CN105967368A - Green and safe wastewater treatment method for methyl tin mercaptide - Google Patents
Green and safe wastewater treatment method for methyl tin mercaptide Download PDFInfo
- Publication number
- CN105967368A CN105967368A CN201610468801.XA CN201610468801A CN105967368A CN 105967368 A CN105967368 A CN 105967368A CN 201610468801 A CN201610468801 A CN 201610468801A CN 105967368 A CN105967368 A CN 105967368A
- Authority
- CN
- China
- Prior art keywords
- wastewater treatment
- methyl
- catalyst
- weight
- tin
- Prior art date
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Links
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 22
- YAHBZWSDRFSFOO-UHFFFAOYSA-L dimethyltin(2+);2-(2-ethylhexoxy)-2-oxoethanethiolate Chemical compound CCCCC(CC)COC(=O)CS[Sn](C)(C)SCC(=O)OCC(CC)CCCC YAHBZWSDRFSFOO-UHFFFAOYSA-L 0.000 title abstract 2
- 239000012528 membrane Substances 0.000 claims abstract description 144
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 131
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000002360 preparation method Methods 0.000 claims abstract description 48
- 238000001914 filtration Methods 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- IUNVCWLKOOCPIT-UHFFFAOYSA-N 6-methylheptylsulfanyl 2-hydroxyacetate Chemical compound CC(C)CCCCCSOC(=O)CO IUNVCWLKOOCPIT-UHFFFAOYSA-N 0.000 claims abstract description 28
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical compound C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 98
- -1 Methyl stannum Chemical compound 0.000 claims description 50
- 239000000654 additive Substances 0.000 claims description 35
- 230000000996 additive effect Effects 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 10
- 235000014121 butter Nutrition 0.000 claims description 8
- 230000026030 halogenation Effects 0.000 claims description 8
- 238000005658 halogenation reaction Methods 0.000 claims description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 8
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical group CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 239000003444 phase transfer catalyst Substances 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical class 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 208000035126 Facies Diseases 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- CZRDZAGTSCUWNG-UHFFFAOYSA-M chloro(dimethyl)tin Chemical compound C[Sn](C)Cl CZRDZAGTSCUWNG-UHFFFAOYSA-M 0.000 claims description 5
- 238000012163 sequencing technique Methods 0.000 claims description 5
- 238000005292 vacuum distillation Methods 0.000 claims description 5
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- 239000004567 concrete Substances 0.000 claims description 2
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 23
- 239000002351 wastewater Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000033558 biomineral tissue development Effects 0.000 abstract 1
- 238000009295 crossflow filtration Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 210000000433 stratum disjunctum Anatomy 0.000 description 103
- 239000011248 coating agent Substances 0.000 description 37
- 238000000576 coating method Methods 0.000 description 37
- 239000002002 slurry Substances 0.000 description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- 102000010637 Aquaporins Human genes 0.000 description 25
- 108010063290 Aquaporins Proteins 0.000 description 25
- 239000003921 oil Substances 0.000 description 23
- 239000003610 charcoal Substances 0.000 description 22
- 239000002904 solvent Substances 0.000 description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 21
- 239000000463 material Substances 0.000 description 21
- 239000011148 porous material Substances 0.000 description 19
- 241001271907 Baphia racemosa Species 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 239000002817 coal dust Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 18
- 239000008187 granular material Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 239000011230 binding agent Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000011162 core material Substances 0.000 description 10
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 108091006146 Channels Proteins 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- 230000004907 flux Effects 0.000 description 8
- 238000009423 ventilation Methods 0.000 description 8
- 235000013162 Cocos nucifera Nutrition 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 6
- 244000060011 Cocos nucifera Species 0.000 description 6
- 241000270295 Serpentes Species 0.000 description 6
- 235000012211 aluminium silicate Nutrition 0.000 description 6
- 239000000440 bentonite Substances 0.000 description 6
- 229910000278 bentonite Inorganic materials 0.000 description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 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 6
- 239000000787 lecithin Substances 0.000 description 6
- 229940067606 lecithin Drugs 0.000 description 6
- 235000010445 lecithin Nutrition 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 239000004575 stone Substances 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 150000004645 aluminates Chemical class 0.000 description 5
- 230000033228 biological regulation Effects 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 4
- 239000011807 nanoball Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229920006335 epoxy glue Polymers 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- QSLPNSWXUQHVLP-UHFFFAOYSA-N $l^{1}-sulfanylmethane Chemical compound [S]C QSLPNSWXUQHVLP-UHFFFAOYSA-N 0.000 description 1
- IRDJCBNSDNPDSA-ZOKJKDLISA-H (Z)-but-2-enedioate methyltin(3+) Chemical compound C[Sn+3].C[Sn+3].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O IRDJCBNSDNPDSA-ZOKJKDLISA-H 0.000 description 1
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 1
- 241000737241 Cocos Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 230000001166 anti-perspirative effect Effects 0.000 description 1
- 239000003213 antiperspirant Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical compound [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical group [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- QZQIWEZRSIPYCU-UHFFFAOYSA-N trithiole Chemical compound S1SC=CS1 QZQIWEZRSIPYCU-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/226—Compounds with one or more Sn-S linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/06—Tubular membrane modules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a wastewater treatment method for organic tin substances, in particular to a green and safe wastewater treatment method for methyl tin mercaptide. The green and safe wastewater treatment method comprises the following steps: (1) performing tin mineralization; (2) synthesizing, namely, adding an obtained methyl tin chloride aqueous solution into isooctyl thioglycolate, adding a second catalyst, stirring for a reaction for 0.2-0.4 hour at 5-15 DEG C, further adding an alkali liquid, continuously stirring for a reaction till the pH value of the reaction system is 7-9, and heating to 60-70 DEG C for a reaction; (3) washing with water; (4) distilling. A process for treating wastewater generated in the preparation process comprises a carrier type membrane module filtering procedure and an activated carbon filter oil removing procedure. The process comprises the following steps: (1) feeding the wastewater into a carrier type membrane module via a circulation pump from a raw water tank; (2) implementing the carrier type membrane module filtering procedure in a cross flow filtration mode; (3) implementing the activated carbon filter oil removing procedure in a dead end filtration mode. The wastewater treatment method provided by the invention has the advantages of low cost and high treatment efficiency.
Description
Technical field
The present invention relates to the method for wastewater treatment of a kind of organic tin material, particularly relate to the methyl sulfur of a kind of green safety
The method of wastewater treatment of alcohol stannum.
Background technology
Organic tin compound is used in polyvinyl chloride resin and makees stabilizer oneself has many patents, as United States Patent (USP) 3222317,
3396185 etc., mainly butyl tin and tin octylate, because propyl group stannum scent of, and ethyl stannum is poisonous and is replaced.
The main kind of organotin has three series such as monoalkyltin, double tin alkyl and trialkyltin, wherein three alkane
Base stannum series toxicity is the strongest, it is impossible to use as stabilizer;Monoalkyltin has monomethyl stannum, Monobutyltin, single tin octylate etc.;Double
Tin alkyl has stannous methide, dibutyl tin, dioctyl tin etc..At present, the own PVC packed in medicine food through given application of European Union
Material prohibits the use of butyl tin and tin octylate series, and methyl stannum series is still widely used in due to its distinctive character
In various high-grade PVC product.
Methyl stannum (SM501) on market is mainly containing 20% tri-thiol 2-ethyl hexyl ethanoate methyl stannum and 80% 2 at home
Isooctyl thioglycolate stannous methide, its Theil indices is 19. 4, in the actual course of processing, this methyl stannum on market
Can move to surface from the inside of goods, finally separate out from product surface, form speckle flower, have impact on the quality of goods, here it is
So-called ooze out (or weighing up antiperspirant);It addition, in the course of processing, the easy roll banding of batch, release property, lubricity are poor, are unfavorable for
The Continuous maching of product produces.
CN102503972B (2015-6-17) discloses a kind of Methyltin maleate and preparation method thereof, but how
Prepare and still have much room for improvement on the Methyl stannum mercaptide stabilizer of the environmental protection that Theil indices reduces, thermal stability is good.Meanwhile, it is prepared
During produce process for treating oil-containing waste water be also required to improve.
Summary of the invention
It is an object of the invention to provide the Methyl stannum mercaptide of the green safety that a kind of Theil indices reduces, thermal stability is good
Method of wastewater treatment.
