CN105597681A - Preparation method of NCC/PVA/PVP blended carbon sponge capable of efficiently removing heavy metal ions and organic dye in water - Google Patents
Preparation method of NCC/PVA/PVP blended carbon sponge capable of efficiently removing heavy metal ions and organic dye in water Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 150000002500 ions Chemical class 0.000 title abstract description 29
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 84
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 84
- 239000000725 suspension Substances 0.000 claims abstract description 84
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 83
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 83
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 81
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000000137 annealing Methods 0.000 claims abstract description 18
- 229920002678 cellulose Polymers 0.000 claims abstract description 17
- 239000001913 cellulose Substances 0.000 claims abstract description 17
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims abstract description 10
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims abstract description 10
- 239000008108 microcrystalline cellulose Substances 0.000 claims abstract description 9
- 229940016286 microcrystalline cellulose Drugs 0.000 claims abstract description 9
- 238000010521 absorption reaction Methods 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 21
- 239000000975 dye Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000003643 water by type Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000003763 carbonization Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 238000006136 alcoholysis reaction Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 5
- 238000005057 refrigeration Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 3
- 229920000573 polyethylene Polymers 0.000 claims 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000000502 dialysis Methods 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 235000010980 cellulose Nutrition 0.000 abstract 2
- 239000000463 material Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 9
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 229960000907 methylthioninium chloride Drugs 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000002114 nanocomposite Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000628997 Flos Species 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 241001290210 Henrya Species 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical compound C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 229940077449 dichromate ion Drugs 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910021432 inorganic complex Inorganic materials 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013339 polymer-based nanocomposite Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a microwave annealing preparation method of an NCC/PVA/PVP blended carbon sponge capable of efficiently removing heavy metal ions and organic dye in water. The method includes the steps that firstly, microcrystalline cellulose is prepared into nano-crystalline cellulose suspension according to a sulfuric acid method; secondly, polyvinyl alcohol is added into the suspension obtained in the first step; thirdly, polyvinylpyrrolidone is added into the suspension obtained in the first step; fourthly, the suspension obtained in the second step and the suspension obtained in the third step are proportionally mixed and then subjected to microwave annealing treatment, and the nano-crystalline cellulose/polyvinyl alcohol/polyvinylpyrrolidone blended carbon sponge can be obtained. The blended carbon sponge prepared according to the preparation method has a stable shape, the product purity is high, and the removal rate on heavy metal ions and organic solvents is high.
Description
Technical field
The present invention relates to a kind of nano-cellulose/polyvinyl alcohol polyethylene pyrrolidones (NCC/PVA/PVP)The preparation method of carbon blended sponge, the particularly standby efficient huge sum of money in water body of removing of a kind of microwave annealing legal systemBelong to the preparation method of the NCC/PVA/PVP carbon blended sponge of ion and organic dyestuff.
Background technology
The porous carbon material that is made up of network structure mutual perforation or blind bore hole is possessing Carbon Materials characterWhen the advantage such as (as high in chemical stability, good conductivity, inexpensive), also there is specific area large etc.Feature. Therefore, porous carbon material can be applicable to isolation of purified, catalysis, optics, stored energy,The fields such as bio-separation film and nano-reactor. The macroporous structure being formed by three-dimensional net structure makes porousCarbon Materials has excellent absorption property. At present, along with going deep into of porous carbon material research, preparation porousCarbon Materials not only needs to control its mesoscopic structure, aperture and duct to be arranged, and to its micron-sized macroscopic viewPattern also has requirement. The different morphologies such as ball, fiber, rod, monocrystalline and block materials are now successfully synthesizedMesoporous carbon material. Make porous carbon materials in sewage disposal, there is important effect in water body purification field.
