in preparing the method for propylene (this method comprises makes ethene contact in the presence of catalyzer with methyl alcohol and/or dme), the conditioned reaction condition, so that the amount that the amount of ethene adds the ethene of this reaction system relatively in the reaction mixture of discharging from reaction system reduces, and, moles of methanol and duple dme mole number sum with the adding reaction system are benchmark, and the productive rate of propylene is at least 40 moles of %.
As the reaction conditions of regulating for this reason, pressure and raw material are formed and reaction when carrying out with continous way material feeding speed be particularly important.
Reaction pressure is less than 2MPa usually.Reaction pressure preferably mostly is most 1MPa, more preferably mostly is most 0.7MPa, comprising pressing (nature pressure) certainly.And the lower limit of pressure is not particularly limited, but is at least 0.1kPa usually, preferred 7kPa at least, more preferably 50kPa at least.
For realizing above-mentioned target, described reaction pressure is adjusted to more than or equal to 0.10kPa and less than 2MPa.In this case, when reaction pressure increases, as the ethene of reaction raw materials or as the propylene of target product may with the alkene generation polymerization that exists in the reaction system, therefore, the productive rate of propylene will reduce, when reaction pressure reduced, speed of response was slack-off.So, should consider these trend when regulating pressure.
Composition for raw material, the amount that adds the ethene of reaction system has surpassed the methyl alcohol of reaction system and the amount of dme of adding, promptly add the amount of ethene of reaction system and the mol ratio of moles of methanol and duple dme mole number sum and be at least 1 usually, preferably at least 1.8, more preferably at least 3.On the other hand, if ethene is excessive, with appearance and the growing amount of cost, by product and the relevant problems such as trouble degree of operation.Therefore, as the upper limit, the amount of the ethene of adding reaction system and the mol ratio of moles of methanol and duple dme mole number sum mostly are 20 most usually, preferably mostly are most 10, preferably mostly are most 6 especially.
For realizing above-mentioned target, the mol ratio of amount and moles of methanol that adds reaction system and duple dme mole number sum that adds the ethene of this reaction system is adjusted to is at least 1 and mostly be 20 scope most.In this case, when the amount of ethene increases, be easy to take place the reaction between the ethene itself, therefore, the growing amount of by product will increase, and when the amount reduction of ethene, be easy to take place the reaction between methyl alcohol and/or the diethyl ether itself, and therefore, ethene etc. will form.So, should be taken into account these trend when regulating consumption.
And, in the mol ratio of the amount of the ethene that regulate to add reaction system and moles of methanol that adds reaction system and duple dme mole number sum to being at least 1 and when mostly being most 20 scope, this does not also mean that the amount of only regulating ethene.Can regulate an aspect in the amount of the amount of ethene and methyl alcohol and/or dme, or these two amounts all regulate, and are adjusted to and are at least 1 and mostly be 20 scope most so that will add the mol ratio of amount and moles of methanol that adds reaction system and duple dme mole number sum of the ethene of reaction system.
As the adding speed of the raw material that reacts with continous way, add the methyl alcohol of reaction system and the weight hourly space velocity (WHSV) of the per unit catalytic active component weight of the dme sum that is scaled methyl alcohol and mostly be about 70hr usually most
-1(hour
-1), preferably mostly be most 50hr
-1, more preferably mostly be most about 30hr
-1, further preferably mostly be most 20hr
-1At this, if WHSV is too little, because the increase of by product, the productive rate of target product may reduce, and separates also will bother.Therefore, WHSV is at least about 0.01hr usually
-1, preferably be at least 0.05hr
-1, more preferably be at least 0.1hr
-1, further preferably be at least 0.5hr
-1
For realizing above-mentioned target, be adjusted to 0.01hr at least with adding the methyl alcohol of reaction system and the weight hourly space velocity (WHSV) of the per unit catalytic active component weight of the dme sum that is scaled methyl alcohol
-1To mostly being most 70hr
-1Scope.If WHSV is little, aforesaid gradual reaction may take place, therefore, by product will increase, and formed propylene will be consumed.So, should be taken into account this trend when regulating WHSV.
Under the situation of reacting, can set the reaction times aptly according to the productive rate of target propylene with intermittent type or semi continuous.
At this, if contain a large amount of unreacted methanol and unreacted dme from the composition that reaction system is discharged, then the utilization ratio of methyl alcohol and dme is low, thereby can not get the cost benefit.Moreover, in the purge process of separating with propylene as target product with propylene, load also will become greatly, and this is unfavorable.And this reaction is thermopositive reaction, if a large amount of methyl alcohol primary first-order equation, because the reaction heat production, then temperature will be difficult to control, and the result can cause further influence, for example the shortening of the reduction of target product productive rate or catalyst life etc.So, preferably add methyl alcohol and dme with batch mode.
