CN113426479B - Preparation method of kaolin-based composite molecular sieve membrane - Google Patents
Preparation method of kaolin-based composite molecular sieve membrane Download PDFInfo
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- 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 88
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 82
- 239000012528 membrane Substances 0.000 title claims abstract description 79
- 239000005995 Aluminium silicate Substances 0.000 title claims abstract description 72
- 235000012211 aluminium silicate Nutrition 0.000 title claims abstract description 72
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- 230000008025 crystallization Effects 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 230000004913 activation Effects 0.000 claims abstract description 14
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 230000010355 oscillation Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- B01J35/59—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The application discloses a preparation method of a kaolin-based composite molecular sieve membrane, which comprises the steps of mixing kaolin and sodium carbonate, carrying out high-temperature activation and alkali activation treatment to obtain active kaolin, pressing the kaolin into a tablet, placing the tablet in a muffle furnace to calcine to obtain a loaded substrate, fixing the prepared substrate on a synthesis frame, placing the synthesis frame in a ZSM-5 synthetic liquid to crystallize the loaded ZSM-5 molecular sieve membrane, placing the ZSM-5 molecular sieve membrane in a modification solution, and carrying out constant-temperature oscillation and impregnation to obtain a surface-modified molecular sieve membrane; drying the modified molecular sieve membrane, fixing the dried molecular sieve membrane on a synthesis frame, transferring the molecular sieve membrane into a crystallization kettle filled with SAPO-34 synthetic liquid to crystallize and load the SAPO-34 molecular sieve membrane, and washing, drying and calcining the molecular sieve membrane to obtain the kaolin-based composite molecular sieve membrane. The composite interface has strong binding force, high arene selectivity and carbon deposition resistance, simple preparation process and low cost, and is beneficial to commercial popularization and industrial production.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of a kaolin-based composite molecular sieve membrane.
Background
Aromatic hydrocarbons are important raw materials for organic chemicals and polymer industries. Based on the basic national conditions of 'rich coal, lean oil and little gas' in China, with the development of coal chemical industry, the methanol-to-aromatics (MTA) becomes a new way for synthesizing high-quality aromatics at low cost in a non-petroleum route. The method not only has the characteristic of sustainable development, but also can solve the problems that the aromatic hydrocarbon is dependent on import and the domestic methanol productivity is seriously excessive, has very important significance for realizing the low-cost synthesis of high-quality aromatic hydrocarbon in a non-petroleum route and expanding the application of methanol, and the preparation of a high-performance catalyst is the key for realizing and popularizing the process. Because of the problems of low selectivity of the existing catalyst to aromatics and easy carbon deposition inactivation, the synthesis of the kaolin-based CHA-MFI molecular sieve catalyst material provided by the invention based on the MTA reaction characteristics shows the catalytic characteristics different from those of the traditional molecular sieve in the MTA catalytic field, and is expected to become a prospective catalytic material with research value and application prospect.
Disclosure of Invention
The technical problem to be solved is as follows:
aiming at the defects of the prior art, the application provides a preparation method of a kaolin-based composite molecular sieve membrane, which solves the problems of low selectivity of the catalyst to aromatic hydrocarbon, easy carbon deposition inactivation and the like, not only can effectively improve the selectivity of the MTA reaction to the aromatic hydrocarbon and inhibit the occurrence of deep side reaction, but also has the advantages of simple preparation, easily obtained raw materials and complete process, and is beneficial to promoting the industrial production of the kaolin-based composite molecular sieve membrane.