Polymer based nanocomposites refers to taking high polymer as matrix, with metal, inorganic non-metallic andOrganic matter nano particles etc. carry out material compound and a kind of excellent performance that obtain. This composite bothHave the advantage of high polymer itself, had both again the special attribute of nano particle, thus make its at mechanics, urgeChange, functional material (optical, electrical, magnetic, sensitivity) etc. is applied in field, even occurs brand-new performanceAnd function, for example high strength, high-modulus, high tenacity, high-fire resistance, high transparent, high conductivity,High barrier to oils and gas etc., thereby have vast potential for future development. Polymer nanocomposite composite woodMaterial can be divided into polymer/inorganic thing nano composite material and Polymer/Polymer Nanocomposites. In recent yearsNext a large amount of research concentrates on prepares the different-shape of one-component and carbon fiber, the carbon aerogels etc. of structureTo the removal of Heavy Metals in Waters ion and organic dyestuff, for multicomponent blend, nano material is with high poly-Thing blend is prepared material with carbon element research seldom. The heavy metal ion of preparation and the sorbing material of organic dyestuff at presentThere are porous fibre, graphene aerogel, carbon nano-composite fiber, starch-carbon film material etc. As by ZhaoDeng propose taking polystyrene as matrix, prepared the fiber with multiple-void structure by ElectrospinningOil is had to very high adsorption rate (JingWu, NuWang, LiWang, HuaDong, YongZhao, andLeiJingACSAppl.Mater.Interfaces, 2012,4,3207-3212); Proposed by Li etc. withCompressible graphene aerogel prepared by self-assembling method is to the removal of the organic solvent (Jihao that can be recycledLi,JingyeLi,HuMeng,SiyuanXie,BowuZhang,LinfanLi,HongjuanMa,JianyongZhangandMingYu, J.Mater.Chem.A, 2014,2,2934 – 2941; By GuoDeng preparing by the method such as microwave annealing and calcining taking cotton fiber as raw material of proposing there is porous can magneticThe carbon nano-composite fiber of property Adsorption of Heavy Metal Ions (JiahuaZhu, HongboGu, JiangGuo,MinjiaoChen,HuigeWei,ZhipingLuo,HenryA.Colorado,NarendranathYerra,DaoweiDing,ThomasC.Ho,NeelHaldolaarachchige,JackHopper,DavidP.Young,ZhanhuGuoandSuyingWei,J.Mater.Chem.A,2014,2,2256–2265)；By the propositions such as Mezzenga with starch and carbon hydridization for the preparation of the film of purifying waste water can removal heavy metal fromSon and organic solvent (SreenathBolisettyandRaffaeleMezzenga, NatureNanotechnology,2016,DOI:10.1038/NNANO.2015.310。
Microwave has been widely used in chemical field in recent years, comprises molecular sieve, radioactivity medicineOrganic reaction under synthetic and insertion reaction, the drying condition of synthetic, the inorganic complexes of thing, etc. fromSample pretreatment and catalysis etc. in daughter chemistry, analytical chemistry. In recent years, microwave method has spy because of itSpecial effect should cause the very big concern of material supply section educational circles. Compared with conventional method, microwave method has reactionSpeed is fast, reaction condition is gentle and reaction efficiency advantages of higher, and product has higher purity, narrowParticle diameter distribute and the form of homogeneous, and be suitable for being generalized in large-scale industrial production and go, thereby receivingRice material has shown good development momentum and wide application prospect in synthetic field. By propositions such as GuoPrepare by microwave annealing method taking cotton fiber as raw material have porous can magnetic absorption heavy metal fromCarbon nano-composite fiber (JiahuaZhu, HongboGu, JiangGuo, MinjiaoChen, the Huige of sonWei,ZhipingLuo,HenryA.Colorado,NarendranathYerra,DaoweiDing,ThomasC.Ho,NeelHaldolaarachchige,JackHopper,DavidP.Young,ZhanhuGuoandSuyingWei, J.Mater.Chem.A, 2014,2,2256 – 2265); But aboutNCC/PVA/PVP carbon blended sponge rarely has report, carries out the research invention of this respect, to water pollutionProcessing, and large-scale production has very important significance.
Summary of the invention
For the problem that present Heavy Metals in Waters ion and organic dyestuff exceed standard and prior art exists, thisAn object of invention has been to provide one can efficiently remove a huge sum of money in water body by microwave annealing legal system is standbyBelong to the preparation method of the NCC/PVA/PVP carbon blended sponge of ion and organic dyestuff.
According to the present inventionly remove Heavy Metals in Waters ion and have by microwave annealing legal system is standby efficientThe preparation method of the NCC/PVA/PVP carbon blended sponge of organic dye, comprises the steps:
1) sulfuric acid that is 40-70% by microcrystalline cellulose (MCC) with mass percent concentration is at 35-80 DEG CReaction temperature under process 10-80min, to prepare nano-cellulose (NCC), wherein said crystallite fibreThe mass percent 1:5-20 of dimension element and described sulfuric acid, is then dispersed in water by the nano-cellulose makingIn, under Ultrasonic Conditions, being mixed with even suspension, gained suspension is first through mechanical agitation 1-3 hour,And then further disperse 30 minutes in ultrasonic cell disrupte machine, hyperacoustic intensity is500-1200W, wherein, with respect to the nano-cellulose making of 1 weight portion, uses 100-500 weight portionDeionized water disperse, thereby make the suspension that mass percent is 0.2-1%;
2) polyvinyl alcohol (PVA) particle is added to step 1) the even suspension that obtains, make suspensionThe mass percent concentration of middle polyvinyl alcohol is 5-20%, then under ultrasonic cell disruptor, continues to divideLoose 2 hours, be mixed with suspension A;
3) polyvinylpyrrolidone (PVP) powder is added to step 1) the even suspension that obtains,The mass percent concentration that makes polyvinylpyrrolidone in suspension is 5-40%, under magnetic stirring apparatus orUnder ultrasonic cell disrupte machine, continue to disperse 2 hours, be mixed with suspension B;
4) by step 2), 3) in the suspension A that obtains and the B ratio that is 5:1 to 1:1 according to volume ratioExample is mixed to get precursor solution, adds that to account for precursor solution volume be that 1% mass concentration is 10%Sulfuric acid annealing in process under microwave can obtain having NCC/PVA/PVP carbon blended sponge, wherein saidMicrowave annealing processing is to react 5min under 600W microwave, and then it is anti-that microwave is adjusted to 900W continuationAnswer 10min.
Preferably, step 1) described in the mass percent concentration of sulfuric acid be 50-60%, further preferredFor 58-60%, be further preferably 58%; Reaction temperature is 40-60 DEG C, more preferably50-60 DEG C, is further preferably 50 DEG C; Reaction time is 30-50min, more preferably35-40min, is further preferably 35min; The mass percent of MCC and sulfuric acid is 1:8-15,More preferably 1:10-15, is further preferably 1:10.