, for example whether adopt single reaction vessel, or do not adopt a plurality of reactors of serial or parallel connection configuration according to the design of reaction system and different with the reinforced method of batch mode.For example, can enumerate following method: a plurality of opening for feeds of methyl alcohol and dme being set for a reactor, reinforced to adopt batch mode; The opening for feed of methyl alcohol and dme perhaps is set respectively to a plurality of reactors, feeds in raw material with the employing batch mode etc.At this, batch mode is reinforced preferably carries out by this way, promptly behind the methyl alcohol and dme consumption at least 90% that adds in the ban, adds remaining methyl alcohol and dme again.
Reaction conditionss such as for example temperature of reaction of manufacture method of the present invention can be set arbitrarily according to currently known methods.If contain a large amount of unreacted methanol and unreacted dme from the composition that reaction system is discharged, then the utilization ratio of methyl alcohol and dme reduces, and can not get the cost benefit.Moreover, in the purge process of separating with propylene as target product with propylene, load also will become greatly, and this is unfavorable.Therefore, as above-mentioned various reaction conditionss, the preferred condition that material benzenemethanol and dme are transformed fully that adopts.
At this, temperature of reaction can be decided according to the kind of the catalyzer that is adopted, but usually at least about 200 ℃, preferably at least about 250 ℃, more preferably at least about 300 ℃, the upper limit mostly is about 700 ℃ usually most, preferably mostly is most about 600 ℃, more preferably mostly is most about 500 ℃.If temperature of reaction is too low, speed of response will diminish, and the speed that forms target product will be significantly slack-off, with a large amount of unreacted raw materials of remnants.On the other hand, if temperature of reaction is too high, then the productive rate of target product will reduce.
And along with the continuation of reaction, catalyzer may coking in reactor, thereby reduces reactive behavior.In this case, this catalyzer is taken out from reactor,, thereby make catalyst regeneration for example by in oxygen containing atmosphere, all or part of coke being removed in the oxidation of accumulative coke.This regenerated catalyst is imported reactor once more.Consider from the angle of this taking-up of catalyzer and importing once more, adopt the method for moving-burden bed reactor or fluidized-bed reactor more easier than the operation of the method that adopts fixed-bed reactor.
In the manufacture method of the present invention, when reaction is carried out, in reaction system, will generate water as by product.But, preferably, by water being added the medium method of reaction raw materials, so that water (being water vapor) begins promptly to coexist reaction system from reacting the starting stage to the reaction system supplied water.There is water by making in this system, can suppresses to cause the formation of the coke of catalyst deactivation, also may produce the effect that prolongs catalyst life, and suppress the formation of paraffinic hydrocarbons or the low dimerization of gained alkene, thereby improve the selectivity of purpose propylene.The water yield that adds reaction system can be decided according to kind or other reaction conditionss of used solid acid catalyst, but, this water yield is at least 0.025 usually with the moles of methanol that adds reaction system and the mol ratio of duple dme mole number sum, and preferably at least 0.1, more preferably at least 0.5.If water is too many, speed of response will reduce, and the problem that exists is that the amount of target product will reduce, or catalyst themselves reacts and the generation sex change with water.So this mol ratio mostly is 15 most usually, preferably mostly is most 10, more preferably mostly is most 5.
The mixture of reaction products of above-mentioned reaction gained is to contain the material that main component is a propylene, in addition, also contains the alkene of unreacting material ethene and at least 4 carbon atoms.About the growing amount of paraffinic hydrocarbons, alkene and the aromatic hydrocarbon by product of at least 4 carbon atoms, in the hydrocarbon composition of reactor outlet, its volumetric molar concentration mostly is 30% most, preferably mostly is most 15%.And, also contain ethene less than the ethene amount that adds reaction system, be benchmark with moles of methanol and the duple dme mole number sum that adds reaction system, the propylene amount that contains is at least 40mol/%, preferably 50mol/% at least.
(4) method of separated product
From above-mentioned mixture of reaction products during separate targets product propylene, the separation known/purifier apparatus can importing this mixture in the cracking of ethylene process can reclaim at each composition, purifying, utilize or discharge and handle.
In the present invention, through ethene and methyl alcohol and/or dme reaction and reaction product contain propylene and unreacted ethene, methyl alcohol and the dme that generates to some extent, in addition, also contain alkene, further contain for example carrier such as ethane as at least 4 carbon atoms of by product.Be the purifying propylene, should provide eparating methanol tower, deethanizing column, depropanizing tower etc. as production of propylene equipment.But, by described reaction product is recycled to above-mentioned through the petroleum naphtha thermolysis produce the equipment of alkene, by the equipment of methyl alcohol and/or dimethyl ether production light alkene or prepare separation/purification system in the equipment of ethene by ethane steam cracking, the part instrument that should provide for production of propylene equipment can be provided, thereby can make described apparatus minimizes.
For example, adopt aforementioned equipment to make ethene through petroleum naphtha thermolysis production alkene, make this ethene and the gas reaction that contains methyl alcohol and/or dme prepare propylene, in the case, preferably reaction product is imported demethanizing tower and/or deethanizing column and/or depropanizing tower in the olefin production plant.Thereby can significantly change productive rate balance at ethene and propylene in the process of petroleum naphtha thermolysis production alkene, to improve the ratio of propylene/ethylene amount, can also improve the efficient of producing the equipment of alkene through the petroleum naphtha thermolysis, the production unit for preparing propylene by ethene is minimized.
