CN112892471A - Preparation method of VOCs adsorbent molecular sieve with ultrahigh hydrophobic property - Google Patents
Preparation method of VOCs adsorbent molecular sieve with ultrahigh hydrophobic property Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 56
- 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 56
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 21
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 18
- 239000003463 adsorbent Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 42
- 239000010703 silicon Substances 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000499 gel Substances 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 4
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 239000011863 silicon-based powder Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 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
- 239000006229 carbon black Substances 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000001282 organosilanes Chemical class 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 2
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 238000002444 silanisation Methods 0.000 abstract description 10
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 24
- 229910021536 Zeolite Inorganic materials 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 11
- 239000010457 zeolite Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000008710 crystal-8 Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—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
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
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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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention discloses a preparation method of a VOCs adsorbent molecular sieve with ultrahigh hydrophobic property, which is characterized in that a molecular sieve product is subjected to surface silanization treatment by a one-step method to obtain an HZSM5 molecular sieve with ultrahigh hydrophobic property, and the molecular sieve is applied to the aspect of VOCs tail gas adsorption degradation.
Description
Technical Field
The invention belongs to the technical field of molecular sieve preparation, and particularly relates to a preparation method of a VOCs adsorbent molecular sieve with ultrahigh hydrophobic property.
Background
Volatile Organic Compounds (VOCs) are organic compounds having a saturated vapor pressure of greater than 0.13kPa under standard conditions, and include more than 300 organic compounds such as hydrocarbons, aldehydes, ketones, alcohols, ethers, esters, heteroatom-substituted hydrocarbons, and the like. VOCs in the atmosphere have the characteristics of various types, wide sources, high toxicity, relatively low concentration, high total pollutant amount and the like. The adsorption method is one of the main purification methods for VOCs, and compared with other methods, the adsorption method has the advantages of mature process, simple operation, low energy consumption, high purification efficiency and the like, is suitable for purifying VOCs with low concentration and high air volume, and has the defects of low adsorption efficiency at high temperature, inhibited adsorption of VOCs at high humidity and the like.
Zeolite molecular sieves are one of the excellent adsorbents, widely used in the production of basic organic chemicals and petrochemical industries, and in the treatment of harmful gases, are also commonly used for the purification of SO2, NOx, CO2, NH3, CCl4, water vapor and gaseous hydrocarbon exhaust gases. Mainly because it has the following characteristics: 1. the molecular sieve has strong adsorption selectivity. The molecular sieve is uniform in pore size and is an ionic adsorbent, so that the molecular sieve can perform selective adsorption according to different molecular sizes and polarities; 2. the molecular sieve has strong adsorption capacity. Even if the composition concentration of the gas is low, the gas still has large adsorption capacity. 3. The molecular sieve still has larger adsorption capacity at higher temperature, but other adsorbents are greatly influenced by the temperature, so that the adsorption capacity of the molecular sieve is large under the same temperature condition.
With the continuous and deep research, the zeolite rotating wheel concentration technology is a new technology developed for the treatment of low-concentration VOCs at present, and is combined with a chemical method to form the zeolite rotating wheel concentration and incineration technology. In the whole zeolite rotary wheel adsorption concentration technology, a hydrophobic zeolite molecular sieve for adsorption concentration is the core of the technology, the advantages of the zeolite molecular sieve as a hydrophobic adsorption material are more and more obvious, a plurality of patents related to the use of the zeolite molecular sieve as an adsorbent for treating VOCs at home and abroad at present mainly include US6281406B1, US4705909, CN1781885A, CN11055906A, CN1280977A, CN1749226A, CN201710375783 and the like, and when the synthesized molecular sieve in the patents is used as the adsorbent, the following main defects exist: firstly, when the molecular sieve is used as an adsorbent, some inorganic or organic materials are required to be added to be used as a binder, so that the product synthesis steps are complicated, toxic and harmful substances are required to be added in the process, and the industrial production is not facilitated; and secondly, the hydrophobic property and the hydrothermal stability of the molecular sieve need to be further improved, because the VOCs belong to organic waste gas with low concentration and high water content, the absorption efficiency is directly influenced by the level of the hydrophobic property. Therefore, how to improve the hydrophobic property of the molecular sieve product becomes a critical technology which needs to be solved urgently at present.