The technical scheme is as follows:
in order to achieve the purpose, the application is realized by the following technical scheme:
a preparation method of a kaolin-based composite molecular sieve membrane comprises the following steps:
the first step is as follows: mixing kaolin and sodium carbonate uniformly, wherein the mass fraction ratio of the sodium carbonate to the kaolin is 1-5: 100; placing the mixture in a muffle furnace for high-temperature activation; naturally cooling the kaolin after high-temperature activation, and then adding NaOH solution with the concentration of 3.0-5.0 mol/L for alkali activation treatment, wherein the mass ratio of the NaOH solution to the kaolin is 3-5: 1, cleaning the powder to be neutral and drying to prepare active kaolin;
the second step is that: pressing the active kaolin treated in the first step into a sheet with the thickness of less than 1mm under the pressure of 10Mpa, and placing the sheet in a muffle furnace for calcining again for 2-5 hours at the temperature of 1000-1300 ℃ to prepare a load substrate;
the third step: fixing the prepared load substrate on a special fixing frame, wherein the special fixing frame is formed by fixing two pieces of hollowed polytetrafluoroethylene materials together through screws, so that the load substrate is kept stable in a ZSM-5 synthetic liquid, placing the load substrate in the ZSM-5 synthetic liquid for crystallization, carrying out washing by deionized water, and drying in an oven to obtain a ZSM-5 kaolin-based molecular sieve membrane;
the fourth step: placing a ZSM-5 kaolin-based molecular sieve membrane in a TPABr aqueous solution, and carrying out constant-temperature oscillation dipping treatment at 40 ℃ to obtain a surface-modified molecular sieve membrane, wherein the modification treatment time is 40-140 min, and the concentration of the TPABr aqueous solution is 5000-20000 mg/L;
the fifth step: and drying the modified molecular sieve membrane, fixing the dried molecular sieve membrane on a synthesis frame, transferring the molecular sieve membrane into a crystallization kettle filled with SAPO-34 synthetic liquid for crystallization to load the SAPO-34 molecular sieve membrane, washing the molecular sieve membrane by deionized water, drying the molecular sieve membrane by an oven, and calcining the molecular sieve membrane at 550 ℃ for 3 hours to obtain the kaolin-based composite molecular sieve membrane.
Furthermore, the particle size of the kaolin in the first step is 200-300 meshes.
Further, the first step is calcined at the high temperature of 800-860 ℃ for 2-5 hours.
Further, in the first step, leaching for 2-3 hours at 80 ℃.
Further, in the first step, deionized water is repeatedly used for washing until the pH value is 7.
Further, in the first step, the drying temperature is 60 ℃, and the drying is carried out by using an oven.
Further, the molar ratio of the ZSM-5 synthetic solution in the third step is as follows: n (TPAOH): n (SiO) 2 ）n（Al 2 O 3 ）：n（H 2 O）=0.32:1:0.02:150~165。
Further, the crystallization time in the third step is 5-10 hours.
Further, in the fifth step, the mole ratio of the SAPO-34 synthetic liquid is as follows: n (Al) 2 O 3 ): n(P 2 O 5 ): n(SiO 2 ): n(Mor): n(H 2 O)= 1: 1: 0.6~0.9: 3: 70。
Further, the crystallization time in the fifth step is 20-24 hours.
The principle of the invention is as follows: the new material combines the high olefin selectivity advantage of the SAPO-34 membrane layer and the high aromatic selectivity advantage of the ZSM-5 membrane layer, simultaneously utilizes the rapid diffusion advantage of mesoporous and macroporous pore canals of the coal-based layer, divides the traditional MTA reaction into three stages of preparing olefin by methanol catalytic conversion, preparing aromatic by olefin catalytic conversion and rapidly diffusing aromatic, improves the selectivity of aromatic hydrocarbon and inhibits deep side reaction. Meanwhile, the crystal structures of the two materials are considered to be completely different, and symbiotic growth is difficult. Through a cation surface modification means, the ZSM-5 molecular sieve with the surface being negative charge is converted into positive charge, so that electrostatic attraction can be generated between the ZSM-5 molecular sieve with the surface being negative charge and the SAPO-34 molecular sieve with the surface being negative charge, and the repulsion between the two molecular sieves with the surfaces being negative charge is converted into attraction. Simultaneously, TPA + The method can also be used as a growth site for SAPO-34 to grow on the surface of ZSM-5 and as a template structure guide, increases the nucleation probability of SAPO-34 molecular sieve grains on the surface of the ZSM-5 molecular sieve and the bonding force between molecular sieve crystal interfaces, and can prepare the composite molecular sieve membrane with strong crystal face bonding force by using the scheme.
Has the advantages that:
the application provides a preparation method of a kaolin-based composite molecular sieve membrane, which has the following beneficial effects:
1. not only can effectively improve the selectivity of MTA reaction aromatic hydrocarbon and inhibit the occurrence of deep side reaction, but also has simple preparation, easily obtained raw materials and complete process, and is beneficial to promoting the industrial production of the kaolin-based composite molecular sieve membrane.
2. The invention adopts the kaolin substrate, has cheap and easily obtained materials, can meet the requirement of rapid diffusion of reactant molecules, realizes comprehensive utilization of coal-series materials, and can provide higher mechanical strength for the molecular sieve film layer.
3. Compared with the reported documents, the kaolin-based composite molecular sieve membrane prepared by the invention has stronger continuity, compactness and stability on the surface, has high selectivity on MTA reaction aromatic hydrocarbon, and also has high carbon deposition resistance.
4. The invention provides an excellent composite molecular sieve synthesis process, which is simple to operate, has loose conditions and is easy for industrial popularization.
