CN105983346B - Sapo-34分子筛膜渗透汽化与汽相渗透分离气液/液体混合物的方法 - Google Patents
Sapo-34分子筛膜渗透汽化与汽相渗透分离气液/液体混合物的方法 Download PDFInfo
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- CN105983346B CN105983346B CN201510054331.8A CN201510054331A CN105983346B CN 105983346 B CN105983346 B CN 105983346B CN 201510054331 A CN201510054331 A CN 201510054331A CN 105983346 B CN105983346 B CN 105983346B
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- molecular sieve
- sapo
- sieve membrane
- fluoride
- aluminum
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- 239000012528 membrane Substances 0.000 title claims abstract description 87
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 87
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000007788 liquid Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 238000005373 pervaporation Methods 0.000 title claims abstract description 30
- 239000012808 vapor phase Substances 0.000 title claims abstract description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 177
- 238000000926 separation method Methods 0.000 claims abstract description 41
- 239000013078 crystal Substances 0.000 claims abstract description 34
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims abstract description 23
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005371 permeation separation Methods 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
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- 238000005406 washing Methods 0.000 claims abstract description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 19
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- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 12
- 150000004673 fluoride salts Chemical class 0.000 claims description 10
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- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
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- 239000001301 oxygen Substances 0.000 claims description 5