The above-mentioned technical purpose of the present invention has the technical scheme that the methyl of a kind of green safety
The method of wastewater treatment of tin mercaptides, the preparation of Methyl stannum mercaptide comprises the following steps:
(1) stannum: metallic tin and the first catalyst are put in reactor, then passes to chloromethanes and carry out halogenation, add again
Distribution is after agent carries out stannum reaction, distills and accepts gas temperature at 150-230 DEG C of interior fraction, then obtaining by absorbing pure water
Methyl tin chloride aqueous solution；Described methyl alkene chloride includes dimethyltin chloride and monomethyl tin trichloride；
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, adds the second catalyst, in temperature
At spending 5-15 DEG C, stirring reaction 0.2-0.4 hour, adds the continuously stirred reaction of alkali liquor until pH value of reaction system reaches 7-9,
Then heat to 60-70 DEG C, react 1-1.5 hour, static, lower the temperature, be layered；
Described metallic tin, chloromethanes, reallocation agent, the mol ratio of isooctyl thioglycolate are 1:(1.5-2): (0.2-0.5):
(3-4)；
(3) washing: separate organic facies and wash 1-2 time；
(4) distillation: obtain Methyl stannum mercaptide after vacuum distillation drying；
The waste water treatment process produced in preparation process includes carrier type membrane module filtration stage and active carbon filter oil removing rank
Section, concrete technology is as follows:
(1) carrier type membrane module is injected by raw water box through circulating pump；
(2) carrier type membrane module filtration stage is carried out in cross flow filter mode, and crossflow velocity is 0.1-5m/s, and transmembrane pressure is
0.01-0.3MPa, membrane module filtering accuracy is 0.001-100 micron, and recycle ratio is 80-99%；
(3) the active carbon filter oil removing stage is carried out in dead-end filtration mode, and filtering velocity is 3-5m/s.
The Methyl stannum mercaptide finally obtained is (CH3)2Sn(SCH2CO2C8H17)2(stannous methide) and CH3Sn
(SCH2CO2C8H17)3The mixture of (monomethyl stannum), wherein the quality accounting of stannous methide is 40-60%.
The present invention uses specific stannum, synthesis technique, especially controls distillation and accepts gas temperature at 150-230 DEG C
Interior fraction, is more beneficial for the carrying out of follow-up synthetic reaction, makes finally prepd Methyl stannum mercaptide material as stabilizer for plastics
Stablizing effect more preferable.
Product of the present invention has high transparent, weatherability, the compatibility and resistance to volatilization precipitation property, and avirulence, high heat stability
Property is good, and low tin content, the thermostable effect of the methyl stannum of this low tin content is better than existing methyl stannum, for final PVC
Goods to reach same stablizing effect, and the addition of Methyltin stabiliser will be less, just can reduce stannum consumption further,
Reduce the production cost of client terminals eventually.
The deficiencies such as, product water water quality low for existing oil removing process oil removal efficiency is unstable, inventor uses carrier type film group
The method that part filtration oil removing and active carbon filter oil removing combine is solved, carrier type membrane module single carrier type membrane module
Most of ferrum in waste water and greasy dirt can be filtered and remove by filtration, and=activated carbon filters can absorb single carrier type membrane module
Filter the most of greasy dirt produced in water, filter and produce water and meet the standard of make-up water and it is with low cost.Therefore, inventor uses load
Body formula membrane module filters and activated carbon filters the mode combined and processes waste water.
For reducing the waste water impact to carrier type membrane module, inventor have employed cross-flow endless form and filters, therefore film group
Part transmembrane pressure is little, produces Water transport resistance little, improves the work efficiency of membrane module, thus low to water water quality requirement, water resistant
Body impact capacity is strong.Different from carrier type membrane module filter type, inventor uses dead-end filtration side at activated carbon filtration stage
Formula carries out filtering oil removing, uses dead-end filtration mode can farthest remove greasy dirt in water, it is ensured that water produced water quality.
As preferably, described first catalyst is that quaternary ammonium salt-type phase transfer catalyst and dimethyl sulfide are according to molal weight
Mixture than 1:2-3 composition；Described second catalyst is that phthalic acid dibutyl ester and dimethyl sulfoxide are according to molal weight ratio
The mixture of 1:1-4 composition.
Specific first catalyst of the present invention and the second catalyst is used to be conducive to the reaction of halogenation, stannumization and follow-up conjunction
Become the carrying out of reaction, make finally prepd methyl stannum material more preferable as the stablizing effect of stabilizer for plastics.
As preferably, described step (1) stannum specifically includes and puts in pressure acid-resistant reacting kettle by metallic tin and catalyst,
Then pass to chloromethanes at a temperature of 150-170 DEG C, heat mix homogeneously, after carrying out halogenation 0.2-0.4h, add and divide again
Ingredients and be warmed up to 235-245 DEG C, be forced into 0.5-0.8MPa carry out stannumization react 1-2 hour.
Use the present invention specific stannum method to be conducive to the carrying out of follow-up synthetic reaction, make finally prepd methyl mercaptan
Stannum material is more preferable as the stablizing effect of stabilizer for plastics.
As preferably, described quaternary ammonium salt phase catalyst is that tetrabutyl ammonium bromide, tetrabutyl chlorination are by, tetrabutyl hydrogen sulfate
Ammonium or tri-n-octyl methyl ammonium chloride.
As preferably, described reallocation agent is butter of tin.
As preferably, the weight of described first catalyst accounts for the 1-3% of metallic tin weight.
As preferably, the weight of described second catalyst accounts for the 6-9% of isooctyl thioglycolate weight.
As preferably, in described step (2), the mass fraction of alkali liquor is 10-20%.
As preferably, in synthesis step, in the addition continuously stirred reaction of alkali liquor until pH value of reaction system reaches 7-9,
Then, during heating up, add first solid additive of the 1-3% accounting for isooctyl thioglycolate weight according to sequencing and account for
Second solid additive of the 3-6% of isooctyl thioglycolate weight.
As preferably, the particle size range of the first solid additive is 0.8-5 micron；Wherein, the granule of 0.8-1 micron accounts for institute
State the 20-40% of the first solid additive gross weight；The granule of 1-2 micron accounts for the 10-30% of described first solid additive gross weight；Remaining
Amount is the granule of 3-5 micron；
Described first solid additive is following formula I polymer, and wherein Mw is 6.10 × 106, Mn is 2.0 × 106, molecular weight divides
Cloth index is 3.1:
I
Described second solid additive be the molybdenum disulfide nano ball of particle diameter 10-20 nanometer with the regulation grain of particle diameter 6-9 micron by
Mixture according to mass ratio 1:2-5 composition.
Different-grain diameter and the first solid additive of kind and the second solid additive increase Methyl stannum mercaptide stability,
While reducing Theil indices, moreover it is possible to give Methyl stannum mercaptide more preferable resistance to volatilization precipitation property.
As preferably, described carrier type membrane module includes that film core, film core periphery are surrounded by shell；Described shell top and the bottom are provided with
Upper and lower port, wherein upper port is connected with dense water outlet pipe and lower port is connected with raw water box outlet pipe；Shell side is provided with
Filter out the mouth of a river and be connected with active carbon filter water inlet by pipeline.
As preferably, described film core is inorganic carbon membrane film core, and it includes main body, filtration channel, product aquaporin and guiding gutter.
Described main body is the supporter of membrane filtration；Described filtration channel is for be in a row distributed in main body, and often row's filtration channel is parallel to each other,
And along main body longitudinally through main body；Produce aquaporin to be the most in a row distributed in main body and along main body longitudinal extension, adjacent two
Being spaced 1-10 between scheduling aquaporin and arrange filtration channel, filtration channel is parallel to each other with producing aquaporin；Guiding gutter is opened in main body side
On wall and through main body, it is being spaced with same scheduling aquaporin along main body longitudinal direction, is collecting the mistake produced in aquaporin
Drainage.Inorganic carbon film is silicon carbide material, and heat resistance is good, is suitable for the condensed water in high temperature that treatment temperature is high；Additionally, it is selected
The contact angle of inorganic carbon membrane film core material is only 0.4 °, and oil rub resistance ability is good.
As preferably, described filtration channel inwall is also assembled with filter course.
As preferably, described carrier type membrane module filters condensing water temperature and is 50-120 DEG C.Carrier type membrane module is crossed and is filtered
Oil and the condensed water in high temperature that combines of active carbon filter oil removing degrease mode to oil content in the temperature of condensed water in high temperature, water
Restriction scope all compare extensively, it is adaptable to all kinds of condensed water in high temperature oil removal process.
