CN116409792A - Method for recovering organic template agent in molecular sieve synthesis mother liquor - Google Patents
Method for recovering organic template agent in molecular sieve synthesis mother liquor Download PDFInfo
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- CN116409792A CN116409792A CN202111681114.3A CN202111681114A CN116409792A CN 116409792 A CN116409792 A CN 116409792A CN 202111681114 A CN202111681114 A CN 202111681114A CN 116409792 A CN116409792 A CN 116409792A
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- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 138
- 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 138
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000012452 mother liquor Substances 0.000 title claims abstract description 36
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 32
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 32
- 238000002425 crystallisation Methods 0.000 claims abstract description 44
- 230000008025 crystallization Effects 0.000 claims abstract description 44
- 239000002131 composite material Substances 0.000 claims abstract description 39
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 24
- 238000004064 recycling Methods 0.000 claims description 24
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 239000001632 sodium acetate Substances 0.000 claims description 8
- 235000017281 sodium acetate Nutrition 0.000 claims description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- 238000005194 fractionation Methods 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 19
- 239000010413 mother solution Substances 0.000 abstract description 14
- 239000012535 impurity Substances 0.000 abstract description 8
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 49
- 239000000243 solution Substances 0.000 description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000001914 filtration Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 238000005216 hydrothermal crystallization Methods 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000004115 Sodium Silicate Substances 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 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 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Images
Classifications
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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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- 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
-
- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a method for recovering an organic template agent in a molecular sieve synthesis mother solution, which comprises the following steps: adding a composite extractant into a molecular sieve crystallization product, and carrying out liquid-solid separation to obtain the molecular sieve product and a crystallization mother liquor rich in a template agent; fractionating the crystallization mother liquor, and recovering to obtain a template agent and a composite extractant; wherein the compound extractant is a mixture of acetate and isopropanol, and the mass ratio of acetate to isopropanol is 1: (7-10). According to the invention, the specific composite extractant is added into the molecular sieve crystallization product, so that the enrichment problem of decomposition products and impurities in the recovered template agent can be effectively solved, the content of inorganic salt ions such as sodium ions in the recovered template agent is reduced, and the template agent can be repeatedly recovered and used for not less than 3 times, namely, the template agent recovered for the 3 rd time can be used for preparing a molecular sieve material, and the problem that the quality of the molecular sieve is affected because the purity of the template agent is reduced due to the enrichment of ionic impurities is avoided.
Description
Technical Field
The invention relates to the field of molecular sieve synthesis, in particular to a method for extracting and recovering an organic amine template agent in a molecular sieve synthesis mother solution.
Background
The organic template agent is widely applied to the synthesis process of special molecular sieves such as nanometer and mesoporous molecular sieves, and the substances generally have the characteristics of strong toxicity, high unit price and large pollution, so that a large amount of waste water with strong alkalinity and high ammonia nitrogen is inevitably generated in the synthesis, washing and other processes of the special molecular sieves, and the environment is polluted. However, in the production process of the molecular sieve, only a small part of the template agent is absorbed and decomposed by the molecular sieve, and a large part of the template agent still exists in the crystallized mother liquor, so that the template agent is not utilized efficiently. At present, the template agents used in the molecular sieve synthesis process comprise Cetyl Trimethyl Ammonium Bromide (CTAB), tetraethylammonium hydroxide (TEAOH), cetyl trimethyl para-toluene sulfonic ammonium (CTATos), triethylamine (TEA), n-butylamine, ethylenediamine and the like, and the cost of the template agents accounts for about 50-70% of the cost of raw materials, so that the template agents in the synthesized molecular sieve mother solution are of great significance in terms of environmental protection and economic cost.
The template machine is recycled and recycled for preparing the molecular sieve by the person skilled in the art, but the problem that inorganic salts accumulate in the template agent recycling process, so that recycling efficiency of the recycled template agent is low and effect of recycling the template agent for multiple times is poor still exists.