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000010413 mother solution Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- -1 vacuum Substances 0.000 claims description 2
- 159000000013 aluminium salts Chemical class 0.000 claims 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 15
- 238000005216 hydrothermal crystallization Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000012466 permeate Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229920001661 Chitosan Polymers 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
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- 238000005265 energy consumption Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 235000007119 Ananas comosus Nutrition 0.000 description 1
- 244000099147 Ananas comosus Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
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- GUNDKLAGHABJDI-UHFFFAOYSA-N dimethyl carbonate;methanol Chemical compound OC.COC(=O)OC GUNDKLAGHABJDI-UHFFFAOYSA-N 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/0051—Inorganic membrane manufacture by controlled crystallisation, e,.g. hydrothermal growth
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- C07C68/00—Preparation of esters of carbonic or haloformic acids
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- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明公开了一种SAPO‑34分子筛膜渗透汽化与汽相渗透分离气液/液体混合物的方法,包括:1)将铝源、四乙基氢氧化铵、水、硅源与磷源混合溶解后,水热晶化,离心,洗涤,干燥,得SAPO‑34分子筛晶种;2)将SAPO‑34分子筛晶种涂布到多孔载体管的内表面;3)合成SAPO‑34分子筛膜管;4)焙烧SAPO‑34分子筛膜管,得SAPO‑34分子筛膜;5)采用渗透汽化分离工艺或汽相渗透分离工艺,利用步骤4)得到的SAPO‑34分子筛膜对气液混合物或液体混合物进行分离。本发明具有非常高的甲醇选择性及渗透通量,而且渗透汽化或汽相渗透分离是一种高效、节能的分离方法。
Description
技术领域
本发明涉及一种利用SAPO-34分子筛膜分离混合物的方法,特别涉及一种SAPO-34分子筛膜渗透汽化与汽相渗透分离气液或液体混合物的方法。
背景技术
碳酸二甲酯(DMC),分子式为CO(OCH3)2,是一种良好的溶剂,挥发性低,毒性值与无水乙醇相近,而且可以完全生物降解,是一种环境友好型化学品,在医药、化工、能源等领域内都有广泛的应用。DMC分子含氧量达53%,三倍于甲基叔丁基醚(MTBE),可作为汽油添加剂提高辛烷值并抑制一氧化碳和烃类的排放。它的化学性质非常活泼,是有机合成重要的中间体及起始原料,被称为有机合成的新基石。