Preferably, step 1) in respect to the nano-cellulose making of 1 weight portion, preferably use 150-300Weight portion, more preferably 200-250 weight portion, be further preferably 200 weight portions go fromSub-aqueous dispersion, is 0.33-0.66% thereby make mass percent, more preferably 0.4-0.5%, moreMore preferably 0.5% suspension.
Preferably, step 1) described in the hyperacoustic intensity of ultrasonic wave in disperseing be 700-1000W,More preferably 800-1000W, is further preferably 800W.
Preferably, step 2) described in PVA particle be weight average molecular weight be 17-22 ten thousand and alcoholysis degree approximatelyBe 88% PVA particle, more preferably PVA17-88. Described PVA particle is added to 1) instituteIn the even suspension obtaining, making the mass percent concentration of polyvinyl alcohol in suspension is 7-15%, entersOne step is preferably 8-10%, is further preferably 8%.
Preferably, step 3) described in PVP powder be that weight average molecular weight is the PVP powder of 1-7 ten thousand,Be preferably PVP powder K-30, described PVP powder added to step 1) the even suspension that obtainsIn, the mass percent concentration that makes the polyvinylpyrrolidone in suspension is 10-25%; Further preferablyFor 20-25%, be further preferably 20%.
Preferably, step 4) described in step 2), 3) in the suspension A that obtains and the mixture of BLong-pending than being 3:1 to 2:1, more preferably 7-5:3, is further preferably 7:3.
Preparation method according to the present invention, it comprises the steps:
1) getting the mass percent concentration preparing is that 58% sulfuric acid 50mL is placed in round-bottomed flask, addsEnter 5gMCC and react 35min under 50 DEG C of conditions, reacted rear product is transferred to beakerMiddlely be diluted to 800mL by deionized water and leave standstill 4h, then turn centrifugal 30min under condition 3000, thoroughlyAnalyse 24h, the NCC of the 1g that under-50 DEG C of conditions, vacuum refrigeration 36h obtains, will obtain under Ultrasonic ConditionsNCC add in 200mL deionized water and be mixed with suspension, gained suspension is again through mechanical agitation 2Hour, and then further disperse 30 minutes in the ultrasonic cell disrupte machine of 800W, finally obtain0.5% even suspension;
2) by 35gPVA particle (PVA17-88, molecular weight is 17-22 ten thousand, alcoholysis degree is about 88%)Add 300mL step 1) under Ultrasonic Conditions, be mixed with in suspension in the even suspension that obtainsThe mass percent concentration of polyvinyl alcohol is 8% PVA suspension;
3) 5gPVP powder (PVP powder K-30, molecular weight 1-7 ten thousand) is joined to 20mL step1) in the even suspension obtaining, under Ultrasonic Conditions, be mixed with the polyvinylpyrrolidone in suspensionThe mass percent concentration PVP suspension that is 20%;
4) precursor solution preparation
By step 2) the PVA suspension and the step 3 that obtain) the PVP suspension that obtains is by volumeAfter the ratio mixing and stirring of 7:3, add the mass percent concentration that accounts for mixed liquor volume 1% to be10% sulfuric acid obtains precursor solution;
5) microwave annealing
By step 4) in the precursor solution that obtains under 600W microwave, react 5min, make presoma moltenNCC, PVA and PVP reaction in liquid, and then microwave is adjusted to 900W continuation reaction 10min,Make presoma annealing carbonization obtain efficiently removing Heavy Metals in Waters ion and organic dyestuffNCC/PVA/PVP carbon blended sponge.
In preparation method according to the present invention, do not adopt any crosslinking agent.
According to another aspect of the present invention, provide one can efficiently remove Heavy Metals in Waters ionWith the NCC/PVA/PVP carbon blended sponge of organic dyestuff, described carbon blended sponge passes through above-mentioned according to thisPreparation method's preparation of invention, it is to Cr6+Absorption reached 9.3948mg/g more than.
Beneficial effect
1, according in the preparation method of NCC/PVA/PVP carbon blended sponge of the present invention, PVA and PVPAll high polymer simple and easy to get, and carbon sponge environment-friendly degradable; NCC/PVA/PVP three's blendJust can efficiently be removed the NCC/PVA/PVP carbon blended sea of Heavy Metals in Waters ion and organic dyestuffContinuous;
2, prepared according to the methods of the invention is efficiently removed Heavy Metals in Waters ion and organic dyestuffNCC/PVA/PVP carbon blended sponge has stable form, heavy metal ion and having in adsorbed water bodyRecoverable after organic dye, does not form secondary pollution to water body;
3, prepared according to the methods of the invention NCC/PVA/PVP carbon blended sponge Fourier infared spectrumShow that product is at wave number 1500cm-1Do not have peak to occur before, NCC/PVA/PVP carbon blended sponge is describedHave highly purified carbon skeleton, the product purity that microwave annealing obtains is very high;
4, the NCC/PVA/PVP carbon blended sponge that the method according to this invention is prepared is to heavy metal ionHigher with the clearance of organic solvent;
6, NCC/PVA/PVP carbon blended sponge prepared according to the methods of the invention, raw material sources are extensive,Low price, the production cost of reduction product, is beneficial to industrialization promotion and uses.