As preferably, described carrier type membrane module filtering accuracy is 0.01-3 micron.Carrier type membrane module filters needs and goes
Except the most of greasy dirt in water, ferrum and other magazines, the raising of filtering accuracy contributes to lifting carrier formula membrane module filter capacity,
Remove the removal of impurity and greasy dirt to greatest extent, promote and produce water water quality.
As preferably, it is 0.01 ~ 0.25MPa that described carrier type membrane module filters transmembrane pressure.
As preferably, in described active carbon filter, activated carbon used is cocoanut active charcoal or active fruit shell carbon or honeycomb is lived
Property charcoal, granularity is 8-30 mesh, more preferably 16-24 mesh.Activated carbon granule micropore is numerous, specific surface area is huge, therefore
There is the strongest physical absorption ability.Different types of activated carbon is otherwise varied to the absorbability of greasy substances, wherein with coconut palm
Shell activated carbon adsorption performance is optimum.Removed in view of ferrum all loaded body formula membrane modules filtration most of in condensed water in high temperature and only had
Greasy dirt content slightly exceeds standard, and inventor selects cocoanut active charcoal, active fruit shell carbon and the honeycomb stronger to greasy dirt absorbability
Activated carbon, preferably cocoanut active charcoal.It addition, have some oxygen-containing functional groups on activated carbon surface non-crystallized part, by charcoal bed
Organic pollution also effectively can be adsorbed by activated carbon.
As preferably, described carrier type membrane module is flat inorganic carbon membrane assembly, and it includes the flat of laid out in parallel
Inorganic carbon membrane and for seal described inorganic carbon membrane two ends and for collect produce water termination；
It is provided with multiple hollow duct running through diaphragm in the lamina membranacea of described flat inorganic carbon membrane or diaphragm；
Described flat inorganic carbon membrane is the rectangular tabular of cross section or laminated structure；
The hollow duct running through lamina membranacea or diaphragm arranged in described flat inorganic carbon membrane mutually in parallel and be uniformly distributed, in
Empty flow channel cross-section is rectangle, square, circular or other shape.
Using the flat inorganic carbon membrane assembly of present configuration, have flux high, contamination resistance is strong, to the pre-place that intakes
The features such as reason requires low, easily cleans, film length in service life.Can be as common filtration or membrane bioreactor etc..
As preferably, described flat inorganic carbon membrane includes supporter and stratum disjunctum；
The supporter of described inorganic carbon membrane is to be made up of the carbofrax material with larger aperture；The stratum disjunctum of described inorganic carbon membrane
It is the outside at lamina membranacea or diaphragm, the filter course being made up of carbofrax material.
Supporter aperture is generally higher than 50 microns, and the preferably aperture of supporter part is more than 100 microns.
Stratum disjunctum is coated on supporter by secondary painting method, according to pore size filter needs, can carry out once or
Repeatedly coat.Stratum disjunctum thickness is the least, have less pore size filter and narrow pore-size distribution.
It is highly preferred that stratum disjunctum thickness is 0.05 ~ 1 micron；
Stratum disjunctum filtering accuracy includes ultrafiltration and microfiltration scope, pore diameter range 20nm ~ 10 micron；At pore size filter more than 1 micron
Time, stratum disjunctum is to be completed by primary coating；
When pore size filter is less than 1 micron, stratum disjunctum is by twice or repeatedly to have coated, and first coats on supporter and has
The filter course of 1 micron pore size, is then coated with one layer of filter course with requirement pore size filter on this filter course.
It is highly preferred that stratum disjunctum thickness is 0.1 ~ 0.5 micron.
Supporter and stratum disjunctum two parts use commaterial, and after high-temperature process, two parts become same phase.By
Being commaterial in stratum disjunctum and supporting layer, both thermal coefficient of expansions are identical, thus avoid stratum disjunctum and supporting layer
Between the problem of stripping damage.
The inorganic carbon membrane of the present invention have employed composite inorganic Carbon Materials, has extremely low water contact angle (0.3 °), is known
Minima in all membrane materials (including organic film material, inorganic material film and metal membrane material), the parent of the most inorganic carbon membrane material
Aqueous is best, and contamination resistance is the highest.Meanwhile, by manufacturing process control, the porosity diaphragm more than 45% can be prepared,
The processing flux making inorganic carbon membrane is high, can reach more than 5 times of ceramic membrane.These special performances so that it is containing greasy dirt
In water treatment applications, demonstrate unique advantage, reduce the cost of investment of film, solve in existing technique organic membrane and
The problem that metal film exists in terms of technology or Technological Economy.
Membrane aperture is determined by stratum disjunctum, and inorganic carbon membrane is by unique paint-on technique, and the most different chargings is suitable
Sequence and ladder are dried, and this guarantees and are precisely controlled membrane aperture, make it have membrane aperture and the narrowest aperture accurately
Distribution.So, the most fundamentally ensure that the control to float size.Meanwhile, inorganic carbon membrane structure is designed with
Integrated module formula designs, and the structure design of this uniqueness has high integration and excellent sealing structure, the most also pole
The earth improves the bulk strength of film, and these features are that the long period of film, operation stable and up to standard provide guarantee.
As preferably, described stratum disjunctum thickness is 0.05 ~ 1 micron；
Described stratum disjunctum thickness and supporting layer thickness are than for 1:50-100；Stratum disjunctum filtering accuracy includes ultrafiltration and microfiltration scope,
Pore diameter range 20nm ~ 10 micron；
Stratum disjunctum is formed by repeatedly coating, and the aperture being consequently formed supporting layer, stratum disjunctum internal layer and stratum disjunctum outer layer gradually becomes
Little bore diameter gradient.The gross thickness of supporting layer, stratum disjunctum internal layer and stratum disjunctum outer layer is filter course thickness.
The flat inorganic carbon membrane of described laid out in parallel is provided with the product aquaporin of parallel distribution, produces aquaporin cross section permissible
Being square, rectangle, circle, ellipse and other polygon, producing aquaporin cross sectional shape on a diaphragm can be identical,
It can also be difformity.
As preferably, it is 1:1.5-20 that described diaphragm thickness and flat inorganic carbon membrane produce aquaporin height ratio, optimizes
Ground ratio is 1:2-10.
Stratum disjunctum, through repeatedly coating, thus can get the aperture of supporting layer, stratum disjunctum internal layer and stratum disjunctum outer layer gradually
The bore diameter gradient diminished；On the one hand ensure that membrane filtration efficiency and flux, and film backwash effect, i.e. flux recovery rate are high,
On the other hand improve filtering accuracy further, make inorganic carbon membrane have membrane aperture and the narrowest pore-size distribution accurately.So,
The most fundamentally ensure that the control to float size.Inventor finds, flat inorganic carbon membrane diaphragm thickness
Control proper with described product aquaporin height ratio, diaphragm life-span and assembly life-span can be made all to be improved.Flat inorganic charcoal
If film diaphragm thickness and described product aquaporin height ratio are too big, then filter membrane thickness is excessive, and producing water resistance increases, and flux drops
Low；If this ratio is the least, the most inorganic carbon membrane diaphragm mechanical strength reduces, and affects service life.Simultaneously control stratum disjunctum thickness with
The ratio of supporting layer thickness and produce aquaporin height and described flat inorganic carbon membrane thickness proportion, can make membrane ruggedness reach
Preferably demand, and make diaphragm and membrane module designs be more conducive to solve filtering film component dirt to block up problem and cleaning problem simultaneously.
Inorganic carbon membrane have employed membrane material and the membrane structure of uniqueness.Membrane material is a kind of novel inorganic carbon composite, should
Material has good hydrophilic property, and porosity is high, and chemical stability and heat stability are high, intensity and abrasion resistance properties high.Nothing
Machine carbon membrane is a kind of anisotropic membrane, and membrane body includes film top layer (stratum disjunctum) and macropore carrier (supporting layer) two parts, two parts
Have employed commaterial, after high-temperature process, become inorganic carbon membrane.Owing to stratum disjunctum and supporting layer are commaterials, high
Temperature processes and makes both be integrally forming, and both thermal coefficient of expansions are identical, thus avoids stratum disjunctum and breaks with supporting splitting
Bad problem.Owing to chemical stability and the corrosion resistance of membrane material are high, thus overcome the film caused due to corrosion
The problem that integrity violations and strainability decline.