CN 103787370B proposes a method for recovering template agent in the process of preparing molecular sieve, which comprises mixing raw materials of silicon source, aluminum source, phosphorus source and template agent for preparing silicoaluminophosphate molecular sieve with solution to prepare silicoaluminophosphate molecular sieve, after reaction for 1-72 hours, introducing gas phase substance in reaction system into separating equipment, separating template agent from solvent by the introduced gas phase substance, and reusing the separated template agent through pipeline. The method adopts the recycled template agent to prepare the molecular sieve, does not have adverse effect on the structure and the morphology of the molecular sieve, can reduce the production cost of the molecular sieve, reduces the discharge amount of chemicals, reduces the environmental pollution, has simple operation and low energy consumption, and can realize large-scale use. However, in the template separation process, the decomposition products and impurities are continuously enriched, so that the purity of the recovered template is reduced.
CN 104030499A proposes a comprehensive treatment method for special molecular sieve synthetic mother liquor, the special molecular sieve synthetic mother liquor is mother liquor containing silicate radical and quaternary ammonium hydroxide template agent, the special molecular sieve synthetic mother liquor is subjected to primary filtration by using tubular ceramic membrane with pore diameter of 0.1-1.2 μm, acid is added to adjust pH value to 7-8, first filtration is carried out by using a sling centrifuge, pH value of filtrate is adjusted to 5-6, stirring and flocculation are carried out, second filtration is carried out by using a sling centrifuge, the obtained filtrate is subjected to precise filtration by using tubular ceramic membrane with pore diameter of 10-50nm after standing, the filtrate is treated by using a bipolar membrane electrodialysis system, and aqueous solution and sulfuric acid solution of quaternary ammonium hydroxide pure product corresponding to quaternary ammonium hydroxide template agent contained in mother liquor wastewater are respectively prepared. The invention adopts a ceramic membrane centrifugal filtration mode to effectively recycle the quaternary ammonium alkali template agent. However, the invention generates acidic aqueous solution during the template recovery process, which pollutes the environment.
CN 112694186A proposes a method for treating organic amine wastewater, which is used for washing and treating wastewater in the production process of molecular sieves. The method firstly adopts a flocculating agent complexing method to reduce the content of suspended matters in the washing molecular sieve wastewater, then removes organic amine pollutants which are difficult to degrade and have strong toxicity in the wastewater by a membrane separation method, and the treated wastewater can reach the discharge standard. The method has high separation cost and complex separation process.
CN 109721071B proposes a method for preparing titanium-silicon molecular sieve, which comprises the steps of under hydrolysis reaction condition, first contacting aqueous solution containing template agent with organosilicon source, under hydrolysis condensation reaction condition, second contacting first hydrolysis mixture with aqueous solution containing titanium source, and during the first contact and second contact, leading out generated vapor and condensing; and mixing the hydrolytic condensation mixture with part of condensate, and performing hydrothermal crystallization. The titanium-silicon molecular sieve produced by the method can effectively inhibit the decomposition of the template agent in the hydrothermal crystallization process, and more template agent is recycled; meanwhile, the quality of hydrothermal crystallization can be improved, so that the prepared titanium-silicon molecular sieve has more uniform particle size and narrower particle size distribution, and can obtain improved catalytic activity and selectivity when used as a catalyst for hydroxylation reaction. However, the method has the advantages of complex process, long period and no industrial application prospect.
The organic template agent is widely applied to the synthesis process of special molecular sieves such as nanometer and mesoporous molecular sieves, and generally has the characteristics of strong toxicity, high unit price, large pollution, high synthesis cost of the molecular sieves, large amount of wastewater generation, environmental pollution and the like. At present, related technicians perform research on recycling of template machine and recycling of the template machine for preparing the molecular sieve, but inorganic salts accumulate in the template agent recycling process, so that the recycling efficiency of the template agent is low, the template agent recycling effect is poor for a plurality of times, the purity of the recycled template agent is reduced, and the quality of the molecular sieve is seriously influenced.
Disclosure of Invention
The invention mainly aims to provide a method for recycling an organic template agent in a molecular sieve synthesis mother solution, so as to solve the problems of low recycling efficiency of the template agent and poor effect of recycling the template agent for multiple times in the molecular sieve synthesis process in the prior art.