This reaction product contains propylene and the unreacted ethene that generates to some extent, in addition, also contain alkene as at least 4 carbon atoms of by product, and, overhead fraction in above-mentioned front end demethanizing process and the above-mentioned front end depropanizing process is being used as under the situation of ethylene raw, and this reaction product also will contain ethane, in addition, overhead fraction in the above-mentioned front end deethanizing process is being used as under the situation of ethylene raw, and this reaction product can also contain ethane, methane and hydrogen etc.Therefore, in the purifying of propylene, the production of propylene evaluation method selecting optimal equipment possesses demethanizing tower, deethanizing column, depropanizing tower etc. in the method for the invention, but, operational situation according to olefin production plant, can near small part reaction product import demethanizing tower and/or deethanizing column and/or depropanizing tower in this equipment, thereby, the operation efficiency of the equipment of alkene is produced in raising through the petroleum naphtha thermolysis, simultaneously the machine quantity that is disposed for production of propylene equipment is minimized, and/or make the energy minimization of institute's configuration machine.
Disposing for production of propylene equipment under the situation of demethanizing tower and/or deethanizing column and/or depropanizing tower, operational situation according to olefin production plant and production of propylene equipment, can demethanizing tower and/or the deethanizing column and/or the depropanizing tower of production of propylene equipment will be imported from the product of olefin production plant, thereby can enlarge the tolerable limit of olefin production plant, also can change operational condition as required, so that comprise the method overall efficiency maximization of olefin production plant and production of propylene equipment.
Under the situation of ethene as ethene that adopts by aforementioned light alkene production unit gained, preferably the reaction product that mainly contains propylene with gained is recycled in the separation/purification system of aforementioned light alkene production unit.
In this case, the separation/purification system as for the aforementioned light alkene production unit of reaction product round-robin for example can be washing tower or its pipe arrangement in the aforementioned producing apparatus, or take off ethylene/ethane tower or its pipe arrangement.
At this, the cut that preferably will contain ethene utilizes as reaction raw materials again.
And, in above-mentioned reaction, also can form water as by product.Therefore, also preferably the portion water that forms in the reaction system is added in the raw material, in reaction system, utilize again.
Embodiment
Following embodiment will show object lesson of the present invention.But, be to be understood that the present invention is in no way limited to these embodiment.
Embodiment 1-1
Adopt atmospheric fixed bed circulation reaction unit to react, the mixture that will contain 0.1g catalyzer and the 0.5g thinner quartz sand external diameter of being made by PYREX (registered trademark) of packing into is in the reaction tubes of 6mm.Employing is according to United States Patent (USP) 4,440, and the SAPO34 of 871 preparations is reflected under the following reaction conditions and carries out as catalyzer.Show reaction result in the table 1, adopted the gas chromatography assay products.70 minutes values at the end behind the composition of conversion of methanol, hydrocarbon and the productivity of propylene representative setting reaction conditions.
＜reaction conditions 〉
Temperature of reaction: 400 ℃
Methyl alcohol: 6.5 moles of %
Ethene/methyl alcohol (mol ratio)=5
Water/methyl alcohol (mol ratio)=4
Methyl alcohol WHSV=0.5hr
-1
Embodiment 1-2
Adopt the mode identical with embodiment 1-1 to react, difference is to adopt according to the Chi of oil association, 24, and (5), the synthetic ZSM5 (SiO of method institute of 275-280 (1981) record
2/ Al
2O
3=300) as catalyzer.
Comparative example 1
Adopt the mode identical with embodiment 1-1 to react, difference is to adopt SAPO34 as catalyzer, and changes ethene/methyl alcohol (mol ratio) into 0.5.
Table 1
| Embodiment 1-1 | Embodiment 1-2 | Comparative example | |
| Catalyzer ETY/MeOH (mol ratio) H 2Hydrocarbon in O/MeOH (mol ratio) MeOH conversion ratio (%) the reactor exhaust constituent form the productive rate of (%) ethylene, propylene butylene take the MeOH that adds as the propylene of benchmark (% by mole) | SAPO-34 5 4 100 61.1 28.2 3.0 120.4 | ZSM-5 5 4 100 60.1 14.2 10.8 56.6 | SAPO-34 0.5 4 100 73.3 18.2 5.1 15.7 |
(ETY=ethene, MeOH=methyl alcohol)
Embodiment 2～14
The preparation of＜solid acid catalyst 〉
Preparation example 1
According to the Chi of oil association, 24, (5), the method for 275-280 (1981) record makes the crystallinity porous aluminum silicate H type ZSM5 (SiO with MFI structure
2/ Al
2O
3=300).Adopt fluorescent x-ary analysis to analyze the composition of this crystallinity porous aluminum silicate, the result is as shown in table 2.
Preparation example 2
The crystallinity porous aluminum silicate of gained in the 1g preparation example 1 is directly mixed in mortar with solid-state with 0.36g lime carbonate, to obtain being mixed with the crystallinity porous aluminum silicate of calcium, described lime carbonate, was made 550 ℃ of calcinings 500 ℃ of calcinings 10 hours then by lime acetate in 6 hours.