The molecular sieve modification mainly comprises two methods, namely dealumination modification and grafting modification, wherein the dealumination modification comprises a high-temperature hydrothermal method, an acid-base modification method and the like; the grafting modification is silanization reaction, organic functional groups are grafted on the surface through the action of a silanization reagent and silicon hydroxyl on the surface of the molecular sieve, and the grafting modification is mainly realized through a covalent structure of the silicon hydroxyl Si-OH and organic silicon. The invention changes the traditional silanization technology, and the silanization reaction is directly introduced into the synthesis of the molecular sieve by a one-step method, thereby obtaining excellent use effect.
Disclosure of Invention
The invention aims to provide a preparation method of an HZSM5 zeolite molecular sieve which is an ultrahigh hydrophobic VOCs adsorbent with low cost and low energy consumption and can realize industrial production aiming at the defects and the defects in the prior art.
In order to achieve the purpose of the invention, the invention is realized by adopting the following scheme:
a preparation method of a VOCs adsorbent molecular sieve with ultrahigh hydrophobic property is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing a silicon source, an alkali source, a template agent, ZSM-5 molecular sieve seed crystals and water to form gel;
(2) placing the gel obtained in the step (1) in a reaction kettle for hydrothermal crystallization, and after the reaction is finished, carrying out quenching and cooling to obtain a product A;
(3) after the temperature of the product in the step (2) is reduced to room temperature, adding an organic alcohol solvent and an organic silane reagent into the reaction kettle according to a certain proportion, uniformly stirring, and continuously crystallizing for 6-12 hours at the temperature of 100-;
(4) carrying out solid-liquid separation, washing, drying and roasting on the product obtained in the step (3) to obtain molecular sieve raw powder;
(5) and (4) putting the molecular sieve raw powder obtained in the step (4) into a dilute acid solution for ion exchange, and then drying and roasting to obtain the HZSM-5 molecular sieve.
Furthermore, the water, the alkali source, the template agent and the silicon source in the step (1) are calculated by the oxides thereof, the molar ratio of each component in the mixture is (2-10): 0.03-0.20): 0.03-0.50):1, and the addition amount of the seed crystal in the step (1) is 0.05-10% of the mass of the SiO 2.
Further, the silicon source in the step (1) is selected from any one or a mixture of more of solid silica gel, sodium silicate nonahydrate, silicon powder, white carbon black, diatomite, silicate and ethyl orthosilicate; the alkali source is any one or mixture of sodium hydroxide and potassium hydroxide; the template agent is selected from one or a mixture of more of methylamine, diethylamine, tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, 1, 6-hexanediamine, n-butylamine and hexadecyltrimethylammonium bromide.
Further, the seed crystal in the step (1) is a commercial or self-made ZSM5 molecular sieve seed crystal.
Further, the hydrothermal crystallization temperature in the step (2) is 150-.
Further, the organic alcohol solvent in the step (3) is selected from any one or a mixture of methanol, ethanol, cyclohexanol, isobutanol and ethylene glycol; the organosilane reagent is selected from one or more of trimethylchlorosilane, hexamethylsilane and hexamethyldisilazane.
Further, in the step (3), the mass ratio of the product A, the organic alcohol solvent and the organic silane reagent is 1:0.5: 5.
Further, in the step (4), the drying temperature is 120 ℃, the drying time is 12 hours, the roasting temperature is 500-550 ℃, and the roasting time is 6-12 hours.