DMC的工业生产方法主要有甲醇氧化羰基化法、酯交换法、光气法等[Appl.Catal.A Gen.,221(2001)241-251],无论采取何种方法,反应后都会得到甲醇(MeOH)与DMC的混合物。常压下,MeOH和DMC形成二元共沸液(MeOH 70wt.%,DMC 30wt.%),共沸温度为64℃。因此,需要从共沸液中分离回收DMC。目前对于MeOH/DMC共沸液的分离方法主要有低温结晶法、吸附法、萃取精馏法、共沸精馏法和加压精馏法。这些分离方法都存在着能耗大、溶剂难于选取、操作难度大和安全性差等缺点和不足。相比之下,膜分离法具备能耗低、效率高、操作条件要求较低等优点。
膜分离技术利用膜两侧某组分化学势差为驱动力,膜对进料液中不同组分亲和性和传质阻力的差异实现选择分离。按材质分类,膜材料主要可分为高分子膜、无机膜和复合膜。近年来,国内外在利用膜技术分离MeOH/DMC混合物方面的研究已取得了一定进展,主要集中在高分子膜方面,发现聚乙烯醇(PVA)、聚丙烯酸(PAA)、壳聚糖等材料均可制成优先脱除甲醇的渗透汽化膜,且具备较好的分离性能。
Wooyoung等采用交联的壳聚糖膜对MeOH/DMC进行渗透汽化分离,并系统研究了操作温度及进料浓度对分离因数及通量的影响,得到了较好的结果[Sep.Purif.Technol.31(2003)129-140]。Wang等制备了PAA/PVA的混合膜,其中含70wt.%PAA的混合膜分离因子为13,渗透通量为577g/(m2h)[J.Membr.Sci.305(2007)238–246]。Pasternak等测试了PVA膜对MeOH/DMC分离性能,渗透侧的MeOH浓度由进料时的70wt.%提浓至93~97wt.%,通量为100~1130g/(m2h)[US 4798674(1989)]。Chen等采用壳聚糖与氨基丙基三乙氧基硅烷交联制备出壳聚糖-氧化硅的杂化膜,在50℃条件下,进料浓度为MeOH/DMC为70/30,分离因子达到30,渗透通量为1265g/(m2h)[J.Colloid Interf.Sci.316(2007)580–588]。
但是高分子膜面对的诸多问题影响了其分离性能和应用范围,如在分离过程中会出现溶胀现象,化学稳定性下,特别是机械强度和热稳定性低下限制了其在高温、高压等严苛条件下的应用。而以分子筛为代表的无机膜则能很好地解决这些问题,因为其具有均一的分离孔径,良好的热稳定性、机械稳定性和化学稳定性,适用于高温、高压等苛刻的分离环境。因此,利用分子筛膜在相对高的温度和压力条件下进行液相混合物的汽相分离成为可能。但是,目前分子筛膜主要用于有机物脱水方面的应用,而MeOH/DMC混合物的分离特别是高温汽相分离方面的应用则鲜有报道。Pina等在氧化铝载体上合成NaA分子筛膜,用来做水/乙醇渗透汽化分离,分离因子能达到3600,水的渗透通量达到3800g/(m2h)[J.Membr.Sci.244(2004)141–150]。Hidetoshi等系统研究了NaX及NaY分子筛膜渗透汽化分离性能,表明对醇及苯具有很高的选择性,同时研究了MeOH/DMC选择性,进料浓度为50/50,分离因子达到480,渗透通量为1530g/(m2h)[Sep.Purif.Technol.25(2001)261–268]。
发明内容
本发明要解决的技术问题是提供一种SAPO-34分子筛膜渗透汽化与汽相渗透分离气液或液体混合物的方法,即本发明主要提供一种SAPO-34分子筛膜合成及其渗透汽化或汽相渗透分离气液混合物或液体混合物的方法。本发明利用制备的高性能SAPO-34分子筛膜可进行汽化或汽相渗透分离混合物(例如:甲醇/碳酸二甲酯),而且本发明的方法具有非常高的甲醇(MeOH)选择性及渗透通量,而且渗透汽化或汽相渗透分离是一种高效、节能的分离方法。
为解决上述技术问题,本发明的SAPO-34分子筛膜渗透汽化或汽相渗透分离气液混合物或液体混合物(例如,分离含甲醇混合物)的方法,包括步骤:
1)将铝源、四乙基氢氧化铵(TEAOH)、水、硅源与磷源混合溶解后,得到晶种反应液,在170~210℃加热下,晶化4~7小时(即进行水热晶化),离心,洗涤,干燥,得到SAPO-34分子筛晶种;
其中,铝源、磷源、硅源、四乙基氢氧化铵与晶种反应液中的总水量的摩尔比为:1Al2O3:1~2P2O5:0.3~0.6SiO2:1~3(TEA)2O:55~150H2O;
本步骤中,晶种反应液的具体配制方法可按如下操作:
将铝源加入到四乙基氢氧化铵TEAOH溶液中,水解后,依次加入硅源和磷源,搅拌,得到晶种反应液;更进一步说,该操作可为:在四乙基氢氧化铵溶液与去离子水混合,再将铝源加入到前述溶液中,室温搅拌2~3小时后,滴加硅源,搅拌0.5~2小时后,缓慢滴加磷源溶液,搅拌12~24小时,得到晶种反应液。
2)将SAPO-34分子筛晶种涂布到多孔载体管的内表面,得到涂覆了SAPO-34分子筛晶种的多孔载体管;
3)SAPO-34分子筛膜管的合成
A、将铝源、磷源、硅源、四乙基氢氧化铵(TEAOH)、二正丙胺、水与氟化物混合均匀后,形成分子筛膜合成母液;
其中,铝源、磷源、硅源、四乙基氢氧化铵、二正丙胺、氟化物与分子筛膜合成母液中的总水量的摩尔比为:1Al2O3:0.5~3.5P2O5:0.05~0.6SiO2:0.5~8TEAOH:0.1~4.0二正丙胺:0.01~1F-:50~300H2O;
B、将步骤2)得到的涂覆了SAPO-34分子筛晶种的多孔载体管置于分子筛膜合成母液中,在室温~80℃下老化2~8小时后,于150~240℃下晶化3~24小时,合成SAPO-34分子筛膜管;
4)焙烧去除模板剂
将步骤3)得到的SAPO-34分子筛膜管在370~700℃下焙烧2~8小时,得到去除模板剂(四乙基氢氧化铵)的SAPO-34分子筛膜;
5)采用渗透汽化分离工艺或汽相渗透分离工艺,利用步骤4)得到的SAPO-34分子筛膜对气液混合物或液体混合物进行分离。其中,气液混合物中的气体包括常见的气体,如包括:惰性气体、氢气、氧气、二氧化碳或气态的烃;气液混合物中的液体包括:水、醇类、酮类或芳香族类等常见的溶剂;
其中,惰性气体包括:氮气;
气态的烃包括:甲烷;
醇类包括:甲醇、乙醇或丙醇;
酮类包括:丙酮或丁酮;
芳香族类包括:苯;
另外,步骤5)中,SAPO-34分子筛膜对液体混合物进行分离中,所述液体混合物为甲醇与甲醇以外的液体的混合物,该甲醇以外的液体包括:碳酸二甲酯、乙醇、甲基叔丁基醚中的一种。
所述步骤1)、3)中,铝源包括:异丙醇铝、Al(OH)3、单质铝和铝盐中的一种或多种;其中,所述铝盐包括:硝酸铝、氯化铝、硫酸铝和磷酸铝中的一种或多种。
步骤1)、3)中,磷源包括:磷酸;
步骤1)、3)中,硅源包括:正硅酸乙酯、正硅酸甲酯、硅溶胶、白炭黑、硅酸钠和水玻璃中的一种或多种。
所述步骤1)中,加热的方式优选为微波加热;步骤1)中,SAPO-34分子筛晶种的尺寸为50~1000纳米。
所述步骤2)中,多孔载体管包括:多孔陶瓷管;其中,多孔陶瓷管的孔径为5纳米~2000纳米,其材质包括:Al2O3、TiO2、ZrO2、SiC或氮化硅。
所述步骤2)的晶种涂布中,其具体步骤为:多孔载体管两端封釉、洗净烘干、外表面密封后,再将SAPO-34分子筛晶种涂布到多孔载体管的内表面;
涂布方法包括:刷涂法或浸涂法。
所述步骤3)中,氟化物包括:氟化氢和氟化物盐中的一种或其混合物;其中,氟化物盐包括:氟化铵、主族金属的氟化物盐或过渡金属的氟化物盐。优选地,所述氟化物盐包括:氟化钾、氟化钠和氟化铵中的一种或多种。
所述步骤3)中,形成分子筛膜合成母液的操作步骤如下:
将铝源、磷源与水混合,搅拌1~5小时后,加入硅源,搅拌0.5~2小时后,加入四乙基氢氧化铵,搅拌0.5~2小时后,加入二正丙胺,搅拌0.5~2小时后,加入氟化物,在室温~60℃下,搅拌12~96小时,得到均匀的分子筛膜合成母液。
所述步骤4)中,焙烧的气氛包括:惰性气体、真空、空气、氧气或任意比例的稀释氧气;焙烧中,升温和降温速率不超过2K/分钟。
所述步骤5)中,渗透汽化分离工艺或汽相渗透分离工艺的条件为:进料甲醇浓度为1~99wt%(质量百分比),渗透操作温度为室温~150℃,进料压力为常压~20大气压,渗透侧压力控制在0.06~2000Pa,进料流量为1~500ml/min。
本发明采用渗透汽化分离工艺或汽相渗透分离工艺,将SAPO-34分子筛膜用于分离气液混合物或液体混合物,例如甲醇/碳酸二甲酯时,当操作温度和压力分别120℃和0.3MPa时,SAPO-34分子筛膜分离甲醇/碳酸二甲酯(70/30)恒沸物的分离系数在1000以上,甲醇的含量达到99.99wt%以上。因此,本发明为甲醇/碳酸二甲酯的分离提供了一种高效、节能的分离方法。同时,本发明的膜法分离甲醇-碳酸二甲酯具有能耗低、不受恒沸物限制、且具有甲醇通量大、分离系数高等优点,具有极大经济价值。
另外,本发明的SAPO-34分子筛膜除了能用于分离甲醇/碳酸二甲酯混合物以外,还可用于甲醇与其它液体混合物的渗透汽化或汽相渗透分离,如甲醇-乙醇,甲醇-甲基叔丁基醚等。