Preparation example 3
The crystallinity porous aluminum silicate of gained in the 1g preparation example 1 is directly mixed in mortar with solid-state with the 0.36g Strontium carbonate powder, and to obtain being mixed with the crystallinity porous aluminum silicate of strontium, described Strontium carbonate powder was made 500 ℃ of calcinings by strontium acetate in 18 hours.
Preparation example 4
According to the Chi of oil association, 24, (5), the method for 275-280 (1981) record makes the crystallinity porous aluminum silicate H type ZSM5 (SiO with MFI structure
2/ Al
2O
3=50).With the described crystallinity porous aluminum of 2g silicate with 1.23g one hydration lime acetate is dissolved in the formed water-soluble liquid-phase mixing of 20ml water, with this mixture about 80 ℃ of stir abouts 20 hours, then at 100 ℃～120 ℃ evaporates to dryness, then in air, calcined about 2 hours at 200 ℃, 500 ℃ of calcinings 18 hours, the crystallinity porous aluminum silicate of calcium is arranged then to obtain load.With the composition of this aluminosilicate of x-ray fluorescence analysis, the result is as shown in table 2.
Preparation example 5
According to the Chi of oil association, 24, (5), the method for 275-280 (1981) record further adopts boric acid in raw material, make the crystallization of zeolites porous aluminum borosilicate with MFI structure.Analyze the composition of this crystallinity porous aluminum borosilicate with chemical analysis and fluorescent x-ary analysis, the result is as shown in table 2.With the described crystallinity porous aluminum of 1g borosilicate with 0.4g one hydration lime acetate is dissolved in the formed water-soluble liquid-phase mixing of 10ml water, with this mixture about 80 ℃ of stir abouts 20 hours, then at 100 ℃～120 ℃ evaporates to dryness, then in air, calcined 2 hours at 200 ℃, 500 ℃ of calcinings 18 hours, the crystallinity porous aluminum borosilicate of calcium is arranged then to obtain load.
Preparation example 6
0.38g ANN aluminium nitrate nonahydrate and 0.45g one hydration lime acetate are dissolved in 30g water make the aqueous solution, adding 20g contains the colloid silica (changing into (strain) system by catalyst) and the 14g water of 30 weight % silicon-dioxide under stirring, and adding is dissolved in the formed aqueous solution of 6.67g water by 0.42g sodium hydroxide.Further add and be dissolved in the formed aqueous solution of 10g water by 2.7g bromination tetra-n-butyl ammonium, vigorous stirring 2 hours.The mol ratio that add material this moment is SiO
2/ Al
2O
3=200, CaO/SiO
2=0.025.With this gel mixture internal capacity of packing into is in the autoclave of 100ml, under the pressure of itself, carries out hydrothermal treatment consists 48 hours at 180 ℃.Filtration product, washing 120 ℃ of dried overnight, was calcined 6 hours at 550 ℃ in air.With respect to the hydrochloric acid of every 1g product mixing 15ml 0.8N, and at room temperature stirred 24 hours, then, behind the water cleaning down,, in air, calcined 6 hours, thereby obtain the calcareous crystallinity porous aluminum of H type silicate at 550 ℃ 120 ℃ of dried overnight.Analyze the composition of this calcareous crystallinity porous aluminum silicate with fluorescent x-ary analysis, the result is as shown in table 2.This calcareous crystallinity porous aluminum silicate is directly mixed in mortar with solid-state with 0.36g lime carbonate, to obtain being mixed with the H type calcic crystallinity porous aluminum silicate of calcium, described lime carbonate, was made 550 ℃ of calcinings 500 ℃ of calcinings 10 hours then by lime acetate in 6 hours.
Preparation example 7
The calcic crystallinity porous aluminum silicate of gained in the 1g preparation example 6 is directly mixed in mortar with solid-state with the 0.36g Strontium carbonate powder, and to obtain being mixed with the H type calcic crystallinity porous aluminum silicate of strontium, described Strontium carbonate powder is made 500 ℃ of calcinings 18 by strontium acetate.
Preparation example 8
0.38g ANN aluminium nitrate nonahydrate and 0.45g four hydration magnesium acetates are dissolved in 30g water make the aqueous solution, adding 20g contains the colloid silica (changing into (strain) system by catalyst) and the 14g water of 30 weight % titanium dioxide silicon under stirring, and adding is dissolved in the aqueous solution that 6.67g water forms by 0.42g sodium hydroxide.Further add and be dissolved in the aqueous solution that 10g water forms by 2.7g bromination tetra-n-butyl ammonium, vigorous stirring 2 hours.The mol ratio that add material this moment is SiO
2/ Al
2O
3=200, CaO/SiO
2=0.025.With this gel mixture internal capacity of packing into is in the autoclave of 100ml, under the pressure of itself, carries out hydrothermal treatment consists 48 hours at 180 ℃.Filtration product, washing 120 ℃ of dried overnight, was calcined 6 hours at 550 ℃ in air.With respect to the hydrochloric acid of every 1g product mixing 15ml 0.8N, and at room temperature stirred 24 hours, then, behind the water cleaning down,, in air, calcined 6 hours, thereby obtain the magniferous crystallinity porous aluminum of H type silicate at 550 ℃ 120 ℃ of dried overnight.Analyze the composition of this magniferous crystallinity porous aluminum silicate with fluorescent x-ary analysis, the result is as shown in table 2.