Further, the ion exchange conditions in the step (5) are as follows: the raw materials are placed in a 0.5-2 mol.L < -1 > diluted acid solution and stirred for 1-4 hours, wherein the liquid-solid mass ratio of the exchange solution to the molecular sieve raw powder is 10-20:1, the exchange temperature is 60-95 ℃, and the ion exchange process is repeated for 1-3 times.
Further, the dilute acid solution is any one or a mixture of more of sulfuric acid, hydrochloric acid or nitric acid solution.
The HZSM5 molecular sieve prepared by the synthesis method is applied to the adsorption and degradation of VOCs.
Compared with the prior art, the method for synthesizing the HZSM5 zeolite molecular sieve with ultrahigh hydrophobic property has the following advantages:
1) the synthesis process is simple and feasible, the used raw materials are low in price, no toxic substance is added in the preparation process, the product cost is low, and the environmental protection pressure is low.
2) The HZSM5 molecular sieve obtained by the invention has stronger hydrophobic property, ultrahigh hydrothermal stability and strong VOCs adsorption property.
3) The molecular sieve silanization treatment process is simplified into one-step silanization treatment, so that the method is better realized and has more industrial value.
Drawings
FIG. 1 is an XRD pattern for examples 1-5 and a comparative sample.
FIG. 2a is an SEM image of a silanized sample of example 1;
fig. 2b is an SEM image of a comparative non-silanized sample.
Wherein: in fig. 1, the abscissa represents the 2 θ angle range scanned by the XRD diffractometer, and the ordinate represents the lightness of diffraction peak. In FIG. 1, A, B, C, D, E, F show XRD patterns of examples 1 to 5 and a comparative sample, respectively, A to E are silanized samples, and F is a sample which has not been silanized. It can be seen from the figure that the crystal structure of the sample is well maintained before and after the silanization treatment while maintaining good hydrophobic properties.
The ten-small grid in FIG. 2 represents 1 μm. Fig. 2a is a silanized sample and fig. 2b is an un-silanized sample. As can be seen from FIGS. 2a and 2b, the morphology of the sample before and after the silanization treatment has not changed significantly while maintaining good hydrophobic property, and the morphology of the crystal is well maintained.
Detailed Description
The present invention is further illustrated by the following specific examples, but the present invention is not limited to the following examples.
The raw materials used in the examples are as follows:
the synthesis method of the ZSM-5 molecular sieve seed crystal comprises the following steps: 3.0g of sodium hydroxide, 70g of silica gel and 120g of deionized water are dissolved in 11g of TPAOH, the gel is put into a crystallization kettle after being evenly stirred, and crystallization is carried out for 24 hours at 160 ℃. Washing the crystallized product until the pH value is 8, and drying the product at 100 ℃ for 12 h; example 1
Silicon source (silicon powder), alkali source (NaOH) and template agent (tetrapropylammonium hydroxide) are mixed according to the weight ratio of 200SiO 2: 25 NaOH: mixing 10TPAOH and 800H2O in proportion to prepare gel, placing the gel in a crystallization kettle, crystallizing the gel for 48 hours at 160 ℃, cooling the gel by water after the crystallization is finished, adding 5g of methanol and 15g of hexamethylsilane solvent, uniformly mixing, placing the mixture in a condition of 150 ℃ for reacting for 6 hours, washing, drying and roasting the mixture, and exchanging the mixture to obtain the high-silicon ZSM-5 molecular sieve (sample 1).
Example 2
A silicon source (solid silica gel), an alkali source (NaOH), a template (tetrapropylammonium hydroxide), according to a ratio of 200SiO 2: 25 NaOH: a gel was prepared by mixing 10 TPABr: 3000H2O, and 1% of commercial ZSM5 seed crystals (based on the mass of SiO 2) were added. And (3) placing the mixture in a crystallization kettle, crystallizing the mixture at 160 ℃ for 48h, cooling the crystallized mixture by water, adding 5g of methanol and 15g of methylsilane solvent into the crystallized mixture, uniformly mixing the mixture, placing the mixed mixture at 150 ℃ for reacting for 10h, washing, drying, roasting and exchanging the mixture to obtain the high-silicon ZSM-5 molecular sieve (sample 2).