同时,本发明的SAPO-34分子筛膜还可用于上述气液混合物的渗透汽化或汽相渗透分离。
附图说明
下面结合附图与具体实施方式对本发明作进一步详细的说明:
图1是实施例1中的SAPO-34晶种的SEM(扫描电镜)图;
图2是实施例1中的SAPO-34晶种的XRD(X射线衍射)图谱;
图3是实施例1中的SAPO-34分子筛膜的表面SEM图(加入0.1mol HF);
图4是实施例1中的SAPO-34分子筛膜的剖面SEM图(加入0.1mol HF);
图5是渗透汽化分离工艺示意图。其中,1为进料液,2为蠕动泵,3为分子筛膜组件和热源,4为截止阀,5为冷阱,6为真空表,7为真空泵。
图6是实施例4中的SAPO-34分子筛膜的表面SEM图(加入0.1mol NH4F);
图7是实施例4中的SAPO-34分子筛膜的剖面SEM图(加入0.1mol NH4F)。
具体实施方式
实施例1不同进料浓度下SAPO-34分子筛膜分离甲醇/碳酸二甲酯
步骤1:在31.13g四乙基氢氧化铵溶液(TEAOH,35wt%)中加入2.46g去离子水,再称取7.56g异丙醇铝加入到前述溶液中,室温搅拌2-3小时;然后,滴加1.665g硅溶胶(40wt%),搅拌1小时;最后,缓慢滴加8.53g磷酸溶液(H3PO4,85wt%),搅拌过夜(如搅拌12小时)。采用微波加热,在180℃下晶化7小时。产物取出后,离心,洗涤,烘干,得到SAPO-34分子筛晶种。其中,该晶种的SEM图如图1所示。该晶种的XRD图,如图2所示。从SEM图可以看出晶种的尺寸约为300纳米×300纳米×100纳米,且XRD图反映出晶种是纯SAPO-34相,结晶良好,无杂相。
步骤2:选取孔径为5nm的多孔陶瓷管(氧化铝材质)作为载体,载体两端封釉,洗净烘干后,外表面用四氟带密封,将SAPO-34分子筛晶种刷涂到陶瓷管的内表面,得到涂覆了SAPO-34分子筛晶种的多孔陶瓷管。
步骤3:将4.27g磷酸溶液(H3PO4,85wt%)与43.8g去离子水混合,搅拌5min,然后加入7.56g异丙醇铝,在室温下搅拌3小时;加入0.83g硅溶胶(40wt%),室温下搅拌30min;然后,滴加7.78g四乙基氢氧化铵溶液(TEAOH,35wt%),室温下搅拌1小时;最后加入3.0g二正丙胺,室温下搅拌30min后,加入0.045g氢氟酸(HF,40wt%),在50℃下搅拌过夜(如搅拌12小时),得到均匀的SAPO-34分子筛膜的合成母液。将上述步骤2制备的涂覆了SAPO-34晶种的多孔陶瓷管置于反应釜中,加入SAPO-34分子筛膜的合成母液,将反应釜拧紧置于室温下老化3小时,然后,在220℃下水热晶化5小时,取出后冲洗干净,放入烘箱中烘干,得到SAPO-34分子筛膜管。
步骤4:将步骤3得到的SAPO-34分子筛膜管在400℃下真空焙烧4小时,脱除模板剂(升温和降温速率均为1℃/min),得到活化的SAPO-34分子筛膜。
其中,SAPO-34分子筛膜的表面和剖面SEM图(加入0.1mol HF),分别如图3-4所示。可以看出,载体表面被方形的SAPO-34晶体完全覆盖,晶体之间交联完美,晶体大小为4~7微米,分子筛膜表面平整。剖面照片显示膜厚约为5~6微米。
步骤5:采用渗透汽化分离工艺分离甲醇/碳酸二甲酯(即MeOH/DMC)恒沸物,渗透操作温度为120℃,进料压力为0.3MPa,进料流量为1毫升/分钟,渗透侧压力为100Pa,进料浓度MeOH/DMC的质量比为90/10、70/30、50/50、30/70、10/90。其中,渗透汽化工艺示意图如图5所示。
分离系数计算公式:α=(w2m/w2d)/(w1m/w1d)。其中,w2m为渗透侧甲醇的质量浓度;w2d为渗透侧碳酸二甲酯的质量浓度;w1m为进料甲醇的质量浓度;w1d为进料碳酸二甲酯的质量浓度。
渗透通量计算公式:J=Δm/(s×t),其中,Δm为渗透侧收集到的产物质量,单位为g;s为分子筛膜面积,单位为m2;t为收集时间,单位为h。
表1实施例1的MeOH/DMC渗透汽化分离测试结果
从表1可以看出,在不同的进料浓度下,氟化物体系下合成的SAPO-34分子筛膜具有非常高的甲醇选择性,分离系数在30-70wt%进料时为最低值,2620;70-30wt%进料时取得最大值,约8600。渗透产物中的甲醇浓度至少为99.8wt%。随着进料中甲醇浓度的提高,渗透通量逐渐升高,这是由于甲醇分压上升所致。
实施例2不同操作温度下SAPO-34分子筛膜分离甲醇/碳酸二甲酯