In order to achieve the above purpose, the invention provides a method for recycling an organic template agent in a molecular sieve synthesis mother solution, which comprises the following steps:
adding a composite extractant into a molecular sieve crystallization product, and carrying out liquid-solid separation to obtain the molecular sieve product and a crystallization mother liquor rich in a template agent;
fractionating the crystallization mother liquor, and recovering to obtain a template agent and a composite extractant;
wherein the compound extractant is a mixture of acetate and isopropanol, and the mass ratio of acetate to isopropanol is 1: (7-10).
The invention relates to a method for recycling an organic template agent in a molecular sieve synthesis mother solution, wherein the molecular sieve crystallization product is obtained after crystallization is completed in the process of synthesizing a molecular sieve in the presence of the template agent.
The invention relates to a method for recycling an organic template agent in a molecular sieve synthesis mother solution, wherein the template agent is an ammonium cationic surfactant, and acetate is a soluble salt taking acetate ions as anions.
The invention relates to a method for recycling an organic template agent in a molecular sieve synthesis mother solution, wherein the template agent is at least one of cetyl trimethyl ammonium bromide, tetraethyl ammonium hydroxide and cetyl trimethyl para-toluene ammonium sulfonate; the acetate is at least one of sodium acetate, potassium acetate and ammonium acetate.
The invention relates to a method for recovering an organic template agent in a molecular sieve synthesis mother solution, wherein the molecular sieve product is at least one of an MCM molecular sieve, a ZSM-5 molecular sieve and an SBA-15 molecular sieve.
The invention relates to a method for recycling an organic template agent in a molecular sieve synthesis mother solution, wherein the temperature of adding a molecular sieve crystallization product into a composite extracting agent is 35-55 ℃.
The invention relates to a method for recycling an organic template agent in a molecular sieve synthesis mother solution, wherein the fractionation treatment is normal pressure distillation, and the distillation temperature is 80-120 ℃.
The invention relates to a method for recycling an organic template agent in a molecular sieve synthesis mother solution, wherein the recycled template agent is circularly used for synthesizing a molecular sieve, and a recycled composite extractant is circularly added into a molecular sieve crystallization product for liquid-solid separation.
The invention relates to a method for recycling organic template agent in a molecular sieve synthesis mother solution, wherein the recycling time of the template agent obtained by recycling is 1-3 times.
The invention has the beneficial effects that:
according to the invention, the specific composite extractant is added into the molecular sieve crystallization product, so that the enrichment problem of decomposition products and impurities in the recovered template agent can be effectively solved, the content of inorganic salt ions such as sodium ions in the recovered template agent is reduced, and the template agent can be repeatedly recovered and used for not less than 3 times, namely, the template agent recovered for the 3 rd time can be used for preparing a molecular sieve material, and the problem that the quality of the molecular sieve is affected because the purity of the template agent is reduced due to the enrichment of ionic impurities is avoided.
Drawings
FIG. 1 is an XRD spectrum of an MCM-41 molecular sieve obtained in an embodiment of the invention.
Detailed Description
The following describes the present invention in detail, and the present examples are implemented on the premise of the technical solution of the present invention, and detailed embodiments and processes are given, but the scope of protection of the present invention is not limited to the following examples, in which the experimental methods of specific conditions are not noted, and generally according to conventional conditions.
The invention provides a method for recycling an organic template agent in a molecular sieve synthesis mother solution, which comprises the following steps:
adding a composite extractant into a molecular sieve crystallization product, and carrying out liquid-solid separation to obtain the molecular sieve product and a crystallization mother liquor rich in a template agent;
fractionating the crystallization mother liquor, and recovering to obtain a template agent and a composite extractant;
wherein the compound extractant is a mixture of acetate and isopropanol, and the mass ratio of acetate to isopropanol is 1: (7-10).