Preparation example 9
The magnesium crystallinity porous aluminum silicate that contains of 1g preparation example 8 gained is directly mixed in mortar with solid-state with 0.36g lime carbonate, contain magnesium crystallinity porous aluminum silicate with the H type that obtains being mixed with calcium, described lime carbonate, was made 550 ℃ of calcinings 500 ℃ of calcinings 10 hours then by lime acetate in 6 hours.
Preparation example 10
The magnesium crystallinity porous aluminum silicate that contains of 1g preparation example 8 gained is directly mixed in mortar with solid-state with 0.36g magnesium oxide, contain magnesium crystallinity porous aluminum silicate with the H type that obtains being mixed with magnesium, described magnesium oxide was made 500 ℃ of calcinings by magnesium acetate in 18 hours.
Preparation example 11
1g preparation example 8 gained are contained magnesium crystallinity porous aluminum silicate and 0.36g manganese oxide (Mn
2O
3) directly in mortar, mix with solid-state, containing magnesium crystallinity porous aluminum silicate with the H type that obtains being mixed with manganese, described manganese oxide was made 500 ℃ of calcinings by manganous oxalate in 18 hours.
Preparation example 12
0.38g ANN aluminium nitrate nonahydrate and 0.65g one hydration barium acetate are dissolved in 30g water make the aqueous solution, adding 20g contains the colloid silica (changing into (strain) system by catalyst) and the 14g water of 30 weight % silicon-dioxide under stirring, and adding is dissolved in the formed aqueous solution of 6.67g water by 0.42g sodium hydroxide.Further add and be dissolved in the formed aqueous solution of 10g water by 2.7g bromination tetra-n-butyl ammonium, vigorous stirring 2 hours.The mol ratio that add material this moment is SiO
2/ Al
2O
3=200, BaO/SiO
2=0.025.With this gel mixture internal capacity of packing into is in the autoclave of 100ml, under the pressure of itself, carries out hydrothermal treatment consists 48 hours at 180 ℃.Filtration product, washing 120 ℃ of dried overnight, was calcined 6 hours at 550 ℃ in air.With respect to the hydrochloric acid of every 1g product mixing 15ml 0.8N, and at room temperature stirred 24 hours, then, behind the water cleaning down, 120 ℃ of dried overnight, in air 550 ℃ of calcinings 6 hours, thereby obtain the crystallinity porous aluminum silicate of H type baric.Analyze the composition of the crystallinity porous aluminum silicate of this baric with fluorescent x-ary analysis, the result is as shown in table 2.The crystallinity porous aluminum silicate of this baric of 1g is directly mixed in mortar with solid-state with 0.36g lime carbonate, to obtain being mixed with the H type baric crystallinity porous aluminum silicate of calcium, described lime carbonate, was made 550 ℃ of calcinings 500 ℃ of calcinings 10 hours then by lime acetate in 6 hours.
Preparation example 13
0.09g aluminum phosphate and 0.34g one hydration lime acetate are dissolved in 25g water make the aqueous solution, adding 15g contains the colloid silica (changing into (strain) system by catalyst) of 30 weight % silicon-dioxide under stirring, and adding is dissolved in the formed aqueous solution of 7.5g water by 0.4g sodium hydroxide.Further, adding is dissolved in the formed aqueous solution of 10g water by 1.96g bromination tetra-n-butyl ammonium, vigorous stirring 2 hours.The mol ratio that add material this moment is SiO
2/ Al
2O
3=200, MgO/SiO
2=0.025, SiO
2/ P
2O
5=200.With this gel mixture internal capacity of packing into is in the autoclave of 100ml, under the pressure of itself, carries out hydrothermal treatment consists 48 hours at 180 ℃.Filtration product, washing 120 ℃ of dried overnight, was calcined 6 hours at 550 ℃ in air.With respect to the hydrochloric acid of every 1g product mixing 15ml 0.8N, and at room temperature stirred 24 hours, then, behind the water cleaning down,, in air, calcined 6 hours, thereby obtain the calcareous crystallinity porous aluminum of H type silicophosphate at 550 ℃ 120 ℃ of dried overnight.Analyze the composition of this calcareous crystallinity porous aluminum silicophosphate with fluorescent x-ary analysis, the result is as shown in table 2.This calcareous crystallinity porous aluminum silicophosphate of 1g is directly mixed in mortar with solid-state with 0.36g lime carbonate, to obtain being mixed with the H type calcic crystallinity porous aluminum silicophosphate of calcium, described lime carbonate, was made 550 ℃ of calcinings 500 ℃ of calcinings 10 hours then by lime acetate in 6 hours.