Brief description of the drawings
Fig. 1 is according to NCC/PVA/PVP carbon blended sponge preparation technology flow chart of the present invention.
Fig. 2 be the NCC/PVA/PVP carbon blended sponge of preparing according to embodiment 1 and reactant NCC,Fourier's infared spectrum figure of PVA and PVP.
Fig. 3 adsorbs potassium bichromate according to the NCC/PVA/PVP carbon blended sponge of EXPERIMENTAL EXAMPLE 1The uv-spectrophotometric spectrogram of process.
Fig. 4 adsorbs potassium bichromate according to the NCC/PVA/PVP carbon blended sponge of EXPERIMENTAL EXAMPLE 1The change in concentration of front and back.
Fig. 5 is before lead ion being adsorbed according to the NCC/PVA/PVP carbon blended sponge of EXPERIMENTAL EXAMPLE 2After change in concentration.
Fig. 6 is before mercury ion being adsorbed according to the NCC/PVA/PVP carbon blended sponge of EXPERIMENTAL EXAMPLE 3After change in concentration.
Fig. 7 is to methylene blue adsorption number according to the NCC/PVA/PVP carbon blended sponge of EXPERIMENTAL EXAMPLE 4The uv-spectrophotometric spectrogram of process.
Fig. 8 is to methylene blue adsorption number according to the NCC/PVA/PVP carbon blended sponge of EXPERIMENTAL EXAMPLE 4The change in concentration of front and back.
Fig. 9 is the porosity comparison diagram of the product that obtains according to embodiment 1,2 and 3.
Figure 10 is that the product obtaining according to embodiment 1,2 and 3 is removed heavy metal ion and organic dyestuffRate comparison diagram.
Detailed description of the invention
In preparation in accordance with the present invention, come with high polymer PVA and PVP and MCC preparationNCC, first has MCC to prepare NCC with sulfuric acid process, and then NCC is distributed in water ultrasonicUnder effect, be mixed with evenly unified suspension, then prepare respectively PVA taking NCC suspension as solventWith PVP solution, PVA solution and PVP solution are mixed under acid condition according to certain ratioPrecursor solution reacts Formed sponge under microwave, and this process is without any complex experiment equipment, noAdd any crosslinking agent, component inside forms microwave degeneration carbonization after stable network structure by self assemblyJust form the carbon sponge of high porosity, green non-pollution, technique is succinct, easy to operate, and yield is higher,That Heavy Metals in Waters ion and organic dyestuff are efficiently removed in the eco-friendly preparation of a kind of efficient quickThe preparation method of NCC/PVA/PVP carbon blended sponge.
In preparation in accordance with the present invention, described PVA particle is that molecular weight is 17-22 ten thousand and alcoholysis degreeBe about 88% PVA particle, be preferably PVA17-88. In the time that the molecular weight of PVA is too high, PVA'sPrice is higher, and cost rises, and owing to easily solidifying and being difficult for being mixed with suspension; And dividing as PVAWhen son amount is too low, although price may be cheap, because strand is too short, can not with PVP and NCCStructure has potent adsorbing three-dimensional net structure. Therefore described in preparation in accordance with the present inventionThe molecular weight of PVA particle is preferably 17-22 ten thousand.
In preparation in accordance with the present invention, described PVP powder can be K-30PVP powder, and it is heavyAverage molecular weight is about 1-7 ten thousand, comparatively suitable, and simultaneously PVPK-30 has obtained national medical administrative departmentApproval official listing, environment friendly and pollution-free.
The efficient removal Heavy Metals in Waters ion of preparing in preparation in accordance with the present invention and have an engine dyeingThe NCC/PVA/PVP carbon blended sponge of material, PVA and PVP are the production that polymer simple and easy to get isCost reduces greatly, and because PVA and PVP itself are exactly long molecular chain structure, for building carbonIn sponge, network structure is favourable, and then has promoted the absorption property of carbon sponge.
Below, will describe the present invention in detail. Before being described, should be understood that, in this theoryThe term using in bright book and appending claims should not be construed as and is limited to general sense and dictionary containsJustice, and should allow inventor suitably to define term to carry out on the basis of principle of best interpretations, rootAccording to making an explanation with the corresponding implication of technical elements of the present invention and concept. Therefore the description, proposing hereBe only preferred embodiment for purposes of illustration, be not intended to limit the scope of the invention, thus shouldWhen understand, without departing from the spirit and scope of the present invention in the situation that, can by its obtain other etc.Valency mode or improved procedure.
Embodiment 1
1) getting the mass percent concentration preparing is that 58% sulfuric acid 50mL is placed in round-bottomed flask, addsEnter 5gMCC and react 35min under 50 DEG C of conditions, reacted rear product is transferred to beakerMiddlely be diluted to 800mL by deionized water and leave standstill 4h, then turn centrifugal 30min under condition 3000, thoroughlyAnalyse 24h, the NCC of the 1g that under-50 DEG C of conditions, vacuum refrigeration 36h obtains, will obtain under Ultrasonic ConditionsNCC add in 200mL deionized water and be mixed with suspension, gained suspension is again through mechanical agitation 2Hour, and then further disperse 30 minutes in the ultrasonic cell disrupte machine of 800W, finally obtain0.5% even suspension; Can be according to document (ShanLiu, Yan-JunLiu, FuDeng, Ming-GuoMaandJingBian, RSCAdv., 2015,5,74198 – 74205) method recorded carries out.