According to the invention, the specific composite extractant is added into the molecular sieve crystallization product, so that the enrichment problem of decomposition products and impurities in the recovered template agent can be effectively solved, the content of inorganic salt ions such as sodium ions in the recovered template agent is reduced, and the template agent can be repeatedly recovered and used for not less than 3 times, namely, the template agent recovered for the 3 rd time can be used for preparing a molecular sieve material, and the problem that the quality of the molecular sieve is affected because the purity of the template agent is reduced due to the enrichment of ionic impurities is avoided.
The method can be used for recovering template agents in molecular sieves prepared by using the template agents, wherein the molecular sieves are MCM molecular sieves, ZSM-5 molecular sieves, SBA-15 molecular sieves and the like. The composite extractant is added in the preparation process of the molecular sieve, but the preparation method of the molecular sieve is not particularly limited, for example, the preparation process of the molecular sieve comprises a crystallization step, and the composite extractant is added in a crystallization product of the molecular sieve.
In one embodiment, the invention provides a method for preparing a crystallized product of a molecular sieve, comprising mixing a template agent, a silicon source and an aluminum source to form a gel solution. And adding the gel solution into a crystallization kettle for hydrothermal crystallization treatment, and obtaining a crystallization product after crystallization.
And (3) cooling the crystallized product to room temperature, adding the composite extractant, stirring, and carrying out liquid-solid separation to obtain a molecular sieve product and a crystallized mother liquor rich in the template agent.
The silicon source and the aluminum source are not particularly limited, and the silicon source and the aluminum source are conventional in the art. The template agent is an organic amine template agent; in one embodiment, the templating agent of the present invention is an ammonium based cationic surfactant; in another embodiment, the templating agent of the present invention is at least one of cetyltrimethylammonium bromide, tetraethylammonium hydroxide, cetyltrimethyl-p-toluenesulfonammonium.
The composite extractant is a mixture of acetate and isopropanol, and the mass ratio of the acetate to the isopropanol is 1: (7-10). In one embodiment, the acetate salt of the present invention is a soluble salt having acetate ion as anion, such as sodium acetate, potassium acetate, ammonium acetate. The dosage of the composite extractant of the invention is that the composite extractant: the mass ratio of the molecular sieve crystallization products is 1: (1-3).
The present invention is not particularly limited to the liquid-solid separation method, and examples thereof include filtration, centrifugation, and the like. The solid obtained after liquid-solid separation is a molecular sieve product, and the type of the molecular sieve depends on the preparation raw materials and the preparation method, and the added composite extractant does not influence or change the type of the prepared molecular sieve. The molecular sieve product obtained by filtration can be subjected to operation treatments such as drying, roasting and the like, and finally the expected molecular sieve is obtained.
And (3) fractionating the crystallization mother liquor, and recovering to obtain the template agent and the composite extractant. The present invention is not particularly limited in the specific manner of fractionation, and is, for example, distillation treatment, more particularly, atmospheric distillation at a distillation temperature of 80 to 120℃and at an atmospheric pressure.
In one embodiment, the recovered template agent is recycled for synthesizing the molecular sieve, and the recovered composite extractant is recycled for adding the molecular sieve crystallization product for liquid-solid separation.
The template agent recovered by the method has less impurities, can be circularly used for preparing the molecular sieve, can still synthesize the molecular sieve material with high specific surface area and large pore volume, and the specific surface area of the prepared molecular sieve can be kept at 800m 2 About/g, the pore volume is 1.60-1.93 mL/g, the template agent can be reused for 1-3 times, and the total recovery rate of the template agent can reach 73.8%.
The technical scheme of the invention is further described in detail through specific examples.
Evaluation analysis method:
specific surface area and pore volume test: specific surface area and pore structure of the silica alumina material and the catalyst were measured on ASAP2020M specific surface area and porosity analyzer manufactured by Micromeritics company, and the specific surface area was calculated according to BET method; the BJH method calculates pore volume.