Description of the drawings:
fig. 1 is an XRD pattern of the kaolin-based composite molecular sieve membrane prepared in example 1 of the present application.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be illustrative only and not to limit the scope of the invention.
Example 1:
a preparation method of a kaolin-based composite molecular sieve membrane comprises the following steps:
the first step is as follows: weighing 10.0g of kaolin powder and 0.1g of sodium carbonate, uniformly mixing, placing in a muffle furnace for high-temperature activation at 860 ℃ for 4h, naturally cooling to room temperature, leaching with 30g of 5.0 mol/L NaOH solution in 80 ℃ water bath for 2h, repeatedly washing with deionized water until the pH value of the solution is 7, and drying in a 60 ℃ oven to obtain active kaolin powder;
the second step is that: pressing 0.1g of active kaolin powder into a sheet with the thickness of less than 1mm under the pressure of 10MPa, and placing the sheet in a muffle furnace for high-temperature calcination at 1200 ℃ for 2h to prepare a load substrate;
the third step: fixing the prepared load substrate on a special fixing frame, wherein the special fixing frame is used for fixing two pieces of hollow polytetrafluoroethylene materials together through screws, so that the load substrate is kept stable in a synthetic solution, and is placed in 40ml of a ZSM-5 synthetic solution for crystallization for 5 hours, and then the load substrate is washed by deionized water and is placed in an oven for drying at 60 ℃ to prepare the ZSM-5 kaolin-based molecular sieve membrane, wherein the ZSM-5 synthetic solution comprises the following components in molar ratio: n (TPAOH): n (SiO) 2 ）n（Al 2 O 3 ）：n（H 2 O）=0.32:1:0.02:160。
The fourth step: 0.2g of TPABr was dissolved in 400ml of deionized water to prepare a surface modification treatment solution. Dipping the molecular sieve membrane prepared in the third step into the surface modification treatment liquid, oscillating for 140min, drying, then placing the membrane into SAPO-34 synthetic liquid for crystallization for 20h, washing, drying, then placing the membrane into a muffle furnace for calcining for 3h at 550 ℃ to obtain a kaolin-based composite molecular sieve membrane material; the mol ratio of the SAPO-34 synthetic liquid is as follows: n (Al) 2 O 3 ): n(P 2 O 5 ): n(SiO 2 ): n(Mor): n(H 2 O)= 1: 1: 0.6: 3: 70。
FIG. 1 is an XRD pattern of the kaolin-based composite molecular sieve membrane prepared in example 1 of the present invention, and the results show that the ZSM-5 molecular sieve classified as MFI type and the SAPO-34 molecular sieve classified as CHA type have complete structures and good crystal growth.
Example 2:
a preparation method of a kaolin-based composite molecular sieve membrane comprises the following steps:
the first step is as follows: weighing 25.0g of kaolin powder and 1.25g of sodium carbonate, uniformly mixing, placing in a muffle furnace for high-temperature activation at 850 ℃ for 4h, naturally cooling to room temperature, leaching with 40g of 3.0 mol/L NaOH solution in water bath at 80 ℃ for 2h, repeatedly washing with deionized water until the pH value of the solution is 7, and drying to obtain active kaolin powder;
the second step is that: 0.08g of active kaolin powder is pressed into a sheet with the thickness of less than 1mm by using the pressure of 10MPa, and the sheet is placed in a muffle furnace for high-temperature calcination at 1100 ℃ for 2h to prepare a load substrate;
the third step: fixing the prepared load substrate on a special fixing frame, wherein the special fixing frame is used for fixing two pieces of hollow polytetrafluoroethylene materials together through screws, so that the load substrate is kept stable in a synthetic solution, and is placed in 40ml of a ZSM-5 synthetic solution for crystallization for 5 hours, and then the load substrate is washed by deionized water and is placed in an oven for drying at 60 ℃ to prepare the ZSM-5 kaolin-based molecular sieve membrane, wherein the ZSM-5 synthetic solution comprises the following components in molar ratio: n (TPAOH): n (SiO) 2 ）n（Al 2 O 3 ）：n（H 2 O）=0.32:1:0.02:150~165。
The fourth step: 4.0g of TPABr was dissolved in 500ml of deionized water to prepare a surface modification treatment solution. Dipping the molecular sieve membrane prepared in the third step into the surface modification treatment liquid, oscillating for 120min, drying the molecular sieve membrane in an oven, then placing the molecular sieve membrane in SAPO-34 synthetic liquid for crystallization for 20h, washing the molecular sieve membrane with deionized water, placing the molecular sieve membrane in the oven for drying at 60 ℃, then placing the molecular sieve membrane in a muffle furnace for calcining for 3h at 550 ℃ to obtain a kaolin-based composite molecular sieve membrane material, and testing the selectivity of aromatic hydrocarbon to 46% by MTA reaction; the mol ratio of the SAPO-34 synthetic liquid is as follows: n (Al) 2 O 3 ): n(P 2 O 5 ): n(SiO 2 ): n(Mor): n(H 2 O)= 1: 1: 0.6: 3: 70。
Example 3:
a preparation method of a kaolin-based composite molecular sieve membrane comprises the following steps:
the first step is as follows: weighing 5.0g of kaolin powder and 0.25g of sodium carbonate, uniformly mixing, placing in a muffle furnace for high-temperature activation at 860 ℃ for 4h, naturally cooling to room temperature, leaching with 20g of 4.0 mol/L NaOH solution in water bath at 80 ℃ for 2h, repeatedly washing with deionized water until the pH value of the solution is 7, and placing in a 60 ℃ oven for drying to obtain the active kaolin powder.