2) by 35gPVA particle (PVA17-88, molecular weight is 17-22 ten thousand, alcoholysis degree is about 88%)Add 300mL step 1) under Ultrasonic Conditions, be mixed with in suspension in the even suspension that obtainsThe mass percent concentration of polyvinyl alcohol is 8% PVA suspension;
3) 5gPVP powder (PVP powder K-30, molecular weight 1-7 ten thousand) is joined to 20mL step1) in the even suspension obtaining, under Ultrasonic Conditions, be mixed with the polyvinylpyrrolidone in suspensionThe mass percent concentration PVP suspension that is 20%;
4) precursor solution preparation
By step 2) the PVA suspension and the step 3 that obtain) the PVP suspension that obtains is by volumeAfter the ratio mixing and stirring of 7:3, add the mass percent concentration that accounts for mixed liquor volume 1% to be10% sulfuric acid obtains precursor solution;
5) microwave annealing
Precursor solution is reacted to 5min under 600W microwave, make NCC in precursor solution, PVAWith PVP reaction, make precursor solution become thickness, and then microwave is adjusted to 900W continuation reaction10min, makes presoma annealing carbonization efficiently be removed Heavy Metals in Waters ion and organic dyestuffNCC/PVA/PVP carbon blended sponge.
Adopt Fourier's infrared spectrum to NCC, PVA, PVP and reacted NCC/PVA/PVPThe structural change of carbon blended sponge is analyzed, as shown in Figure 2. 4000-in Fourier's infrared spectrogram1500cm-1Carbon sponge does not have absworption peak to occur, illustrates that annealed precursor solution is afterwards basic only remainingCavernous carbon skeleton.
EXPERIMENTAL EXAMPLE 1: the absorption of heavy metal chromium
Adopt the NCC/PVA/PVP carbon blended sea of Ultravioblet spectrophotometer to preparation in embodiment 1Silk floss is studied the absorption property of heavy metal ion. Accurately weigh 500mg potassium bichromate with assay balanceBe dissolved in 500mL deionized water, be mixed with that to contain hexavalent chromium concentration be the molten of 372ppm (mg/L)Liquid is stand-by. Measure 40mL potassium bichromate solution in beaker with graduated cylinder, add in 1g embodiment 1 madeStandby carbon sponge, transfers to Temperature Setting and is in the shaking table of 30 DEG C, every 3min UV absorption light splittingPhotometer (TechcompUV2310) is measured once. Fig. 3 is according to Cr6+The ultraviolet spectrometry light of adsorption processDegree spectrogram, when in figure, curve is followed successively by not absorption (0min) from top to bottom, 3min, 6min, 9min,When 12min, 15min, 18min, 21min, 24min, 27min, 30min and 40min adsorbUltraviolet absorption curve, as can be seen from the results along with time lengthening, absorbance reduce, this means waterDichromate ion in body reduces gradually, and in the time adsorbing 40 minutes, absorbance changes not quite, and water body is describedIn dichromate ion substantially removed totally. Fig. 4 is prepared according to embodiment 1NCC/PVA/PVP carbon blended sponge, to change in concentration before and after potassium bichromate absorption, as shown in Figure 4, inhalesAttached front Cr6+Concentration is 372ppm, and after absorption, concentration is 0.012ppm, and clearance has reached 99.99%,The content of the Heavy Metals in Waters chromium after absorption is 0.012ppm, has almost reached the mark of a class drinking waterAccurate (GB7467-87).
EXPERIMENTAL EXAMPLE 2: the absorption of heavy metal lead
Adopt the NCC/PVA/PVP carbon blended sea of Ultravioblet spectrophotometer to preparation in embodiment 1Silk floss is studied the absorption property of heavy metal ion. Accurately weigh 170mg lead acetate with assay balance moltenIn 500mL deionized water, be mixed with and contain the solution that lead (II) ion concentration is 128ppm (mg/L)Stand-by. Measure 40mL lead acetate solution in beaker with graduated cylinder, add in 1g embodiment 1 preparedCarbon sponge, transfers to Temperature Setting and is in the shaking table of 30 DEG C, every 3min UV absorption spectrophotometricMeter (TechcompUV2310) is measured once. Result as shown in Figure 5, is adsorbed front Pb2+Concentration is128ppm, Pb after absorption2+Concentration is 0.015ppm, and clearance has reached 99.98%, water after absorptionThe content of the heavy metal lead in body is better than national standard (experiment atomic absorption spectrophotometry (chelate extractionMethod) GB7475-87 or dithizone spectrophotometry GB7470-87).