Table 2
| SiO 2/Al 2O 3(mol ratio) | MO (weight %) | MO/SiO 2(mol ratio) | B 2O 3(weight %) | SiO 2/B 2O 3(mol ratio) | P 2O 5(weight %) | SiO 2/P 2O 5(mol ratio) | |
| Preparation example 1 | 323 | - | - | - | - | - | - |
| Preparation example 4 | 53 | 14.0 | 0.27 | - | - | - | - |
| Preparation example 5 | 110 | - | - | 0.88 | 129 | - | - |
| Preparation example 6 | 382 | 0.4 | 0.004 | - | - | - | - |
| Preparation example 8 | 285 | 0.1 | 0.002 | - | - | - | - |
| Preparation example 12 | 271 | 1.2 | 0.015 | - | - | - | - |
| Preparation example 13 | 527 | 0.4 | 0.004 | - | - | 0.07 | 3040 |
M: metal
＜reaction 〉
Adopt atmospheric fixed bed circulation reaction unit to react, in the external diameter of being made by PYREX (registered trademark) is the reaction tubes of 6mm, pack into and contain the mixture of following material: as the 0.1g of solid acid catalyst crystallinity porous aluminum silicate (embodiment 2) by preparation example 1 gained, or 0.136g is by the crystallinity porous aluminum silicate or the crystallinity porous aluminum borosilicate (embodiment 3～14) through the metallic element modification of preparation example 2～13 gained, as the 0.5g quartz sand of thinner, this is reflected under the reaction conditions shown in the table 3 and carries out.Adopt gas chromatography analytical reaction result, the result is as shown in table 3.
Table 3
| Reaction conditions | Reaction result | |||||||||||
| Catalyzer | Methyl alcohol (mole %) | Ethene/methyl alcohol (mol ratio) | Methyl alcohol WHSV (hr -1) | Water/methyl alcohol (mol ratio) | Temperature of reaction (℃) | Reaction times | Methanol conversion (%) | The composition of hydrocarbon in the reactor exhaust constituent (mole %) | With the methyl alcohol that adds is the productivity of propylene (mole %) of benchmark | |||
| Ethene | Propylene | Butylene | ||||||||||
| Embodiment 2 | Preparation example 1 | 6.5 | 5 | 0.5 | 4 | 400 | 40 minutes 8 hours | 100 100 | 66.3 88.3 | 12.8 6.1 | 8.7 2.6 | 54.8 30.4 |
| Embodiment 3 | Preparation example 2 | 6.5 | 5 | 0.4 | 4 | 400 | 40 minutes 8 hours | 100 100 | 50.2 71.0 | 13.7 10.6 | 13.4 8.2 | 50.8 45.9 |
| Embodiment 4 | Preparation example 3 | 6.5 | 5 | 0.4 | 4 | 400 | 40 minutes 8 hours | 100 100 | 21.2 68.3 | 14.6 11.5 | 15.9 9.1 | 44.3 48.9 |
| Embodiment 5 | Preparation example 4 | 6.5 | 5 | 0.1 | 4 | 450 | 40 minutes 8 hours | 100 100 | 38.1 45.8 | 21.2 19.8 | 15.3 14.4 | 73.5 72.9 |
| Embodiment 6 | Preparation example 5 | 6.5 | 5 | 0.1 | 4 | 430 | 40 minutes 8 hours | 100 100 | 38.5 34.1 | 24.0 24.1 | 15.8 16.8 | 85.7 82.6 |
| Embodiment 7 | Preparation example 6 | 6.5 | 5 | 0.4 | 4 | 400 | 40 minutes 8 hours | 100 100 | 14.1 46.3 | 14.6 16.4 | 14.3 13.1 | 39.5 58.3 |
| Embodiment 8 | Preparation example 7 | 6.5 | 5 | 0.4 | 4 | 400 | 40 minutes 8 hours | 100 100 | 16.6 45.8 | 14.5 17.1 | 14.8 14.1 | 13.7 60.8 |
| Embodiment 9 | Preparation example 8 | 6.5 | 5 | 0.5 | 4 | 400 | 40 minutes 7 hours | 100 100 | 49.8 72.8 | 22.3 13.2 | 12.1 5.9 | 85.0 58.8 |
| Embodiment 10 | Preparation example 9 | 6.5 | 5 | 0.4 | 4 | 400 | 40 minutes 8 hours | 100 100 | 55.3 73.7 | 21.1 12.9 | 10.4 5.9 | 84.0 57.7 |
| Embodiment 11 | Preparation example 10 | 6.5 | 5 | 0.4 | 4 | 400 | 40 minutes 8 hours | 100 100 | 53.4 71.9 | 22.4 13.8 | 10.6 5.9 | 88.2 61.2 |
| Embodiment 12 | Preparation example 11 | 6.5 | 5 | 0.4 | 4 | 400 | 40 minutes 8 hours | 100 100 | 31.9 59.2 | 24.7 18.0 | 14.3 9.0 | 81.6 73.0 |
| Embodiment 13 | Preparation example 12 | 6.5 | 5 | 0.4 | 4 | 400 | 40 minutes 8 hours | 100 100 | 24.0 67.1 | 21.2 15.7 | 12.6 7.0 | 65.3 67.8 |
| Embodiment 14 | Preparation example 13 | 6 5 | 5 | 0.4 | 4 | 400 | 40 minutes 8 hours | 100 100 | 39.6 80.3 | 21.3 9.5 | 15.0 4.6 | 73.8 44.3 |
By result shown in the table 3 as seen, embodiment 2 adopts unmodified crystallinity porous silicate as catalyzer, compare with the situation of embodiment 2, embodiment 3 or 4 adopts crystallinity porous silicate by calcium or strontium modification as catalyzer, in this case, methyl alcohol with adding is benchmark, even the productivity of propylene height of the productivity of propylene after the reaction times is 8 hours after also being 40 minutes than the reaction times, simultaneously between this two reaction times the difference of productive rate be respectively-4.9% or+4.6%, and the productive rate in embodiment 2 is low, and the productive rate between two reaction times has reduced by 24.4%.That is to say that this is proof just, the method according to this invention can obtain high yield, the reduction of productive rate in the time of can suppressing long-time operation simultaneously.And, shown in embodiment 5～12, as seen, under the situation of metal-modified crystallinity porous silicate as solid acid catalyst, can obtain high yield by other, the reduction of productivity of propylene in the time of can suppressing long-time operation simultaneously in employing.