The inorganic carbon membrane of the present invention have employed composite inorganic Carbon Materials, has extremely low water contact angle (0.3 °), is known
Minima in all membrane materials (including organic film material, inorganic material film and metal membrane material), the parent of the most inorganic carbon membrane material
Aqueous is best, and contamination resistance is the highest.Meanwhile, by manufacturing process control, the film group with 45% porosity can be prepared
Part so that the processing flux of inorganic carbon membrane is high, can reach more than 5 times of ceramic membrane.These special performances so that it is at oil-containing
In sewage disposal application, demonstrating unique advantage, the cost of investment reducing film solves organic membrane in existing technique
The problem existed in terms of technology or Technological Economy with metal film.
As preferably, the preparation process of described supporting layer is:
(1) dispensing: by certain weight ratio by two kinds of varigrained sic powders, binding agent and water, mix in a mixer
0.1-5 hour, obtain pug；
(2) by prepared pug by extruder for shaping, extrudate size is determined had by cross-head mould
There is certain overall dimensions and produce the blank of aquaporin size；
(3) prepared blank is dried 0.5-24 hour under room temperature ventilation condition；
(4) blank after drying at room temperature is put in calcining furnace, in 24 hours, temperature is increased to 2000 ~ 2400 DEG C, and
Keep 1 ~ 10 hour at a temperature of this, then in 24 hours, cool the temperature to room temperature, obtain film supporting layer.
As preferably, the preparation process of described stratum disjunctum is:
(1) by having the sic powder of certain particle size, binding agent and water mixing, slurry is made；
(2) film support lateral surface is uniformly coated gained slurry；
(3) lamina membranacea after coating is dried 0.5-24 hour under room temperature ventilation condition；
(4) dried lamina membranacea is put in calcining furnace, in 24 hours, temperature is increased to 1800 ~ 2400 DEG C, and temperature at this
The lower holding of degree 1 ~ 10 hour, then cooled the temperature to room temperature in 24 hours, obtains film and has the most right of supporting layer and filter course
Claim diaphragm.
The preparation process (2) of stratum disjunctum can use various painting method, such as spraying, blade coating, dip-coating etc..Can once be coated with
Cover, it is also possible to repeatedly coat.
Carbon membrane formula of the present invention by: carborundum, binding agent, water and surface modifier form, wherein:
Binding agent: use polymer adhesive, it is preferred to use TPO binding agent, such as polyethylene, polypropylene etc..
Surface modifier: with hydrophilic group organic solvent, such as ethanol, glycerol etc..
Polyolefin is widely used in industrial every field with its light weight, inexpensive and agent of low hygroscopicity.But due to it
Nonpolar, surface can low result in its dyeability, cohesive, hydrophilic, antistatic behaviour and with other high molecular polymers
Or the poor compatibility of inorganic filler.The present invention uses polyolefin as binding agent, introduces again the surface modifier of band hydrophilic group,
Take on the crane span structure effect between water and polyolefin-based adhesive, improve the intermiscibility of masking batch system of the present invention, the most both protected
Hold polyolefin polymer binding agent light weight, the inexpensive and advantage of agent of low hygroscopicity, in turn ensure that system intermiscibility, thus ensure this
Invent that inorganic carbon membrane supporter is homogeneous, mechanical strength is secure；
Membrane aperture is determined by stratum disjunctum, inorganic carbon membrane by unique paint-on technique, the most different charging sequence and
Ladder is dried, and this guarantees and is precisely controlled membrane aperture, makes it have membrane aperture and the narrowest pore-size distribution accurately.
So, the most fundamentally ensure that the control to float size.Meanwhile, inorganic carbon membrane structure has been designed with integrated
Modular designs, the structure design of this uniqueness has high integration and excellent sealing structure, the most greatly carries simultaneously
The high bulk strength of film, these features are that the long period of film, operation stable and up to standard provide guarantee.
As preferably, the coating preparation of described stratum disjunctum is rear in described support body layer obtains primary inorganic carbon membrane, described nothing
The preparation of machine carbon membrane includes sintering inorganic for described primary carbon membrane, and sintering is specifically with the ramp of 5-15 DEG C/min to 500-
550 DEG C and be incubated 0.3-0.5h, to 800-1000 DEG C with the ramp of 10-20 DEG C/min and it is incubated 0.5-0.8h and obtains the most again
Obtain inorganic charcoal Flat Membrane finally.
Control sintering process further, it is possible to reach more preferable film properties: effectively operating flux can reach traditional ceramics film
More than 5 times, the contact angle of top layer membrance separation layer and water is only up to 0.3 °, good hydrophilic property, and oil resistant class pollution capacity is strong, water inlet
Middle float and oil pollutant can reach more than 10mg/L；The cross flow filter mode using low crossflow velocity is carried out at filtration
Reason, is effectively prevented from oil pollution and carrys out the impact that film itself is caused by water slug, and filtering accuracy is high, suspended solids particle diameter
Intermediate value≤1 micron.
As preferably, described coating liquid solvent also includes 3-5 weight portion silane coupler or aluminate coupling agent.
As preferably, described coating liquid solvent also includes 0.6-1.5 weight portion irgasfos 168.
As preferably, described supporting layer and/or stratum disjunctum consisting of by weight:
Aggregate: coal dust 42-48 part, phenolic resin 12-14 part, white carbon 23-28 part, bentonite 5-9 part, burn Kaolin 4-8 part；
Pore former: camwood knag 0.5-1 part, snake stone powder 0.3-0.8 part；
Additive: copper nitrate 1.2-1.6 part, silicon dioxide that dimethyl two sample is silane-modified or fatty acid modified calcium carbonate
2.5-3.2 part；
Dispersant: lecithin 0.8-1.2 part.
It is highly preferred that the preparation process of described supporting layer and/or stratum disjunctum is:
(1) dispensing: by weight preparation white carbon 15-20 part, coal dust 26-28 part, camwood knag 0.6-0.8 part；
(2) coating liquid solvent preparation: glycerol, ethylene glycol and BDO 11-14:10-15:20-26 by volume is claimed
Amount mixing；
(3) stratum disjunctum slurry preparation: described coal dust 26-28 part is initially charged in described coating liquid solvent mixing 2-4min, then
Described camwood knag 0.6-0.8 part is added mixing 1-3min, finally described white carbon 15-20 part is added mixing 8-12min,
To uniform stratum disjunctum slurry；
(4) stratum disjunctum slurry coating: by described stratum disjunctum slurry even application in described support body layer, then first at 75-85
DEG C dry 3-4h, then 130-140 DEG C dry 1.5-2h obtain stratum disjunctum.
It is highly preferred that described coating liquid solvent also includes 3.5-4.5 weight portion silane coupler or aluminate coupling agent；
Described coating liquid solvent also includes 0.9-1.1 weight portion irgasfos 168.
It is highly preferred that carry out sealing and consolidating by epoxy glue, Polyurethane, glass cement between described inorganic carbon membrane and termination
Fixed.
Figure of description
Fig. 1 is the present invention inorganic charcoal Flat Membrane one schematic diagram；
Fig. 2 is the present invention inorganic charcoal Flat Membrane one schematic diagram；
Fig. 3 is the present invention inorganic charcoal Flat Membrane one schematic diagram；
Fig. 4 is the flat inorganic carbon membrane component diagram of the present invention；
Fig. 5 is the present invention inorganic charcoal Flat Membrane internal structure one schematic diagram；
Fig. 6 is the present invention inorganic charcoal plate film assembly internal structure one schematic diagram；
Fig. 7 is the present invention inorganic charcoal plate film assembly internal structure one schematic diagram；
Fig. 8 is the present invention inorganic charcoal plate film assembly one schematic diagram；
Fig. 9 is the schematic flow sheet of a kind of preparation technology of the present invention inorganic charcoal Flat Membrane supporting layer.
Figure 10 is a kind of condensed water in high temperature oil removing process flow chart.
Figure 11 is carrier film component diagram；
Figure 12 is film core schematic perspective view.