EXPERIMENTAL EXAMPLE 3: the absorption of heavy metal Hg
Adopt the NCC/PVA/PVP carbon blended sea of Ultravioblet spectrophotometer to preparation in embodiment 1Silk floss is studied the absorption property of heavy metal ion. Accurately weigh 180mg mercury chloride with assay balance moltenIn 500mL deionized water, be mixed with that to contain dimercurion concentration be that the solution of 76ppm (mg/L) is treatedWith. Measure 40mL mercuric chloride solution in beaker with graduated cylinder, add carbon prepared in 1g embodiment 1Sponge, transfers to Temperature Setting and is in the shaking table of 30 DEG C, every 3min Ultravioblet spectrophotometer(TechcompUV2310) measure once. Result as shown in Figure 6, is adsorbed front Hg2+Concentration is 76ppm,Concentration after absorption is 0.3ppm, and clearance has reached 99.6%.
EXPERIMENTAL EXAMPLE 4: the absorption of organic dyestuff
Adopt the NCC/PVA/PVP carbon blended sea of Ultravioblet spectrophotometer to preparation in embodiment 1Silk floss is studied the absorption property of organic dyestuff. Accurately weigh 6.4mg methylene blue with assay balance moltenIn 500mL deionized water, be mixed with that to contain methylene blue concentration be that the solution of 12.8ppm (mg/L) is treatedWith. Measure 40mL methylene blue solution in beaker with graduated cylinder, add in 1g embodiment 1 preparedCarbon sponge, transfers to Temperature Setting and is in the shaking table of 30 DEG C, every 3min UV absorption spectrophotometricMeter (TechcompUV2310) is measured once. Fig. 7 is according to the ultraviolet spectrometry of methylene blue adsorption number processLuminosity spectrogram, when in figure, curve is followed successively by not absorption (0min) from top to bottom, 3min, 6min, 9min,When 12min, 15min, 18min, 21min, 24min, 27min, 30min and 40min adsorbUltraviolet absorption curve, as can be seen from the results along with time lengthening, absorbance reduce, this means waterMethylene blue in body reduces gradually, and in the time adsorbing 40 minutes, absorbance changes not quite, illustrates in water bodyMethylene blue has been removed totally substantially. Fig. 8 is the NCC/PVA/PVP blend of preparing according to embodiment 1Carbon sponge is to change in concentration before and after methylene blue adsorption number, and as shown in Figure 8, before absorption, concentration is 12.8ppm,After absorption, concentration is 0.02ppm, and clearance has reached 99.84%.
Embodiment 2
1) getting the mass percent concentration preparing is that 58% sulfuric acid 50mL is placed in round-bottomed flask, addsEnter 5gMCC and react 35min under 50 DEG C of conditions, reacted rear product is transferred to beakerMiddlely be diluted to 800mL by deionized water and leave standstill 4h, then turn centrifugal 30min under condition 3000, thoroughlyAnalyse 24h, the NCC of the 1g that under-50 DEG C of conditions, vacuum refrigeration 36h obtains, will obtain under Ultrasonic ConditionsNCC add in 200mL deionized water and be mixed with suspension, gained suspension is again through mechanical agitation 2Hour, and then further disperse 30 minutes in the ultrasonic cell disrupte machine of 800W, finally obtain0.5% even suspension;
2) by 35gPVA particle (PVA17-88, molecular weight is 17-22 ten thousand, alcoholysis degree is about 88%)Add 300mL step 1) under Ultrasonic Conditions, be mixed with in suspension in the even suspension that obtainsThe mass percent concentration of polyvinyl alcohol is 8% PVA suspension;
3) 5gPVP powder (PVP powder K-30, molecular weight 1-7 ten thousand) is joined to 20mL step1) in the even suspension obtaining, under Ultrasonic Conditions, be mixed with the polyvinylpyrrolidone in suspensionThe mass percent concentration PVP suspension that is 20%;
4) precursor solution preparation
By step 2) the PVA suspension and the step 3 that obtain) the PVP suspension that obtains is by volumeAfter the ratio mixing and stirring of 7:3, add the mass percent concentration that accounts for mixed liquor volume 1% to be10% sulfuric acid obtains precursor solution;
5) tube furnace calcining carbonization
By precursor solution, in nitrogen atmosphere, carbonization 3h in 800 DEG C of condition pipe type stoves, makes presomaSolution carbonization, obtains Powdered black particle.
Embodiment 2 obtains Powdered black particle, obtain powder reason and be because NCC/PVA/PVP itBetween reaction in advance build the network structure that crosses one another, so be not spongy after calcining. AlthoughTo powdery granule, heavy metal ion and organic dyestuff are also had to certain removal effect, but clearanceBe not as high as carbon sponge clearance in embodiment 1, to calculate according to porosity, porosity is higher, and clearance is moreHeight, and be difficult for recycling.