The second step is that: 0.09g of active kaolin powder is pressed into a sheet with the thickness of less than 1mm by using the pressure of 10MPa, and the sheet is placed in a muffle furnace for high-temperature calcination at 1200 ℃ for 2h to prepare a load substrate;
the third step: the prepared load substrate is fixed on a special fixing frame, the special fixing frame fixes two pieces of hollow polytetrafluoroethylene materials together through screws, so that the load substrate is kept stable in the synthetic solution,and placing the mixture in 40ml of ZSM-5 synthetic solution for crystallization for 5 hours, washing the mixture by using deionized water, and placing the mixture in a drying oven for drying at 60 ℃ to obtain the ZSM-5 kaolin-based molecular sieve membrane, wherein the molar ratio of the ZSM-5 synthetic solution is as follows: n (TPAOH): n (SiO) 2 ）n（Al 2 O 3 ）：n（H 2 O）=0.32:1:0.02:160。
The fourth step: 8.0g of TPABr was dissolved in 500ml of deionized water to prepare a surface modification treatment solution. Soaking the molecular sieve membrane prepared in the third step in the surface modification treatment solution, oscillating for 70min, drying and placing in a molar ratio of: n (Al) 2 O 3 ): n(P 2 O 5 ): n(SiO 2 ): n(Mor): n(H 2 O) = 1: 1: 0.7: 3: 70, crystallizing in SAPO-34 synthetic liquid for 20h, washing with deionized water, placing in an oven for drying at 60 ℃, placing in a muffle furnace for calcining at 550 ℃ for 3h to obtain the kaolin-based composite molecular sieve membrane material, and testing by MTA that the selectivity of aromatic hydrocarbon reaches 48%.
Example 4
A preparation method of a kaolin-based composite molecular sieve membrane comprises the following steps:
the first step is as follows: weighing 2.0g of kaolin powder and 0.06g of sodium carbonate, uniformly mixing, placing in a muffle furnace for high-temperature activation at 860 ℃ for 4h, naturally cooling to room temperature, leaching with 30g of 5.0 mol/L NaOH solution in 80 ℃ water bath for 2h, repeatedly washing with deionized water until the pH value of the solution is 7, and placing in a 60 ℃ oven for drying to obtain the active kaolin powder.
The second step is that: 0.15g of active kaolin powder is pressed into a sheet with the thickness of less than 1mm by using the pressure of 10MPa, and the sheet is placed in a muffle furnace for high-temperature calcination at 1200 ℃ for 2h to prepare a load substrate.
The third step: fixing the prepared load substrate on a special fixing frame, wherein the special fixing frame is formed by fixing two pieces of hollow polytetrafluoroethylene materials together through screws, so that the load substrate is kept stable in a synthetic solution and is placed in a mixture ratio of (n (TPAOH): n (SiO) 2 ）n（Al 2 O 3 ）：n（H 2 O) =0.32:1:0.02:165) is crystallized in 40ml of ZSM-5 synthetic liquid for 5 hours, and then the ZSM-5 kaolin-based molecular sieve membrane is prepared by washing and drying.
The fourth step:4.0g of TPABr is dissolved in 500ml of deionized water to prepare a surface modification treatment solution. Soaking the molecular sieve membrane prepared in the third step in the surface modification treatment solution, oscillating for 120min, drying, and placing in a molar ratio (n (Al) 2 O 3 ): n(P 2 O 5 ): n(SiO 2 ): n(Mor): n(H 2 O) = 1: 1: 0.9: 3: 70), crystallizing in SAPO-34 synthetic liquid for 20h, washing with deionized water, drying in an oven at 60 ℃, calcining in a muffle furnace at 550 ℃ for 3h to obtain the kaolin-based composite molecular sieve membrane material, wherein the selectivity of aromatic hydrocarbon reaches 53%.