与实施例1的不同之处在于,步骤5中的进料浓度MeOH/DMC为90/10,操作温度分别为100℃、110℃、120℃、130℃、140℃。其余步骤与实施例1相同。
表2实施例2的MeOH/DMC汽相渗透分离测试结果
从表2可以看出,在不同的操作温度下(100~140℃),氟化物体系下合成的SAPO-34分子筛膜具有非常高的甲醇选择性。随着操作温度的提高,甲醇渗透通量逐渐升高,这是由于甲醇分压上升所致。
实施例3不同进料压力下SAPO-34分子筛膜分离甲醇/碳酸二甲酯
与实施例1的不同之处在于,步骤5中的进料浓度MeOH/DMC为90/10,进料压力分别为0.3MPa、0.4MPa、0.5MPa、0.6MPa。其余步骤与实施例1相同。
表3实施例3的MeOH/DMC渗透汽化分离测试结果
从表3可以看出,在不同的进料压力下,氟化物体系下合成的SAPO-34分子筛膜具有非常高的甲醇选择性;并且随着系统压力的提高,渗透通量逐渐升高。当压力达到0.5MPa时,甲醇通量持平。
实施例4添加不同氟化物合成SAPO-34分子筛膜分离甲醇/碳酸二甲酯
与实施例1的不同之处在于,步骤3中分别添加0.037g氟化钠、0.033g氟化铵。步骤5中的进料浓度MeOH/DMC为90/10,进料压力为0.3MPa。其余步骤与实施例1相同。
表4实施例4的MeOH/DMC渗透汽化分离测试结果
从表4可以看出,不同氟化物体系下合成的SAPO-34分子筛膜具有非常高的甲醇选择性及较高的渗透通量。由此可见,氟化钠和氟化铵的加入也能制备出高性能的SAPO-34分子筛膜。
其中,SAPO-34分子筛膜的表面和剖面SEM图(加入0.1mol NH4F)分别如图6、7所示,可以看出,载体表面被方形的SAPO-34晶体完全覆盖,晶体之间交联完美,晶体大小为4~7微米,分子筛膜表面平整。剖面照片显示膜厚约为5~6微米。
另外,上述制备的SAPO-34分子筛膜还可用于气液混合物的渗透汽化或汽相渗透分离,其中,气液混合物中的气体可为氮气、氢气、氧气、二氧化碳或甲烷等中的一种;气液混合物中的液体可为水、甲醇、丙酮或苯等中的一种。
Claims (9)
1.一种SAPO-34分子筛膜渗透汽化或汽相渗透分离液体混合物的方法,其特征在于,包括步骤:
1)将铝源、四乙基氢氧化铵TEAOH、水、硅源与磷源混合溶解后,得到晶种反应液,在170~210℃加热下,晶化4~7小时,离心,洗涤,干燥,得到SAPO-34分子筛晶种;
其中,铝源、磷源、硅源、四乙基氢氧化铵与晶种反应液中的总水量的摩尔比为:1Al2O3:1~2P2O5:0.3~0.6SiO2:2~6TEAOH:55~150H2O;
2)将SAPO-34分子筛晶种涂布到多孔载体管的内表面,得到涂覆了SAPO-34分子筛晶种的多孔载体管;
3)SAPO-34分子筛膜管的合成
A、将铝源、磷源、硅源、四乙基氢氧化铵TEAOH、二正丙胺、水与氟化物,混合均匀后,形成分子筛膜合成母液;
其中,铝源、磷源、硅源、四乙基氢氧化铵、二正丙胺、氟化物与分子筛膜合成母液中的总水量的摩尔比为:1Al2O3:0.5~3.5P2O5:0.05~0.6SiO2:0.5~8TEAOH:0.1~4.0二正丙胺:0.01~1F-:50~300H2O;
B、将步骤2)得到的涂覆了SAPO-34分子筛晶种的多孔载体管置于分子筛膜合成母液中,在室温~80℃下老化2~8小时后,于150~240℃下晶化3~24小时,合成SAPO-34分子筛膜管;
4)将步骤3)得到的SAPO-34分子筛膜管在370~700℃下焙烧2~8小时,得到SAPO-34分子筛膜;
5)采用渗透汽化分离工艺或汽相渗透分离工艺,利用步骤4)得到的SAPO-34分子筛膜对液体混合物进行分离;所述渗透汽化分离工艺或汽相渗透分离工艺的条件为:进料浓度MeOH/DMC=70/30,渗透操作温度为120℃,进料压力为0.3MPa,渗透侧压力控制在100Pa,进料流量为1ml/min;
其中,所述液体混合物为甲醇与甲醇以外的液体的混合物,其中,该甲醇以外的液体选自:碳酸二甲酯。
2.如权利要求1所述的方法,其特征在于:所述步骤1)、3)中,铝源选自:异丙醇铝、Al(OH)3、单质铝和铝盐中的一种或多种;其中,所述铝盐选自:硝酸铝、氯化铝、硫酸铝和磷酸铝中的一种或多种;
步骤1)、3)中,磷源选自:磷酸;
步骤1)、3)中,硅源选自:正硅酸乙酯、正硅酸甲酯、硅溶胶、白炭黑、硅酸钠和水玻璃中的一种或多种。
3.如权利要求1所述的方法,其特征在于:所述步骤1)中,加热的方式为微波加热;