Detailed description of the invention
As shown in Fig. 1-Fig. 9, flat inorganic carbon membrane assembly includes the inorganic carbon membrane of laid out in parallel and inorganic for sealing
Carbon membrane two ends and for collect produce water termination；It is provided with multiple hollow flow running through diaphragm in the lamina membranacea of inorganic carbon membrane or diaphragm
Road；Inorganic carbon membrane is the laminated structure that cross section is rectangular；Inorganic carbon membrane includes supporting layer and stratum disjunctum.Inorganic carbon membrane and termination
Between seal by epoxy glue, Polyurethane, glass cement and fix.Product aquaporin in assembly can be square, circular
Or hexagon.
As shown in figs. 10-12, carrier type membrane module includes that film core 1, film core 1 periphery are surrounded by shell 2；Shell 2 top and the bottom set
Having upper and lower port, wherein upper port 3 is connected with dense water outlet pipe 6 and lower port 4 is connected with raw water box outlet pipe 5；Shell 2 side
Face is provided with and filters out the mouth of a river 7 and be connected with active carbon filter water inlet by pipeline.Film core 1 is inorganic carbon membrane film core, it
Including main body 11, filtration channel 12, produce aquaporin 13 and guiding gutter 14.
Embodiment one
The preparation method of the Methyl stannum mercaptide of green safety, comprises the following steps:
(1) stannum: metallic tin and catalyst are put in pressure acid-resistant reacting kettle, then passes to chloromethanes at a temperature of 150 DEG C
Heating mix homogeneously, after carrying out halogenation 0.2h, adds reallocation agent butter of tin and is warmed up to 235 DEG C, is forced into
0.5MPa carries out stannumization and reacts 1 hour, then, distills and accepts gas temperature at 150 DEG C of interior fractions, then using absorbing pure water
Obtain methyl tin chloride aqueous solution；
Methyl alkene chloride includes dimethyltin chloride and monomethyl tin trichloride；First catalyst is quaternary ammonium salt phase transfer
The mixture that catalyst and dimethyl sulfide form than 1:2 according to molal weight；The weight of the first catalyst accounts for metallic tin weight
1%.
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, adds the second catalyst,
Stirring reaction 0.2 hour at temperature 5 DEG C, adds the continuously stirred reaction of alkali liquor that mass fraction is 10% until reaction system
PH value reaches 7, then heats to 60 DEG C, reacts 1 hour, static, lower the temperature, be layered；
The mixing that second catalyst is quaternary ammonium salt-type phase transfer catalyst and dimethyl sulfoxide forms than 1:1 according to molal weight
Thing；The weight of the second catalyst accounts for the 6% of isooctyl thioglycolate weight；
Metallic tin, chloromethanes, reallocation agent butter of tin, the mol ratio of isooctyl thioglycolate are 1:1.5:0.2:4；
(3) washing: separate organic facies and wash 1 time；
(4) distillation: obtain Methyl stannum mercaptide after vacuum distillation drying.
The Methyl stannum mercaptide finally obtained is (CH3)2Sn(SCH2CO2C8H17)2(stannous methide) and CH3Sn
(SCH2CO2C8H17)3The mixture of (monomethyl stannum), wherein the quality accounting of stannous methide is 40-60%.
Quaternary ammonium salt phase catalyst is tetrabutyl ammonium bromide.
The waste water produced in preparation process passes through circulating pump by the condensed water in high temperature in raw water box by carrier type membrane module mistake
Filter device lower port is injected wherein, filters with cross-current flow, crossflow velocity 0.1m/s, transmembrane pressure 0.001MPa；Regulation
Concentrated water drainage is high-volume so that the water yield of carrier type membrane module filtration treatment is 80%.The filtration of inorganic carbon film in carrier type membrane module
Precision is 0.001 micron.Carrier type membrane module filters and produces water and be passed through active carbon filter and filter by producing water export mouth, activity
Charcoal filters and carries out in dead-end filtration mode；Activated carbon used is cocoanut active charcoal, and granularity is 8 mesh；Produce water to filter from activated carbon
Device water outlet flows out.
Embodiment two
The preparation method of the Methyl stannum mercaptide of green safety, comprises the following steps:
(1) stannum: metallic tin and catalyst are put in pressure acid-resistant reacting kettle, then passes to chloromethanes at a temperature of 170 DEG C
Heating mix homogeneously, after carrying out halogenation 0.4h, adds reallocation agent butter of tin and is warmed up to 235-245 DEG C, pressurization
Carry out stannumization to 0.5-0.8MPa to react 2 hours, then, distill and accept gas temperature at 230 DEG C of interior fractions, then with pure
Water absorbs and obtains methyl tin chloride aqueous solution；
Methyl alkene chloride includes dimethyltin chloride and monomethyl tin trichloride；First catalyst is quaternary ammonium salt phase transfer
The mixture that catalyst and dimethyl sulfide form than 1:3 according to molal weight；The weight of the first catalyst accounts for metallic tin weight
3%.
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, adds the second catalyst,
Stirring reaction 0.4 hour at temperature 5-15 DEG C, adds the continuously stirred reaction of alkali liquor that mass fraction is 20% until reactant
It is that pH value reaches 7-9, then heats to 70 DEG C, react 1.5 hours, static, lower the temperature, be layered；
The mixing that second catalyst is quaternary ammonium salt-type phase transfer catalyst and dimethyl sulfoxide forms than 1:1-4 according to molal weight
Thing；The weight of the second catalyst accounts for the 6-9% of isooctyl thioglycolate weight；
Metallic tin, chloromethanes, reallocation agent butter of tin, the mol ratio of isooctyl thioglycolate are 1:2:0.5:3；
(3) washing: separate organic facies and wash 2 times；
(4) distillation: obtain Methyl stannum mercaptide after vacuum distillation drying.
The Methyl stannum mercaptide finally obtained is (CH3)2Sn(SCH2CO2C8H17)2(stannous methide) and CH3Sn
(SCH2CO2C8H17)3The mixture of (monomethyl stannum), wherein the quality accounting of stannous methide is 60%.
Quaternary ammonium salt phase catalyst is tetrabutylammonium chloride.
The waste water produced in preparation process is entered by the lower port of carrier type membrane module defecator by circulating pump, carrier
In formula membrane module, the filtering accuracy of inorganic carbon film is 0.3 micron, filters with cross-current flow, and crossflow velocity is 3m/s, cross-film
Pressure reduction is 0.03MPa, and producing Water Sproading rate is 90%.Carrier type membrane module filters product water and is passed through active carbon filter, activated carbon used
For cocoanut active charcoal, activated carbon granule degree is 18 mesh；Activated carbon filters and carries out in dead-end filtration mode, produces water and filters from activated carbon
Device water outlet flows out.
Embodiment three
The preparation method of the Methyl stannum mercaptide of green safety, comprises the following steps:
(1) stannum: metallic tin and catalyst are put in pressure acid-resistant reacting kettle, then passes to chloromethanes at a temperature of 160 DEG C
Heating mix homogeneously, after carrying out halogenation 0.3h, adds reallocation agent butter of tin and is warmed up to 240 DEG C, is forced into
0.6MPa carries out stannumization and reacts 1.5 hours, then, distills and accepts gas temperature at 200 DEG C of interior fractions, then inhaling with pure water
Gather in the crops to obtain methyl tin chloride aqueous solution；
Methyl alkene chloride includes dimethyltin chloride and monomethyl tin trichloride；First catalyst is quaternary ammonium salt phase transfer
The mixture that catalyst and dimethyl sulfide form than 1:2.5 according to molal weight；The weight of the first catalyst accounts for metallic tin weight
The 2% of amount.
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, adds the second catalyst,
Stirring reaction 0.3 hour at temperature 10 DEG C, adds the continuously stirred reaction of alkali liquor that mass fraction is 15% until reaction system
PH value reaches 8, then heats to 65 DEG C, reacts 1-1.5 hour, static, lower the temperature, be layered；
The mixing that second catalyst is quaternary ammonium salt-type phase transfer catalyst and dimethyl sulfoxide forms than 1:3 according to molal weight
Thing；The weight of the second catalyst accounts for the 8% of isooctyl thioglycolate weight；
Metallic tin, chloromethanes, reallocation agent butter of tin, the mol ratio of isooctyl thioglycolate are 1:1.8:0.3:3.5；
(3) washing: separate organic facies and wash 1 time；
(4) distillation: obtain Methyl stannum mercaptide after vacuum distillation drying.
The Methyl stannum mercaptide finally obtained is (CH3)2Sn(SCH2CO2C8H17)2(stannous methide) and CH3Sn
(SCH2CO2C8H17)3The mixture of (monomethyl stannum), wherein the quality accounting of stannous methide is 50%.