Example 1
25wt% CTAB solution (CTAB mass G1=22.5G) was placed in a 60 ℃ constant temperature water bath, 29G of deionized water was added, and after stirring until CTAB was dissolved uniformly, 91.6G of 25wt% sodium silicate solution and 72.5G of 20wt% aluminum sulfate solution were sequentially added, and the solution was dynamically treated at 30 ℃ for 4 hours to form an A gel solution. And (3) transferring the mixture gel into a crystallization kettle, and performing hydrothermal crystallization for 48 hours at the temperature of 100 ℃ to obtain a crystallized product B. And cooling the synthesized crystallized product B. And adding a sodium acetate/isopropanol composite extractant with the mass ratio of 1:7 into the cooled crystallized product, wherein the total mass of the composite extractant is 145g, stirring, filtering and separating to obtain mother liquor rich in template agent and a molecular sieve product. And (3) distilling and separating the mother liquor rich in the template agent to obtain the template agent and the weak acid compound extractant, and recovering the obtained template agent for repeatedly synthesizing the molecular sieve material, and repeatedly extracting and separating the crystallization product by the weak acid compound extractant. The template agent M1=14.7g is recovered, the template agent recovery rate is 65.3%, and the texture properties of the synthesized MCM molecular sieve material are shown in table 1.
Example 2
Template M1 recovered in example 1 was used in duplicate to prepare MCM molecular sieve material along with additional fresh template g2=7.7g (22.5G-M1), the procedure was the same as in example 1, and template m2=12.5G was recovered to give the resultant MCM molecular sieve material with texture properties as shown in table 1.
Example 3
Template M2 recovered in example 2 was used in duplicate to prepare MCM molecular sieve material along with additional fresh template g3=9.9G (22.5G-M2), the procedure was the same as in example 1, and template m3=10.9G was recovered to give the resultant MCM molecular sieve material with texture properties as shown in table 1.
Example 4
Template M3 recovered in example 3 was used in duplicate to prepare MCM molecular sieve material along with additional fresh template g4=11.5G (22.5G-M3), the procedure was the same as in example 1, and template m4=9.7G was recovered to give the synthesized MCM molecular sieve material with texture properties as shown in table 1.
Example 5
Template M4 recovered in example 4 was used in duplicate to prepare an MCM molecular sieve material, with additional fresh template g5=12.7g (22.5G-M4), and the procedure was the same as in example 1, and the texture properties of the synthesized MCM molecular sieve material are shown in table 1.
FIG. 1 is an XRD spectrum of the MCM-41 molecular sieve obtained in examples 1-5 of the present invention. As shown in FIG. 1, four (100), (110), (200) and (210) crystal face diffraction characteristic peaks appear at about 2.1 degrees, 3.7 degrees, 4.3 degrees and 5.6 degrees of the molecular sieve, wherein the (100) crystal face peak with high peak intensity is MCM-41 characteristic peak, and the recovery template agent CTAB spontaneously aggregates to form hexagonal liquid crystal phase control molecular sieve synthesis crystallization to form the MCM-41 molecular sieve.
Example 6
CTAB mass G1=22.5G solution with the concentration of 25wt% is placed in a constant-temperature water bath with the temperature of 60 ℃, 29G deionized water is added, after the CTAB solution is stirred until the CTAB solution is uniformly dissolved, 91.6G sodium silicate solution with the concentration of 25wt% and 72.5G aluminum sulfate solution with the concentration of 20wt% are sequentially added, and the solution is dynamically treated for 4 hours at the temperature of 30 ℃ to form an A gel solution. And (3) transferring the mixture gel into a crystallization kettle, and performing hydrothermal crystallization for 48 hours at the temperature of 100 ℃ to obtain a crystallized product B. And cooling the synthesized crystallized product B. And adding a sodium acetate/isopropanol composite extractant with the mass ratio of 1:8 into the cooled crystallized product, wherein the adding amount of the composite extractant is 145g, stirring, filtering and separating to obtain mother liquor rich in template agent and a molecular sieve product. And (3) distilling and separating the mother liquor rich in the template agent to obtain the template agent and the weak acid compound extractant, and recovering the obtained template agent for repeatedly synthesizing the molecular sieve material, and repeatedly extracting and separating the crystallization product by the weak acid compound extractant. Template agent M1=17.57 g is recovered, template agent recovery rate is 78.08%, and texture properties of the synthesized MCM molecular sieve material are shown in table 2.