Finally, it should be understood that the above-described preferred embodiments are merely illustrative of the technical solutions of the present application and are not intended to limit the present application, and although the present application has been described in detail through the above-described preferred embodiments, it should be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the present application, and any changes, equivalents, improvements, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The preparation method of the kaolin-based composite molecular sieve membrane is characterized by comprising the following steps:
firstly, mixing kaolin and sodium carbonate uniformly, wherein the mass fraction ratio of the sodium carbonate to the kaolin is 1-5: 100, respectively; placing the mixture in a muffle furnace for high-temperature activation; naturally cooling the kaolin after high-temperature activation, and then adding NaOH solution with the concentration of 3.0-5.0 mol/L for alkali activation treatment, wherein the mass ratio of the NaOH solution to the kaolin is 3-5: 1, cleaning the powder to be neutral and drying to prepare active kaolin;
secondly, pressing the active kaolin treated in the first step into slices with the thickness of less than 1mm under the pressure of 10MP a, and placing the slices in a muffle furnace to calcine for 2-5 hours again at the temperature of 1000-1300 ℃ to prepare a load substrate;
the third step: fixing the prepared load substrate on a special fixing frame, wherein the special fixing frame is formed by fixing two pieces of hollowed polytetrafluoroethylene materials together through screws, so that the load substrate is kept stable in a ZSM-5 synthetic liquid, placing the load substrate in the ZSM-5 synthetic liquid for crystallization, carrying out washing by deionized water, and drying in an oven to obtain a ZSM-5 kaolin-based molecular sieve membrane;
the fourth step: placing the ZSM-5 kaolin-based molecular sieve membrane in TPABr aqueous solution, and carrying out constant-temperature oscillation dipping treatment at 40 ℃ to obtain a surface-modified molecular sieve membrane, wherein the modification treatment time is 40-140 min, and the concentration of the TPABr aqueous solution is 5000-20000 mg/L;
the fifth step: and drying the modified molecular sieve membrane, fixing the dried molecular sieve membrane on a synthesis frame, transferring the molecular sieve membrane into a crystallization kettle filled with SAPO-34 synthetic liquid for crystallization to load the SAPO-34 molecular sieve membrane, washing the molecular sieve membrane by deionized water, drying the molecular sieve membrane by an oven, and calcining the molecular sieve membrane at 550 ℃ for 3 hours to obtain the kaolin-based composite molecular sieve membrane.
2. The method for preparing the kaolin-based composite molecular sieve membrane according to claim 1, wherein: in the first step, the particle size of kaolin is 200-300 meshes.
3. The method for preparing the kaolin-based composite molecular sieve membrane according to claim 1, wherein: and calcining for 2-5 h at 800-860 ℃ under the high-temperature activation condition in the first step.
4. The method for preparing the kaolin-based composite molecular sieve membrane according to claim 1, wherein: in the first step, the alkali activation treatment is carried out for 2-3 hours at 80 ℃.
5. The method for preparing the kaolin-based composite molecular sieve membrane according to claim 1, wherein: in the first step, the solution is repeatedly washed with deionized water until the pH value is 7.
6. The method for preparing the kaolin-based composite molecular sieve membrane according to claim 1, wherein: in the first step, the drying condition is 60 ℃, and the drying is carried out by using an oven.
7. The method for preparing a kaolin-based composite molecular sieve membrane according to claim 1, wherein: the third step is that the ZSM-5 synthetic solution has the molar ratio: n (TPAOH)）：n（SiO 2 ）n（Al 2 O 3 ）：n（H 2 O）=0.32:1:0.02:150~165。
8. The method for preparing a kaolin-based composite molecular sieve membrane according to claim 1, wherein: and in the third step, the crystallization time is 5-10 h.
9. The method for preparing a kaolin-based composite molecular sieve membrane according to claim 1, wherein: the mol ratio of the SAPO-34 synthetic liquid in the fifth step is as follows: n (Al) 2 O 3 ): n(P 2 O 5 ): n(SiO 2 ): n(Mor): n(H 2 O)= 1: 1: 0.6~0.9: 3: 70。
10. The method for preparing a kaolin-based composite molecular sieve membrane according to claim 1, wherein: and in the fifth step, the crystallization time is 20-24 hours.
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