Quaternary ammonium salt phase catalyst is tri-n-octyl methyl ammonium chloride.
The waste water produced in preparation process is entered by the lower port of carrier type membrane module defecator by circulating pump, carrier
In formula membrane module, the filtering accuracy of inorganic carbon film is 0.3 micron, filters with cross-current flow, and crossflow velocity is 5m/s, cross-film
Pressure reduction is 0.3MPa, and producing Water Sproading rate is 80%.Carrier type membrane module filters product water and is passed through active carbon filter by producing water export mouth
Filtering, activated carbon filters and carries out in dead-end filtration mode；Activated carbon used is cocoanut active charcoal, and granularity is 30 mesh；Produce
Water flows out from active carbon filter water outlet.
Embodiment four
With embodiment one, except for the difference that in synthesis step, adding the continuously stirred reaction of alkali liquor until pH value of reaction system reaches
To 7, then heat up during, according to sequencing add account for isooctyl thioglycolate weight 1% the first solid additive and
Account for isooctyl thioglycolate weight 6% the second solid additive.
The particle size range of the first solid additive is 0.8-5 micron；Wherein, the granule of 0.8-1 micron accounts for the first solid and adds
Add the 20% of agent gross weight；The granule of 1-2 micron accounts for the 30% of the first solid additive gross weight；Surplus is the granule of 3-5 micron；
First solid additive is following formula I polymer, and wherein Mw is 6.10 × 106, Mn is 2.0 × 106, molecular weight distribution refers to
Number is 3.1:
I
Second solid additive is that the regulation grain of molybdenum disulfide nano ball and the particle diameter 6-9 micron of particle diameter 10-20 nanometer is according to matter
Measure the mixture than 1:2 composition.
Embodiment five
With embodiment two, except for the difference that in synthesis step, adding the continuously stirred reaction of alkali liquor until pH value of reaction system reaches
To 9, then heat up during, according to sequencing add account for isooctyl thioglycolate weight 3% the first solid additive and
Account for isooctyl thioglycolate weight 3% the second solid additive.
The particle size range of the first solid additive is 0.8-5 micron；Wherein, the granule of 0.8-1 micron accounts for the first solid and adds
Add the 40% of agent gross weight；The granule of 1-2 micron accounts for the 10% of the first solid additive gross weight；Surplus is the granule of 3-5 micron；
First solid additive is following formula I polymer, and wherein Mw is 6.10 × 106, Mn is 2.0 × 106, molecular weight distribution refers to
Number is 3.1:
I
Second solid additive is that the regulation grain of molybdenum disulfide nano ball and the particle diameter 6-9 micron of particle diameter 10-20 nanometer is according to matter
Measure the mixture than 1:5 composition.
Embodiment six
With embodiment three, except for the difference that in synthesis step, adding the continuously stirred reaction of alkali liquor until pH value of reaction system reaches
To 8, then heat up during, according to sequencing add account for isooctyl thioglycolate weight 2% the first solid additive and
Account for isooctyl thioglycolate weight 5% the second solid additive.
The particle size range of the first solid additive is 0.8-5 micron；Wherein, the granule of 0.8-1 micron accounts for the first solid and adds
Add the 30% of agent gross weight；The granule of 1-2 micron accounts for the 20% of the first solid additive gross weight；Surplus is the granule of 3-5 micron；
First solid additive is following formula I polymer, and wherein Mw is 6.10 × 106, Mn is 2.0 × 106, molecular weight distribution refers to
Number is 3.1:
I
Second solid additive is that the regulation grain of molybdenum disulfide nano ball and the particle diameter 6-9 micron of particle diameter 10-20 nanometer is according to matter
Measure the mixture than 1:3 composition.
Comparative example one
With embodiment one, except for the difference that stannum step distilled and accept gas temperature at 140 DEG C of interior fractions, in synthesis step
Gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, adds the second catalyst, stir at temperature 25 DEG C
React 0.8 hour, add the continuously stirred reaction of alkali liquor until pH value of reaction system reaches 10, then heat to 60 DEG C, react 1
Hour.
Application test contrasts:
Methyl stannum mercaptide comparative example one prepared is applied with the Methyl stannum mercaptide in embodiment one to embodiment six respectively
Carrying out static burn in test in PVC sheet, the amount adding heat stabilizer is 0.8%, and the PVC sheet made is 180 DEG C of guarantors
Temperature, kept sample standby every ten minutes, until all of sheet material all turns yellow, and used time 110 minutes altogether, all samples of sheets are made
Form, obtains aging control experiment data, its result such as table 1 below the most intuitively:
As can be seen from Table 1: the product of developing of the present invention has more excellent thermostable effect, under the conditions of equal consumption,
Than the product xanthochromia time lengthening more than half times of comparative example one, and Theil indices have dropped about 4%.Can significantly drop
The production cost of low PVC producer, reaches cheap purpose.
Embodiment seven
Inorganic carbon membrane includes supporting layer and stratum disjunctum；
Stratum disjunctum thickness is 0.05 micron；
Stratum disjunctum pore size filter is 20nm；
Supporting layer consisting of by weight:
Aggregate: coal dust 40 parts, 10 parts of phenolic resin, white carbon 20 parts, bentonite 5 parts, burns Kaolin 8 parts；
Pore former: camwood knag 0.5 part, snake stone powder 0.3 part；
Additive: copper nitrate 1 part, the silicon dioxide 2 parts that dimethyl two sample is silane-modified；
Dispersant: 0.8 part of lecithin.
The preparation process of stratum disjunctum is:
Dispensing: by weight preparation white carbon 15 parts, coal dust 25 parts, camwood knag 0.5 part；
Coating liquid solvent is prepared: glycerol, ethylene glycol and BDO 10:8:30 by volume is weighed mixing；
Stratum disjunctum slurry preparation: coal dust 25 parts is initially charged in coating liquid solvent mixing 2min, then by camwood knag 0.5 part addition
Mixing 1min, finally adds white carbon 15 parts mixing 8min, obtains uniform stratum disjunctum slurry；
Stratum disjunctum slurry coats: by stratum disjunctum slurry even application on supporting layer 11, then first at 70 DEG C of drying 2h, then
Dry 1h for 120 DEG C and obtain stratum disjunctum 12.
Stratum disjunctum coating preparation is rear on supporting layer obtains primary inorganic carbon membrane, and the preparation of inorganic carbon membrane includes primary nothing
Machine carbon membrane sinter, sintering specifically to 500-550 DEG C and be incubated 0.3-0.5h with the ramp of 5-15 DEG C/min, the most again with
The ramp of 10-20 DEG C/min is to 800-1000 DEG C and is incubated the inorganic charcoal Flat Membrane that 0.5-0.8h acquisition is final.
Embodiment eight
Inorganic carbon membrane includes supporting layer and stratum disjunctum；
Stratum disjunctum thickness is 1 micron；
Stratum disjunctum pore size filter is 10 microns；
Supporting layer consisting of by weight:
Aggregate: coal dust 50 parts, 15 parts of phenolic resin, white carbon 30 parts, bentonite 9 parts, burns Kaolin 4 parts；
Pore former: camwood knag 1 part, snake stone powder 0.8 part；
Additive: copper nitrate 2 parts, fatty acid modified calcium carbonate 4 parts；
Dispersant: 1.2 parts of lecithin.
The preparation process of stratum disjunctum is:
Dispensing: by weight preparation white carbon 20 parts, coal dust 30 parts, camwood knag 1 part；
Coating liquid solvent is prepared: glycerol, ethylene glycol and BDO 15:16:18 by volume is weighed mixing；
Stratum disjunctum slurry preparation: coal dust 30 parts is initially charged in coating liquid solvent mixing 4min, then camwood knag 1 part is added mixed
Close 3min, finally white carbon 20 parts is added mixing 12min, obtains uniform stratum disjunctum slurry；
Stratum disjunctum slurry coats: by stratum disjunctum slurry even application on supporting layer, then first dries 5h at 90 DEG C, then 150
DEG C dry 3h obtain stratum disjunctum.
Stratum disjunctum coating preparation is rear on supporting layer obtains primary inorganic carbon membrane, and the preparation of inorganic carbon membrane 1 includes primary
Inorganic carbon membrane sinter, sintering specifically to 550 DEG C and be incubated 0.5h with the ramp of 15 DEG C/min, the most again with 10-20 DEG C/
The ramp of min is to 1000 DEG C and is incubated the inorganic charcoal Flat Membrane that 0.8h acquisition is final.