Example 7
CTAB solution with the concentration of 25wt% (CTAB mass G1=22.5G) is placed in a constant-temperature water bath with the temperature of 60 ℃, 29G of deionized water is added, after the solution is stirred until CTAB is uniformly dissolved, 91.6G of sodium silicate solution with the concentration of 25wt% and 72.5G of aluminum sulfate solution with the concentration of 20wt% are sequentially added, and the solution is dynamically treated for 4 hours at the temperature of 30 ℃ to form gel A solution. And (3) transferring the mixture gel into a crystallization kettle, and performing hydrothermal crystallization for 48 hours at the temperature of 100 ℃ to obtain a crystallized product B. And cooling the synthesized crystallized product B. And adding a sodium acetate/isopropanol composite extractant with the mass ratio of 1:10 into the cooled crystallized product, wherein the adding amount of the composite extractant is 145g, stirring, filtering and separating, separating mother liquor rich in the template agent by normal pressure distillation to obtain the template agent and the weak acid composite extractant, recovering the obtained template agent for repeatedly synthesizing the molecular sieve material, and repeatedly extracting and separating the crystallized product by the weak acid composite extractant. Template agent M1=18.01 g is recovered, template agent recovery rate is 80.04%, and texture properties of the synthesized MCM molecular sieve material are shown in table 2.
Example 8
A solution was prepared by mixing 23.26g of tetrapropylammonium hydroxide (TPAOH) with 24.22g of tetraethyl orthosilicate (TEOS) and 70g of deionized water, and using 1.09g of Al (NO) 3 ) 39 H 2 O, 0.47g NaOH and 27.75g 27.75g H 2 Mixing O to prepare a solution B; then hydrolyzing the solution A for 3h at 35 ℃, then adding the solution B into the solution A, wherein the molar ratio of each component in the raw materials is n (Na 2 O)∶n(Al 2 O 3 )∶n(SiO 2 )∶n(TPAOH)∶n(H 2 O) =0.05:0.0125:1:0.25:55; the mixture is stirred for 90min at 35 ℃, then transferred into a stainless steel crystallization kettle, and placed in a 170 ℃ oven for standing and crystallization for 24h. After crystallization is completed, separating a solid product, washing the solid product with deionized water for 3 times, drying the solid product at 120 ℃ for 12 hours, and roasting the solid product at 540 ℃ for 4 hours to obtain a sample, namely the ZSM-5 molecular sieve.
Comparative example 1
25wt% CTAB solution (CTAB mass G1=22.5G) was placed in a 60 ℃ constant temperature water bath, 29G of deionized water was added, and after stirring until CTAB was dissolved uniformly, 91.6G of 25wt% sodium silicate solution and 72.5G of 20wt% aluminum sulfate solution were sequentially added, and the solution was dynamically treated at 30 ℃ for 4 hours to form an A gel solution. And (3) transferring the mixture gel into a crystallization kettle, and performing hydrothermal crystallization for 48 hours at the temperature of 100 ℃ to obtain a crystallized product B. And cooling the synthesized crystallized product B. And then 145g of extractant ethanol is added into the cooled crystallized product, and the mixture is stirred, filtered and separated to obtain mother liquor rich in template agent and molecular sieve product. The template recovery rate was 42.3%.
Comparative example 2
25wt% CTAB solution (CTAB mass G1=22.5G) was placed in a 60 ℃ constant temperature water bath, 29G of deionized water was added, and after stirring until CTAB was dissolved uniformly, 91.6G of 25wt% sodium silicate solution and 72.5G of 20wt% aluminum sulfate solution were sequentially added, and the solution was dynamically treated at 30 ℃ for 4 hours to form an A gel solution. And (3) transferring the mixture gel into a crystallization kettle, and performing hydrothermal crystallization for 48 hours at the temperature of 100 ℃ to obtain a crystallized product B. And cooling the synthesized crystallized product B. And adding a sodium acetate/isopropanol composite extractant with the mass ratio of 1:3 into the cooled crystallized product, wherein the total mass of the composite extractant is 145g, stirring, filtering and separating to obtain mother liquor rich in template agent and a molecular sieve product, and the template agent recovery rate is 48.2%.