Embodiment 15
＜Preparation of catalysts 〉
MCM22 precursor: with the NaAlO of 0.8g 70%
2Be dissolved in the 162g deionized water and stirring with 1.4g NaOH.When obtaining transparent aqueous solution, add 9.9g hexamethylene imine and 12g silicon-dioxide (AEROSIL 200, and by NIPPON AEROSIL CO., LTD produces), then stirred 2 hours.The slurries branch of gained is gone in the autoclave of two 100ml, rolled 7 days at 150 ℃.With the autoclave cooling, then, the filtering content thing, washing is 120 ℃ of dryings, to obtain the MCM22 precursor.
ITQ-2: the tetrapropylammonium hydroxide that 4.5g MCM22 precursor is added by 5.1g bromination six decyl trimethyl ammoniums and 5.5g 40% is dissolved in the formed aqueous solution of 12.4g water, then refluxes 16 hours at 80 ℃.The gained slurries are used ultrasonication 1 hour.Then, dropwise add the 0.25M hydrochloric acid soln, make pH, then filter smaller or equal to 2, washing, dry then, 550 ℃ of calcinings 24 hours, to obtain ITQ-2 as catalyzer.
＜reaction 〉
Adopt the mode identical with embodiment 2 to react, difference is that the 0.1g ITQ-2 of gained in the usefulness aforesaid method is as catalyzer.Adopt gas chromatography to carry out product analysis.The reaction beginning is as shown in table 4 with the result after 8 hours after 40 minutes.
Table 4
| Embodiment 15 | Embodiment 2 | ||||
| Catalyzer | ITQ-2 | ZSM-5 | |||
| Reaction times (minute) | 40 | 480 | 40 | 480 | |
| Methanol conversion (%) | 100 | 100 | 100 | 100 | |
| The composition of hydrocarbon (%) in the product | Ethene | 18.6 | 19.3 | 66.3 | 88.3 |
| Propylene | 9.6 | 15 | 12.8 | 6.1 | |
| Butylene | 9.1 | 15.5 | 8.7 | 2.6 | |
| Methyl alcohol with adding is the productivity of propylene (%) of benchmark | 29.3 | 48.7 | 54.8 | 30.4 | |
| The velocity of variation of productivity of propylene (%/hr) | 2.7 | -3.3 | |||
By the result shown in the table 4 as seen, when adopting layered zeolite ITQ-2, from after 40 minutes after 8 hours the velocity of variation of productivity of propylene be 2.7, therefore, even in reaction for a long time, the productive rate of response matrix conversion of methanol and propylene also all maintains high level.But, when adopting ZSM-5, though the productive rate of transformation efficiency and propylene all shows high level after 40 minutes, from after 40 minutes after 8 hours the velocity of variation of productivity of propylene be-3.3, the productive rate of propylene in time prolongation and reduce.
That is to say, can prove, in embodiment 2, because the reduction of catalytic activity, so can not use this catalyzer for a long time, and in embodiment 15, the productive rate of propylene does not reduce, and can stably obtain propylene.
At this full content of introducing following application by reference, comprise its specification sheets, claims and summary: the Japanese patent application 2003-415367 that on December 12nd, 2003 submitted to, the Japanese patent application 2004-45917 that on February 23rd, 2004 submitted to, the Japanese patent application 2004-45918 that on February 23rd, 2004 submitted to, the Japanese patent application 2004-45919 that on February 23rd, 2004 submitted to, the Japanese patent application 2004-101075 that on March 30th, 2004 submitted to, the Japanese patent application 2004-153547 that the Japanese patent application 2004-134145 that on April 28th, 2004 submitted to and on May 24th, 2004 submit to.