Embodiment 3
1) getting the mass percent concentration preparing is that 58% sulfuric acid 50mL is placed in round-bottomed flask, addsEnter 5gMCC and react 35min under 50 DEG C of conditions, reacted rear product is transferred to beakerMiddlely be diluted to 800mL by deionized water and leave standstill 4h, then turn centrifugal 30min under condition 3000, thoroughlyAnalyse 24h, the NCC of the 1g that under-50 DEG C of conditions, vacuum refrigeration 36h obtains, will obtain under Ultrasonic ConditionsNCC add in 200mL deionized water and be mixed with suspension, gained suspension is again through mechanical agitation 2Hour, and then further disperse 30 minutes in the ultrasonic cell disrupte machine of 800W, finally obtain0.5% even suspension;
2) by 35gPVA particle (PVA17-88, molecular weight is 17-22 ten thousand, alcoholysis degree is about 88%)Add 300mL step 1) under Ultrasonic Conditions, be mixed with in suspension in the even suspension that obtainsThe mass percent concentration of polyvinyl alcohol is 8% PVA suspension;
3) 5gPVP powder (PVP powder K-30, molecular weight 1-7 ten thousand) is joined to 20mL step1) in the even suspension obtaining, under Ultrasonic Conditions, be mixed with the polyvinylpyrrolidone in suspensionThe mass percent concentration PVP suspension that is 20%;
4) precursor solution preparation
By step 2) the PVA suspension and the step 3 that obtain) the PVP suspension that obtains is by volumeAfter the ratio mixing and stirring of 7:3, add the mass percent concentration that accounts for mixed liquor volume 1% to be10% sulfuric acid obtains precursor solution;
5) microwave reaction
Precursor solution is reacted to 5min under 600W microwave, make NCC/PVA/PVP in precursor solutionReaction, precursor solution becomes thick;
6) tube furnace calcining carbonization
By 5) viscous liquid that obtains in nitrogen atmosphere, carbonization 3h in 800 DEG C of condition pipe type stoves,Make its carbonization, obtain carbon sponge.
Although the carbon sponge that embodiment 3 obtains also has certain going to heavy metal ion and organic dyestuffExcept effect, but clearance not as carbon sponge clearance in embodiment 1 high because embodiment 3 obtainsCarbon sponge particle porosity is high not as embodiment 1 carbon sponge, cause clearance to reduce, and fragility is frangible greatly,Also be difficult for recycling.
EXPERIMENTAL EXAMPLE 5: nitrogen adsorption/desorption test
Utilize conventional nitrogen adsorption/desorption curve negotiating BJH pore-size distribution computation model to detect embodiment 1 to 3The carbon sponge of middle preparation or the aperture of particle. Fig. 9 is the hole of the product that obtains according to embodiment 1,2 and 3Gap rate comparison diagram. The porosity of the carbon sponge of as can be seen from the figure preparing according to embodiment 1 is far above rootAccording to the porosity of the product of embodiment 2 and 3 preparation, the former is approximately 3 to 6 times of the latter, therefore basisEffectively heavy-metal ion removal and organic dyestuff etc. of carbon sponge prepared by preparation method of the present invention.
EXPERIMENTAL EXAMPLE 6: clearance contrast experiment
Test according to the method for EXPERIMENTAL EXAMPLE 1 to 4 product pair obtaining according to embodiment 2 and 3 respectivelyThe contrast of heavy metal ion and organic dyestuff rate. Figure 10 is the product obtaining according to embodiment 1,2 and 3To heavy metal ion and organic dyestuff clearance comparison diagram. As can be seen from the figure according to enforcement of the present inventionCarbon sponge prepared by the preparation method of example 1 all can reach the clearance of heavy metal ion and organic dyestuffMore than 99%, even reach 99.99%, far above the clearance of the product obtaining according to embodiment 2 and 3.
Above embodiment enumerates as the example of embodiment of the present invention, the present invention is not formedAny restriction, it will be appreciated by those skilled in the art that not departing from the scope of essence of the present invention and designAmendment all fall into protection scope of the present invention.
Claims (10)
1. an efficient nano-cellulose/polyvinyl alcohol of removing Heavy Metals in Waters ion and organic dyestuff/The preparation method of polyvinylpyrrolidone carbon blended sponge, comprises the steps:
1) sulfuric acid that is 40-70% by microcrystalline cellulose with mass percent concentration is the reaction of 35-80 DEG CAt temperature, process 10-80min, to prepare nano-cellulose, wherein said microcrystalline cellulose and described sulfuric acidMass percent 1:5-20, then the nano-cellulose making is dispersed in water, at Ultrasonic ConditionsUnder be mixed with even suspension, gained suspension is first through mechanical agitation 1-3 hour, and then ultrasonic thinIn born of the same parents' pulverizer, further disperse 30 minutes, hyperacoustic intensity is 500-1200W, wherein with respect to 1The nano-cellulose making of weight portion, with the deionized water dispersion of 100-500 weight portion, thereby makesMass percent is the suspension of 0.2-1%;
2) granule of polyvinyl alcohol is added to step 1) the even suspension that obtains, make polyethylene in suspensionThe mass percent concentration of alcohol is 5-20%, then under ultrasonic cell disruptor, continues to disperse 2 hours,Be mixed with suspension A;
3) polyvinylpyrrolidonepowder powder is added to step 1) the even suspension that obtains, make suspensionThe mass percent concentration of middle polyvinylpyrrolidone is 5-40%, under magnetic stirring apparatus or ultrasonic cellUnder pulverizer, continue to disperse 2 hours, be mixed with suspension B;
4) by step 2), 3) in the suspension A that obtains and the B ratio that is 5:1 to 1:1 according to volume ratioExample is mixed to get precursor solution, adds that to account for precursor solution volume be that 1% mass concentration is 10%Sulfuric acid annealing in process under microwave can obtain having NCC/PVA/PVP carbon blended sponge, wherein saidMicrowave annealing processing is to react 5min under 600W microwave, and then it is anti-that microwave is adjusted to 900W continuationAnswer 10min.