Comparative example 3
25wt% CTAB solution (CTAB mass G1=22.5G) was placed in a 60 ℃ constant temperature water bath, 29G of deionized water was added, and after stirring until CTAB was dissolved uniformly, 91.6G of 25wt% sodium silicate solution and 72.5G of 20wt% aluminum sulfate solution were sequentially added, and the solution was dynamically treated at 30 ℃ for 4 hours to form an A gel solution. And (3) transferring the mixture gel into a crystallization kettle, and performing hydrothermal crystallization for 48 hours at the temperature of 100 ℃ to obtain a crystallized product B. And cooling the synthesized crystallized product B. And adding a sodium acetate/isopropanol composite extractant with the mass ratio of 1:14 into the cooled crystallized product, wherein the total mass of the composite extractant is 145g, stirring, filtering and separating to obtain mother liquor rich in the template agent and the template agent recovery rate of the molecular sieve product of 58%.
Table 1 example synthetic molecular sieve properties
Note that: template total recovery = (m1+m2+m3)/(g1+g2+g3+g4)
Table 2 example synthetic molecular sieve properties
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The method for recycling the organic template agent in the molecular sieve synthesis mother liquor is characterized by comprising the following steps of:
adding a composite extractant into a molecular sieve crystallization product, and carrying out liquid-solid separation to obtain the molecular sieve product and a crystallization mother liquor rich in a template agent;
fractionating the crystallization mother liquor, and recovering to obtain a template agent and a composite extractant;
wherein the compound extractant is a mixture of acetate and isopropanol, and the mass ratio of acetate to isopropanol is 1: (7-10).
2. The method for recovering an organic template agent from a molecular sieve synthesis mother liquor according to claim 1, wherein the molecular sieve crystallization product is obtained after crystallization is completed in the process of synthesizing a molecular sieve in the presence of the template agent.
3. The method for recovering an organic template agent from a mother liquor for molecular sieve synthesis according to claim 1, wherein the template agent is an ammonium cationic surfactant, and the acetate is a soluble salt with acetate ion as an anion.
4. The method for recovering an organic template agent from a molecular sieve synthesis mother liquor according to claim 3, wherein the template agent is at least one of cetyltrimethylammonium bromide, tetraethylammonium hydroxide and cetyltrimethyl-p-toluenesulfonammonium; the acetate is at least one of sodium acetate, potassium acetate and ammonium acetate.
5. The method for recovering an organic template agent from a molecular sieve synthesis mother liquor according to claim 1, wherein the molecular sieve product is at least one of an MCM molecular sieve, a ZSM-5 molecular sieve and an SBA-15 molecular sieve.
6. The method for recovering an organic template agent from a molecular sieve synthesis mother liquor according to claim 1, wherein the pH value of the composite extractant is 6-8, and the composite extractant is added in an amount such that the composite extractant: the mass ratio of the molecular sieve crystallization products is 1:1-3.
7. The method for recovering an organic template agent from a molecular sieve synthesis mother liquor according to claim 1, wherein the temperature of adding the composite extractant into the molecular sieve crystallization product is 35-55 ℃.
8. The method for recovering an organic template in a molecular sieve synthesis mother liquor according to claim 1, wherein the fractionation treatment is atmospheric distillation at a distillation temperature of 80 to 120 ℃.
9. The method for recycling organic template in molecular sieve synthesis mother liquor according to claim 1, wherein the recycled template is recycled for synthesizing the molecular sieve, and the recycled composite extractant is recycled to be added into a molecular sieve crystallization product for liquid-solid separation.
10. The method for recovering an organic template in a mother liquor for synthesizing a molecular sieve according to claim 9, wherein the number of cycles of the recovered template for synthesizing the molecular sieve is 1 to 3.
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