Example 3
A silicon source (solid silica gel), an alkali source (NaOH), a template (tetrapropylammonium hydroxide), according to a ratio of 200SiO 2: 25 NaOH: a gel was prepared by mixing 10 TPABr: 3000H2O, and 3% of commercial ZSM5 seed crystals (based on the mass of SiO 2) were added. And (3) placing the mixture in a crystallization kettle, crystallizing the mixture at 160 ℃ for 48h, cooling the crystallized mixture by water, adding 5g of methanol and 15g of methylsilane solvent into the crystallized mixture, uniformly mixing the mixture, placing the mixture at 150 ℃ for reaction for 12h, washing, drying, roasting and exchanging the mixture to obtain the high-silicon ZSM-5 molecular sieve (sample 3).
Example 4
A silicon source (solid silica gel), an alkali source (NaOH), a template (tetrapropylammonium hydroxide), according to a ratio of 200SiO 2: 25 NaOH: a gel was prepared by mixing 10 TPABr: 3000H2O, and 5% of commercial ZSM5 seed crystals (based on the mass of SiO 2) were added. And (3) placing the mixture in a crystallization kettle, crystallizing the mixture for 48 hours at 160 ℃, cooling the mixture by water after the crystallization is finished, washing, drying and roasting the mixture, and exchanging the mixture to obtain the high-silicon ZSM-5 molecular sieve (sample 4).
Example 5
A silicon source (solid silica gel), an alkali source (NaOH), a template (tetrapropylammonium hydroxide), according to a ratio of 200SiO 2: 25 NaOH: a gel was prepared by mixing 10 TPABr: 3000H2O, and 8% of commercial ZSM5 seed crystals (based on the mass of SiO 2) were added. And (3) placing the mixture in a crystallization kettle, crystallizing the mixture at 160 ℃ for 48h, cooling the crystallized mixture by water, adding 5g of methanol and 15g of methylsilane solvent into the crystallized mixture, uniformly mixing the mixture, placing the mixed mixture at 150 ℃ for reaction for 12h, washing, drying, roasting and exchanging the mixed mixture to obtain the high-silicon ZSM-5 molecular sieve (sample 5).
Control sample
Silicon source (silicon powder), alkali source (NaOH) and template agent (tetrapropylammonium hydroxide) are mixed according to the weight ratio of 200SiO 2: 25 NaOH: 10TPABr to 800H2O, adding commercial ZSM5 seed crystal 8% (based on the mass of SiO 2), placing in a crystallization kettle, crystallizing at 160 ℃ for 48H, cooling with water after crystallization, washing, drying, roasting, and exchanging to obtain the high-silicon ZSM-5 molecular sieve (sample 6).
Molecular sieve adsorption performance test
The hydrophobic properties of the molecular sieve samples of examples 1-5 and the comparative sample were tested with reference to national standard GB6287-1986 molecular sieve static water adsorption determination method, and several common organic substances were selected as VOCs source samples for testing. The results are shown in Table 1:
| adsorbed species | Sample 1 | Sample 2 | Sample 3 | Sample No. 4 | Sample No. 5 | Control sample |
| Water (W) | 1.5 | 1.4 | 1.3 | 0.9 | 0.76 | 1.66 |
| Toluene | 11.31 | 11.48 | 11.57 | 12.09 | 12.45 | 11.38 |
| Ethyl acetate | 12.72 | 13.26 | 12.98 | 13.11 | 13.29 | 13.01 |
| N-hexane | 12.34 | 13.18 | 12.79 | 13.21 | 13.54 | 12.16 |
| Methanol | 13.18 | 12.99 | 12.91 | 13.67 | 13.55 | 12.55 |
| Acetone (II) | 13.16 | 13.06 | 13.49 | 13.65 | 14.07 | 13.07 |
| N-butylamine | 12.67 | 13.26 | 12.91 | 13.29 | 13.77 | 12.77 |
| Cyclohexene | 8.15 | 8.07 | 7.99 | 8.19 | 8.28 | 8.03 |
From the data in table 1, it can be seen that: (1) compared with a comparison sample (which is not subjected to silanization treatment), the high-silicon ZSM-5 prepared by the synthesis method disclosed by the invention is weaker in water adsorption effect than the comparison sample, so that the zeolite molecular sieve prepared by the synthesis method disclosed by the invention is stronger in hydrophobicity; (2) the zeolite molecular sieve prepared by the synthesis method of the invention has higher adsorption capacity to various VOCs molecules than a comparison sample.