Embodiment nine
Inorganic carbon membrane includes supporting layer and stratum disjunctum；
Stratum disjunctum thickness is 0.05 micron；
Stratum disjunctum thickness and supporting layer thickness are than for 1:100；Stratum disjunctum pore size filter 20nm；
Stratum disjunctum is formed by repeatedly coating, and the aperture of the layer that is thus supported, stratum disjunctum internal layer and stratum disjunctum outer layer gradually becomes
Little bore diameter gradient；
Formed between flat inorganic carbon membrane and the inorganic carbon membrane of laid out in parallel and produce aquaporin, flat inorganic carbon membrane thickness and product
Aquaporin height ratio is 1:4.
Supporting layer consisting of by weight:
Aggregate: coal dust 45 parts, 13 parts of phenolic resin, white carbon 22 parts, bentonite 6 parts, burns Kaolin 5 parts；
Pore former: camwood knag 0.8 part, snake stone powder 0.5 part；
Additive: copper nitrate 1.2 parts, the silicon dioxide 3 parts that dimethyl two sample is silane-modified；
Dispersant: 0.9 part of lecithin.
The preparation process of stratum disjunctum is:
Dispensing: by weight preparation white carbon 18 parts, coal dust 28 parts, camwood knag 0.8 part；
Coating liquid solvent is prepared: glycerol, ethylene glycol and BDO 11:10:20 by volume is weighed mixing；
Stratum disjunctum slurry preparation: coal dust 28 parts is initially charged in coating liquid solvent mixing 3min, then by camwood knag 0.8 part addition
Mixing 2min, finally adds white carbon 18 parts mixing 10min, obtains uniform stratum disjunctum slurry；
Stratum disjunctum slurry coats: by stratum disjunctum slurry even application on supporting layer, then first dries 3h at 79 DEG C, then 140
DEG C dry 2h obtain stratum disjunctum 12.
Stratum disjunctum coating preparation is rear on supporting layer obtains primary inorganic carbon membrane, and the preparation of inorganic carbon membrane includes primary nothing
Machine carbon membrane is sintered, sintering specifically to 530 DEG C and be incubated 0.4h with the ramp of 10 DEG C/min, the most again with 15 DEG C/
The ramp of min is to 900 DEG C and is incubated the inorganic charcoal Flat Membrane that 0.6h acquisition is final.
Embodiment ten
Inorganic carbon membrane includes supporting layer and stratum disjunctum；
Stratum disjunctum thickness is 1 micron；
Stratum disjunctum thickness and supporting layer thickness are than for 1:50；Stratum disjunctum pore size filter 10 microns；
Stratum disjunctum is formed by repeatedly coating, and the aperture of the layer that is thus supported, stratum disjunctum internal layer and stratum disjunctum outer layer gradually becomes
Little bore diameter gradient；
Formed between flat inorganic carbon membrane and the inorganic carbon membrane of laid out in parallel and produce aquaporin, flat inorganic carbon membrane thickness and product
Aquaporin height ratio is 1:20.
Remaining is with embodiment four, except for the difference that also includes in coating liquid solvent that 3 weight portion silane couplers or Aluminate are even
Connection agent；Coating liquid solvent also includes 0.6 weight portion irgasfos 168；
Supporting layer consisting of by weight:
Aggregate: coal dust 42 parts, 12 parts of phenolic resin, white carbon 23 parts, bentonite 5 parts, burns Kaolin 4 parts；
Pore former: camwood knag 0.5 part, snake stone powder 0.3 part；
Additive: copper nitrate 1.2 parts, the silicon dioxide 2.5 parts that dimethyl two sample is silane-modified；
Dispersant: 0.8 part of lecithin.
The preparation process of stratum disjunctum is:
Dispensing: by weight preparation white carbon 15 parts, coal dust 26 parts, camwood knag 0.6 part；
Coating liquid solvent is prepared: glycerol, ethylene glycol and BDO 11:10:20 by volume is weighed mixing；
Stratum disjunctum slurry preparation: coal dust 26 parts is initially charged in coating liquid solvent mixing 2min, then by camwood knag 0.6 part addition
Mixing 1-3min, finally adds white carbon 15 parts mixing 8-12min, obtains uniform stratum disjunctum slurry；
Stratum disjunctum slurry coats: by stratum disjunctum slurry even application on supporting layer, then first dries 3h at 75 DEG C, then 130
DEG C dry 1.5h obtain stratum disjunctum.
Embodiment 11
Inorganic carbon membrane includes supporting layer and stratum disjunctum；
Stratum disjunctum thickness is 0.08 micron；
Stratum disjunctum thickness and supporting layer thickness are than for 1:80；Stratum disjunctum pore size filter 1 micron；
Stratum disjunctum is formed by repeatedly coating, and the aperture of the layer that is thus supported, stratum disjunctum internal layer and stratum disjunctum outer layer gradually becomes
Little bore diameter gradient；
Formed between flat inorganic carbon membrane and the inorganic carbon membrane of laid out in parallel and produce aquaporin, flat inorganic carbon membrane thickness and product
Aquaporin height ratio is 1:8.
Remaining is with embodiment four, except for the difference that also includes 4.5 weight portion silane coupler or Aluminates in coating liquid solvent
Coupling agent, also includes 1.1 weight portion irgasfos 168s in coating liquid solvent.
Coating liquid solvent also includes 5 weight portion silane coupler or aluminate coupling agents；Coating liquid solvent also includes
1.5 weight portion irgasfos 168s；
Supporting layer consisting of by weight:
Aggregate: coal dust 48 parts, 14 parts of phenolic resin, white carbon 28 parts, bentonite 9 parts, burns Kaolin 8 parts；
Pore former: camwood knag 1 part, snake stone powder 0.8 part；
Additive: copper nitrate 1.6 parts, fatty acid modified calcium carbonate 3.2 parts；
Dispersant: 1.2 parts of lecithin.
The preparation process of stratum disjunctum 12 is:
Dispensing: by weight preparation white carbon 20 parts, coal dust 28 parts, camwood knag 0.8 part；
Coating liquid solvent is prepared: glycerol, ethylene glycol and BDO 14:15:26 by volume is weighed mixing；
Stratum disjunctum slurry preparation: coal dust 28 parts is initially charged in coating liquid solvent mixing 4min, then by camwood knag 0.8 part addition
Mixing 1-3min, finally adds white carbon 15-20 part mixing 8-12min, obtains uniform stratum disjunctum slurry；
Stratum disjunctum slurry coats: by stratum disjunctum slurry even application on supporting layer, then first at 85 DEG C of drying 3-4h, then
Dry 2h for 140 DEG C and obtain stratum disjunctum.
After testing, film properties: effective operating flux can reach more than 5 times of traditional ceramics film, top layer membrance separation layer and water
Contact angle be only up to 0.3 °, good hydrophilic property, oil resistant class pollution capacity is strong, and in water inlet, float and oil pollutant can reach
To more than 10mg/L；The cross flow filter mode using low crossflow velocity carries out filtration treatment, is effectively prevented from oil pollution and comes
The impact that film itself is caused by water slug, and filtering accuracy is high, suspended solids median particle size≤1 micron.
Embodiment 12
With embodiment seven, except for the difference that the preparation process of supporting layer is:
(1) dispensing: by certain weight ratio by two kinds of varigrained sic powders, binding agent and water, mix in a mixer
0.1 hour, obtain the pug with viscosity；
(2) by prepared pug by extruder for shaping, extrudate size is determined had by cross-head mould
There is certain overall dimensions and produce the blank of aquaporin size；
(3) prepared blank is dried 0.5 hour under room temperature ventilation condition；
(4) blank after drying at room temperature is put in calcining furnace, in 24 hours, temperature is increased to 2000 DEG C, and in this temperature
Lower holding 1 hour, then cooled the temperature to room temperature in 24 hours, obtained film supporting layer.
The preparation process of stratum disjunctum is:
(1) by having the sic powder of certain particle size, binding agent and water mixing, slurry is made；
(2) film support lateral surface is uniformly coated gained slurry；
(3) lamina membranacea after coating is dried 0.5 hour under room temperature ventilation condition；
(4) dried lamina membranacea is put in calcining furnace, in 24 hours, temperature is increased to 1800 DEG C, and protects at this temperature
Hold 1 hour, then in 24 hours, cool the temperature to room temperature, obtain film and there is the unsymmetrical diaphragm of supporting layer and filter course.