Claims (12)
1. method for preparing propylene, this method is included in the step that under the existence of catalyzer ethene is contacted with methyl alcohol and/or dme, it is characterized in that, with respect to the ethene amount that adds reaction system, ethene amount from the reaction mixture that reaction system is discharged is reduced, and, be benchmark with moles of methanol and the duple dme mole number sum that adds reaction system, the productive rate of propylene is at least 40%.
2. the method for preparing propylene as claimed in claim 1, it is characterized in that, reaction pressure is adjusted to more than or equal to 0.1kPa to the scope less than 2MPa, so that with respect to the ethene amount that adds reaction system, ethene amount from the reaction mixture that reaction system is discharged is reduced, and, moles of methanol and duple dme mole number sum with the adding reaction system are benchmark, the productive rate of propylene is at least 40%, and, with the moles of methanol and the duple dme mole number sum that add reaction system is benchmark, the ethene amount that adds reaction system is transferred to mol ratio is at least 1 to maximum 20 scope.
3. the method for preparing propylene as claimed in claim 1 or 2 is characterized in that, is adjusted at least 0.01 hour with adding the methyl alcohol of reaction system and the weight hourly space velocity of the per unit catalyst activity component of the dme sum that is scaled methyl alcohol
-1By maximum 70 hours
-1, so that, the ethene amount from the reaction mixture that reaction system is discharged is reduced with respect to the ethene amount that adds reaction system, and, be benchmark with moles of methanol and the duple dme mole number sum that adds reaction system, the productive rate of propylene is at least 40%.
4. as each described method for preparing propylene of claim 1～3, it is characterized in that, is benchmark with moles of methanol and the duple dme mole number sum that adds reaction system, and the mol ratio that adds the ethene amount of reaction system is at least 1.8.
5. as each described method for preparing propylene of claim 1～4, it is characterized in that described catalyzer is a solid acid catalyst.
6. the method for preparing propylene as claimed in claim 5 is characterized in that, described solid acid catalyst is a zeolite.
7. the method for preparing propylene as claimed in claim 6, it is characterized in that, described zeolite is the crystallinity porous silicate of the metallic element modification except that element silicon and aluminium element in periodictable the 1st～14 family, or through the crystallinity porous aluminum phosphoric acid salt of similar modification.
8. the method for preparing propylene as claimed in claim 5, wherein said solid acid catalyst are layered zeolite.
9. as each described method for preparing propylene of claim 1～8, it is characterized in that, water is added described reaction system.
10. as each described method for preparing propylene of claim 1～9, wherein said ethene is to adopt the ethene of olefines production unit through petroleum naphtha thermolysis gained.
11. as each described method for preparing propylene of claim 1～9, wherein said ethene is that the equipment of employing preparation light alkene is the ethene of raw material gained with methyl alcohol and/or dme.
12. as each described method for preparing propylene of claim 1～9, wherein said ethene is to adopt the ethene of the equipment of preparation ethene through the ethane steam cracking gained.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003415367 | 2003-12-12 | ||
| JP415367/2003 | 2003-12-12 | ||
| JP045919/2004 | 2004-02-23 | ||
| JP045918/2004 | 2004-02-23 | ||
| JP045917/2004 | 2004-02-23 | ||
| JP101075/2004 | 2004-03-30 | ||
| JP134145/2004 | 2004-04-28 | ||
| JP153547/2004 | 2004-05-24 |
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| Publication Number | Publication Date |
|---|---|
| CN1894177A true CN1894177A (en) | 2007-01-10 |
| CN100494129C CN100494129C (en) | 2009-06-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800371044A Expired - Fee Related CN100494129C (en) | 2003-12-12 | 2004-12-13 | Method for producing propylene |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009055997A1 (en) * | 2007-10-31 | 2009-05-07 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Process of producing propylene from starting materials of ethylene and methanol (or/and dimethyl ether) |
| CN101157593B (en) * | 2007-03-07 | 2010-09-22 | 中国科学院大连化学物理研究所 | Method for producing light olefins by methanol or/and dimethyl ether |
| CN102276390A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Method for adjusting product proportion in process of preparing olefin from methanol |
| CN102421727A (en) * | 2009-05-08 | 2012-04-18 | 三菱化学株式会社 | Method for producing propylene |
-
2004
- 2004-12-13 CN CNB2004800371044A patent/CN100494129C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157593B (en) * | 2007-03-07 | 2010-09-22 | 中国科学院大连化学物理研究所 | Method for producing light olefins by methanol or/and dimethyl ether |
| WO2009055997A1 (en) * | 2007-10-31 | 2009-05-07 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Process of producing propylene from starting materials of ethylene and methanol (or/and dimethyl ether) |
| CN102421727A (en) * | 2009-05-08 | 2012-04-18 | 三菱化学株式会社 | Method for producing propylene |
| US8759598B2 (en) | 2009-05-08 | 2014-06-24 | Mitsubishi Chemical Corporation | Production process of propylene |
| CN102421727B (en) * | 2009-05-08 | 2014-10-15 | 三菱化学株式会社 | method for producing propylene |
| CN102276390A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Method for adjusting product proportion in process of preparing olefin from methanol |
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|---|---|
| CN100494129C (en) | 2009-06-03 |
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