2. preparation method according to claim 1, is characterized in that step 1) described in sulfuric acidMass percent concentration be 50-60%, more preferably 58-60%, is further preferably 58%;Reaction temperature is 40-60 DEG C, and more preferably 50-60 DEG C is further preferably 50 DEG C; When reactionBetween be 30-50min, more preferably 35-40min, is further preferably 35min; MCC withThe mass percent of sulfuric acid is 1:8-15, and more preferably 1:10-15 is further preferably 1:10.
3. preparation method according to claim 1, is characterized in that step 1) in respect to 1The nano-cellulose making of weight portion, preferably uses 150-300 weight portion, more preferably 200-250Weight portion, the deionized water that is further preferably 200 weight portions is disperseed, thereby makes mass percentFor 0.33-0.66%, more preferably 0.4-0.5%, is further preferably 0.5% suspension.
4. preparation method according to claim 1, is characterized in that step 1) described in ultrasonicHyperacoustic intensity during wavelength-division is loose is 700-1000W, and more preferably 800-1000W, more enters oneStep is preferably 800W.
5. preparation method according to claim 1, is characterized in that step 2) described in poly-secondAlkene particle is that weight average molecular weight is that 17-22 ten thousand and alcoholysis degree are about 88% polyethylene particle, further excellentElect PVA17-88 as; Described polyethylene particle adds 1) in the even suspension that obtains, make suspensionThe mass percent concentration of middle polyvinyl alcohol is 7-15%, and more preferably 8-10% is further excellentElect 8% as.
6. preparation method according to claim 1, is characterized in that step 3) described in poly-secondAlkene pyrrolidone powder is that weight average molecular weight is the polyvinylpyrrolidonepowder powder of 1-7 ten thousand, is preferably poly-secondAlkene pyrrolidone K-30, adds step 1 by described polyvinylpyrrolidonepowder powder) obtain evenly outstandingIn turbid liquid, the mass percent concentration that makes the polyvinylpyrrolidone in suspension is 10-25%; FurtherBe preferably 20-25%, be further preferably 20%.
7. preparation method according to claim 1, is characterized in that,
Preferably, step 4) described in step 2), 3) in the suspension A that obtains and the mixture of BLong-pending than being 3:1 to 2:1, more preferably 7-5:3, is further preferably 7:3.
8. preparation method according to claim 1, is characterized in that, described preparation method comprisesFollowing steps:
1) getting the mass percent concentration preparing is that 58% sulfuric acid 50mL is placed in round-bottomed flask, addsEnter 5g microcrystalline cellulose and react 35min under 50 DEG C of conditions, reacted rear product is transferred toIn beaker, be diluted to 800mL by deionized water and leave standstill 4h, then turn centrifugal 30min under condition 3000,Dialysis 24h, the 1g nano-cellulose that under-50 DEG C of conditions, vacuum refrigeration 36h obtains, under Ultrasonic ConditionsThe nano-cellulose obtaining is added in 200mL deionized water and is mixed with suspension, gained suspension warp againMechanical agitation 2 hours, and then further disperse 30 minutes in the ultrasonic cell disrupte machine of 800W,Finally obtain 0.5% even suspension;
2) 35g granule of polyvinyl alcohol PVA17-88 is added to 300mL step 1) obtain evenly outstandingIn being mixed with suspension in turbid liquid under Ultrasonic Conditions, the mass percent concentration of polyvinyl alcohol is 8%Polyvinyl alcohol suspension;
3) 5g polyvinylpyrrolidonepowder powder K-30 is joined to 20mL step 1) obtain evenlyThe mass percent that is mixed with the polyvinylpyrrolidone in suspension in suspension under Ultrasonic Conditions is denseDegree is 20% polyvinylpyrrolidone suspension;
4) precursor solution preparation
By step 2) the polyvinyl alcohol suspension and the step 3 that obtain) polyvinylpyrrolidone that obtainsSuspension after the ratio mixing and stirring of 7:3, adds the quality that accounts for mixed liquor volume 1% by volumePercent concentration is that 10% sulfuric acid obtains precursor solution;
5) microwave annealing
By step 4) in the precursor solution that obtains under 600W microwave, react 5min, make presoma moltenNano-cellulose, polyvinyl alcohol and polyvinylpyrrolidone reaction in liquid, and then microwave is adjusted to 900WContinue reaction 10min, make presoma annealing carbonization obtain efficiently removing Heavy Metals in Waters ion andNano-cellulose/polyvinyl alcohol polyethylene pyrrolidones carbon blended sponge of organic dyestuff.
9. according to the preparation method described in any one in claim 1 to 8, it is characterized in that, described inIn preparation method, do not adopt any crosslinking agent.
10. can efficiently remove the nano-cellulose/poly-second of Heavy Metals in Waters ion and organic dyestuff for one kindEnol/polyvinylpyrrolidone carbon blended sponge, described carbon blended sponge is by appointing in claim 1 to 9Preparation method's preparation of anticipating described in one, it is to Cr6+Absorption reached 9.3948mg/g more than.
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