Embodiment 13
With embodiment nine, except for the difference that the preparation process of supporting layer is:
(1) dispensing: by certain weight ratio by two kinds of varigrained sic powders, binding agent and water, mix 5 in a mixer
Hour, obtain the pug with viscosity；
(2) by prepared pug by extruder for shaping, extrudate size is determined had by cross-head mould
There is certain overall dimensions and produce the blank of aquaporin size；
(3) prepared blank is dried 24 hours under room temperature ventilation condition；
(4) blank after drying at room temperature is put in calcining furnace, in 24 hours, temperature is increased to 2400 DEG C, and in this temperature
Lower holding 10 hours, then cooled the temperature to room temperature in 24 hours, obtained film supporting layer.
The preparation process of stratum disjunctum is:
(1) by having the sic powder of certain particle size, binding agent and water mixing, slurry is made；
(2) film support lateral surface is uniformly coated gained slurry；
(3) lamina membranacea after coating is dried 0.5-24 hour under room temperature ventilation condition；
(4) dried lamina membranacea is put in calcining furnace, in 18 hours, temperature is increased to 2400 DEG C, and protects at this temperature
Hold 10 hours, then in 24 hours, cool the temperature to room temperature, obtain film and there is the unsymmetrical diaphragm of supporting layer and filter course.
Embodiment 14
With embodiment seven, except for the difference that the preparation process of supporting layer is:
(1) dispensing: by certain weight ratio by two kinds of varigrained sic powders, binding agent and water, mix 3 in a mixer
Hour, obtain the pug with viscosity；
(2) by prepared pug by extruder for shaping, extrudate size is determined had by cross-head mould
There is certain overall dimensions and produce the blank of aquaporin size；
(3) prepared blank is dried 4 hours under room temperature ventilation condition；
(4) blank after drying at room temperature is put in calcining furnace, in 16 hours, temperature is increased to 2300 DEG C, and in this temperature
Lower holding 5 hours, then cooled the temperature to room temperature in 24 hours, obtained film supporting layer.
The preparation process of stratum disjunctum is:
(1) by having the sic powder of certain particle size, binding agent and water mixing, slurry is made；
(2) film support lateral surface is uniformly coated gained slurry；
(3) lamina membranacea after coating is dried 0.5-24 hour under room temperature ventilation condition；
(4) dried lamina membranacea is put in calcining furnace, in 24 hours, temperature is increased to 1900 DEG C, and protects at this temperature
Hold 6 hours, then in 24 hours, cool the temperature to room temperature, obtain film and there is the unsymmetrical diaphragm of supporting layer and filter course.
The flat inorganic carbon membrane assembly inorganic charcoal Flat Membrane of the embodiment of the present invention seven-embodiment 14 being assembled into should
The Performance comparision being used in condensed water in high temperature oil removing process is shown in Table 2 and table 3.
Table 2 processes the contrast of condensed water in high temperature oil removing filter effect
Table 3 processes condensed water in high temperature oil removing and filters backwash and Chemical cleaning Contrast on effect
This specific embodiment is only explanation of the invention, and it is not limitation of the present invention, and those skilled in the art exist
As required the present embodiment can be made after reading this specification and there is no the amendment of creative contribution, but as long as in the present invention
Right in all protected by Patent Law.
Claims (10)
1. the method for wastewater treatment of the Methyl stannum mercaptide of a green safety, it is characterised in that Methyl stannum mercaptide passes through following steps
It is prepared from:
(1) stannum: metallic tin and the first catalyst are put in reactor, then passes to chloromethanes and carry out halogenation, add again
Distribution is after agent carries out stannum reaction, distills and accepts gas temperature at 150-230 DEG C of interior fraction, then obtaining by absorbing pure water
Methyl tin chloride aqueous solution；Described methyl alkene chloride includes dimethyltin chloride and monomethyl tin trichloride；
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, adds the second catalyst, in temperature
At spending 5-15 DEG C, stirring reaction 0.2-0.4 hour, adds the continuously stirred reaction of alkali liquor until pH value of reaction system reaches 7-9,
Then heat to 60-70 DEG C, react 1-1.5 hour, static, lower the temperature, be layered；
Described metallic tin, chloromethanes, reallocation agent, the mol ratio of isooctyl thioglycolate are 1:(1.5-2): (0.2-0.5):
(3-4)；
(3) washing: separate organic facies and wash 1-2 time；
(4) distillation: obtain Methyl stannum mercaptide after vacuum distillation drying；
The waste water treatment process produced in preparation process includes carrier type membrane module filtration stage and active carbon filter oil removing rank
Section, concrete technology is as follows:
(1) carrier type membrane module is injected by raw water box through circulating pump；
(2) carrier type membrane module filtration stage is carried out in cross flow filter mode, and crossflow velocity is 0.1-5m/s, and transmembrane pressure is
0.01-0.3MPa, membrane module filtering accuracy is 0.001-100 micron, and recycle ratio is 80-99%；
(3) the active carbon filter oil removing stage is carried out in dead-end filtration mode, and filtering velocity is 3-5m/s.
The method of wastewater treatment of the Methyl stannum mercaptide of a kind of green safety the most according to claim 1, it is characterised in that: institute
State step (1) stannum to specifically include in metallic tin and the catalyst pressure acid-resistant reacting kettle of input, then pass to chloromethanes and exist
Heat mix homogeneously at a temperature of 150-170 DEG C, after carrying out halogenation 0.2-0.4h, add reallocation agent and be warmed up to 235-
245 DEG C, be forced into 0.5-0.8MPa carry out stannumization react 1-2 hour.
The method of wastewater treatment of the Methyl stannum mercaptide of a kind of green safety the most according to claim 2, it is characterised in that: institute
State carrier type membrane module and include that film core (1), film core (1) periphery are surrounded by shell (2)；Described shell (2) top and the bottom are provided with upper and lower side
Mouthful, wherein upper port (3) is connected with dense water outlet pipe (6) and lower port (4) is connected with raw water box outlet pipe (5)；Shell (2)
Side is provided with and filters out the mouth of a river (7) and be connected with active carbon filter water inlet by pipeline.
The method of wastewater treatment of the Methyl stannum mercaptide of a kind of green safety the most according to claim 3, it is characterised in that: institute
State the mixing that the first catalyst is quaternary ammonium salt-type phase transfer catalyst and dimethyl sulfide forms than 1:2-3 according to molal weight
Thing；Described second catalyst is quaternary ammonium salt-type phase transfer catalyst and dimethyl sulfoxide forms than 1:1-4 according to molal weight
Mixture.
5., according to the method for wastewater treatment of the Methyl stannum mercaptide of a kind of green safety described in claim 3 or 4, its feature exists
In: described quaternary ammonium salt phase catalyst is tetrabutyl ammonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate or tricaprylmethyl
Ammonium chloride.
The method of wastewater treatment of the Methyl stannum mercaptide of a kind of green safety the most according to claim 5, it is characterised in that: institute
Stating reallocation agent is butter of tin.
The method of wastewater treatment of the Methyl stannum mercaptide of a kind of green safety the most according to claim 3, it is characterised in that: institute
The weight stating the first catalyst accounts for the 1-3% of metallic tin weight.
The method of wastewater treatment of the Methyl stannum mercaptide of a kind of green safety the most according to claim 4, it is characterised in that: institute
The weight stating the second catalyst accounts for the 6-9% of isooctyl thioglycolate weight.
The method of wastewater treatment of the Methyl stannum mercaptide of a kind of green safety the most according to claim 6, it is characterised in that: institute
Stating the mass fraction of alkali liquor in step (2) is 10-20%.
The method of wastewater treatment of the Methyl stannum mercaptide of a kind of green safety the most according to claim 6, it is characterised in that:
In synthesis step, in the addition continuously stirred reaction of alkali liquor until pH value of reaction system reaches 7-9, during then heating up,
Add first solid additive of the 1-3% accounting for isooctyl thioglycolate weight according to sequencing and account for isooctyl thioglycolate weight
Second solid additive of the 3-6% of amount.
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| CN108976254A (en) * | 2018-07-04 | 2018-12-11 | 湖北犇星化工有限责任公司 | A kind of dry method for waste water of reduction thiol methyl tin synthesis |
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