Claims (10)
1. A preparation method of a VOCs adsorbent molecular sieve with ultrahigh hydrophobic property is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing a silicon source, an alkali source, a template agent, ZSM-5 molecular sieve seed crystals and water to form gel;
(2) placing the gel obtained in the step (1) in a reaction kettle for hydrothermal crystallization, and after the reaction is finished, carrying out quenching and cooling to obtain a product A;
(3) after the temperature of the product in the step (2) is reduced to room temperature, adding an organic alcohol solvent and an organic silane reagent into the reaction kettle according to a certain proportion, uniformly stirring, and continuously crystallizing for 6-12 hours at the temperature of 100-;
(4) carrying out solid-liquid separation, washing, drying and roasting on the product obtained in the step (3) to obtain molecular sieve raw powder;
(5) and (4) putting the molecular sieve raw powder obtained in the step (4) into a dilute acid solution for ion exchange, and then drying and roasting to obtain the HZSM-5 molecular sieve.
2. The method of claim 1, wherein: the molar ratio of the components in the mixture is (2-10): (0.03-0.20): (0.03-0.50):1, and the addition amount of the seed crystal in the step (1) is 0.05-10% of the mass of the SiO2, based on the oxides of the water, the alkali source, the template agent and the silicon source in the step (1).
3. The method of claim 1, wherein: the silicon source in the step (1) is selected from any one or a mixture of more of solid silica gel, sodium silicate nonahydrate, silicon powder, white carbon black, diatomite, silicate and tetraethoxysilane; the alkali source is any one or mixture of sodium hydroxide and potassium hydroxide; the template agent is selected from one or a mixture of more of methylamine, diethylamine, tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, 1, 6-hexanediamine, n-butylamine and hexadecyltrimethylammonium bromide.
4. The method of claim 1, wherein: the seed crystal in the step (1) is a commercial or self-made ZSM5 molecular sieve seed crystal.
5. The method of claim 1, wherein: the hydrothermal crystallization temperature in the step (2) is 150-180 ℃, and the hydrothermal time is 18-48 h.
6. The method of claim 1, wherein: the organic alcohol solvent in the step (3) is selected from any one or a mixture of methanol, ethanol, cyclohexanol, isobutanol and ethylene glycol; the organosilane reagent is selected from one or more of trimethylchlorosilane, hexamethylsilane and hexamethyldisilazane.
7. The method of claim 1, wherein: in the step (3), the mass ratio of the product A, the organic alcohol solvent and the organic silane reagent is 1:0.5: 5.
8. The method of claim 1, wherein: in the step (4), the drying temperature is 120 ℃, the drying time is 12 hours, the roasting temperature is 500-.
9. The method of claim 1, wherein: the ion exchange conditions in the step (5) are as follows: the raw materials are placed in a 0.5-2 mol.L < -1 > diluted acid solution and stirred for 1-4 hours, wherein the liquid-solid mass ratio of the exchange solution to the molecular sieve raw powder is 10-20:1, the exchange temperature is 60-95 ℃, and the ion exchange process is repeated for 1-3 times.
10. The method of claim 9, wherein: the dilute acid solution is any one or a mixture of more of sulfuric acid, hydrochloric acid or nitric acid solution.
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