步骤1)中,SAPO-34分子筛晶种的尺寸为50~1000纳米。
4.如权利要求1所述的方法,其特征在于:所述步骤2)中,多孔载体管选自:多孔陶瓷管;
其中,多孔陶瓷管的孔径为5纳米~2000纳米;多孔陶瓷管的材质选自:Al2O3、TiO2、ZrO2、SiC或氮化硅。
5.如权利要求1所述的方法,其特征在于:所述步骤2)的晶种涂布中,其具体步骤为:多孔载体管两端封釉、洗净烘干、外表面密封后,再将SAPO-34分子筛晶种涂布到多孔载体管的内表面;
涂布方法选自:刷涂法或浸涂法。
6.如权利要求1所述的方法,其特征在于:所述步骤3)中,氟化物选自:氟化氢和氟化物盐中的一种或其混合物;
其中,氟化物盐选自:氟化铵、主族金属的氟化物盐或过渡金属的氟化物盐。
7.如权利要求6所述的方法,其特征在于:所述氟化物盐选自:氟化钾、氟化钠和氟化铵中的一种或多种。
8.如权利要求1所述的方法,其特征在于:所述步骤3)中,形成分子筛膜合成母液的操作步骤如下:
将铝源、磷源与水混合,搅拌1~5小时后,加入硅源,搅拌0.5~2小时后,加入四乙基氢氧化铵,搅拌0.5~2小时后,加入二正丙胺,搅拌0.5~2小时后,加入氟化物,在室温~60℃下,搅拌12~96小时,得到均匀的分子筛膜合成母液。
9.如权利要求1所述的方法,其特征在于:所述步骤4)中,焙烧的气氛选自:惰性气体、真空、空气、氧气或任意比例的稀释氧气;
焙烧中,升温和降温速率不超过2K/分钟。
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AU2016214471A AU2016214471A1 (en) | 2015-02-03 | 2016-02-02 | Method for the pervaporation and vapor-permeation separation of gas-liquid mixtures and liquid mixtures by SAPO-34 molecular sieve membrane |
US15/547,867 US20180015420A1 (en) | 2015-02-03 | 2016-02-02 | Method for the Pervaporation and Vapor-Permeation Separation of Gas-Liquid Mixtures and Liquid Mixtures by SAPO-34 Molecular Sieve Membrane |
PCT/EP2016/052209 WO2016124614A1 (en) | 2015-02-03 | 2016-02-02 | Method for the pervaporation and vapor-permeation separation of gas-liquid mixtures and liquid mixtures by sapo-34 molecular sieve membrane |
EP16703747.2A EP3253475A1 (en) | 2015-02-03 | 2016-02-02 | Method for the pervaporation and vapor-permeation separation of gas-liquid mixtures and liquid mixtures by sapo-34 molecular sieve membrane |
BR112017014841A BR112017014841A2 (pt) | 2015-02-03 | 2016-02-02 | método para a pervaporação e separação de permeação de vapor de misturas de gás-líquido e misturas líquidas por membrana de peneira molecular sapo-34 |
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US11052346B2 (en) * | 2018-05-23 | 2021-07-06 | Molecule Works Inc. | Device and method for separation of water from mixtures |
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