CN116273153A - Activated carbon@SAPO-11/kaolin composite acidic material and preparation method thereof - Google Patents
Activated carbon@SAPO-11/kaolin composite acidic material and preparation method thereof Download PDFInfo
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- CN116273153A CN116273153A CN202310321928.9A CN202310321928A CN116273153A CN 116273153 A CN116273153 A CN 116273153A CN 202310321928 A CN202310321928 A CN 202310321928A CN 116273153 A CN116273153 A CN 116273153A
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- 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 95
- 239000005995 Aluminium silicate Substances 0.000 title claims abstract description 76
- 235000012211 aluminium silicate Nutrition 0.000 title claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000013067 intermediate product Substances 0.000 claims abstract description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 11
- 238000003763 carbonization Methods 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 229920002472 Starch Polymers 0.000 claims description 9
- 239000003929 acidic solution Substances 0.000 claims description 9
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000008107 starch Substances 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 229940043279 diisopropylamine Drugs 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 abstract description 19
- 238000002425 crystallisation Methods 0.000 abstract description 9
- 230000008025 crystallization Effects 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000003213 activating effect Effects 0.000 abstract description 2
- 238000004537 pulping Methods 0.000 abstract 1
- 239000002808 molecular sieve Substances 0.000 description 24
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 229920002261 Corn starch Polymers 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 239000012876 carrier material Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000008120 corn starch Substances 0.000 description 5
- 239000011799 hole material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- RFRMMZAKBNXNHE-UHFFFAOYSA-N 6-[4,6-dihydroxy-5-(2-hydroxyethoxy)-2-(hydroxymethyl)oxan-3-yl]oxy-2-(hydroxymethyl)-5-(2-hydroxypropoxy)oxane-3,4-diol Chemical compound CC(O)COC1C(O)C(O)C(CO)OC1OC1C(O)C(OCCO)C(O)OC1CO RFRMMZAKBNXNHE-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 244000017020 Ipomoea batatas Species 0.000 description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229920003086 cellulose ether Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229940100445 wheat starch Drugs 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses an activated carbon@SAPO-11/kaolin composite acidic material and a preparation method thereof, wherein the activated carbon@SAPO-11/kaolin composite acidic material is prepared by activating kaolin at high temperature and performing phosphoric acid dealuminization treatment; then adding a silicon source, an aluminum source and a template agent into the dealuminated kaolin, and performing operations such as ball milling, crystallization and the like to obtain an intermediate product of SAPO-11+ kaolin; pulping the high polymer and an intermediate product of SAPO-11+ kaolin together, and performing high-temperature treatment to form a gel structure; finally, the activated carbon@SAPO-11/kaolin composite acidic material with a stepped pore structure is obtained through high-temperature carbonization. The invention takes natural kaolin as a raw material to prepare the composite acidic material with a step hole structure and adjustable micro-mesoporous proportion.
Description
Technical Field
The invention belongs to the field of catalytic materials, and particularly relates to an activated carbon@SAPO-11/kaolin composite acidic carrier material and a preparation method thereof.
Background
Acid catalytic reaction is one of important reactions in the fields of chemistry and chemical industry, and is widely used in the fields of petrochemical industry, medicine, food, environmental protection, bioengineering and the like, so the development of acid materials is one of important research subjects in the catalysis discipline. The molecular sieve is a microporous acid material formed by connecting Si and Al atoms through oxygen bridges, and has become an indispensable catalytic material for petroleum processing and fine chemical engineering due to the advantages of regular pore channel structures and adjustable surface acidity. To date, the molecular sieves have been more than 120 in variety. However, the narrow pore channel structure of the microporous molecular sieve limits the application of the microporous molecular sieve in the field of macromolecular catalysis, and for this reason, the stepped pore molecular sieve containing a certain mesoporous structure is widely studied so as to obtain a molecular sieve acidic material with lower mass transfer resistance, which can be used for macromolecular catalysis, and widen the application of the molecular sieve in the field of macromolecular catalysis.
The pore canal structure of the commercial micro mesoporous SAPO-11 molecular sieve material is not adjustable, and the preparation of the commercial micro mesoporous SAPO-11 molecular sieve material mostly adopts an organic mesoporous template, and the use of the organic template not only pollutes the environment, but also increases the cost. The invention patent ZL 202110962680.5 discloses a method for preparing a stepped pore molecular sieve by using natural clay, which comprises the steps of firstly roasting the natural clay at high temperature, adding alkali liquor to extract part of Si element to obtain clay ore with low silicon content and silicate alkali liquor, wherein the obtained clay ore with low silicon content is used for synthesizing Fe-SAPO molecular sieve, the silicate alkali liquor is used for synthesizing stepped pore MFI, MOR or TS-1, a green synthesis route of the molecular sieve is obtained, and the problem that mesoporous template agent needs to be added into the stepped pore molecular sieve is solved. The invention patent ZL202110735921.2 discloses a method for green synthesis of a cascade pore SAPO-11 molecular sieve based on natural minerals, which is characterized in that kaolin is dissolved in hydrochloric acid solution after high-temperature roasting, then aluminum element and template agent are supplemented, and crystallization is carried out to obtain a final product, and the synthesized SAPO-11 molecular sieve has the characteristics of high crystallinity, large external specific surface area and no need of mesoporous template agent. The invention patent ZL 202111533953.0 discloses a synthesis method of a mesoporous molecular sieve with large unit cell parameters, which adopts a nonionic surfactant and an anionic template auxiliary agent and adds cellulose ether, and a liquid crystal structure formed by the cellulose ether in water limits a silicon source and an aluminum source, so that the mesoporous molecular sieve with large unit cell parameters is obtained. The synthesis of the step hole molecular sieve has the defects of large template agent dosage and difficult control of mesoporous proportion, and is not beneficial to industrial production.
Disclosure of Invention
The invention aims to provide an activated carbon@SAPO-11/kaolin composite acidic carrier material and a preparation method thereof, wherein natural kaolin is used as a raw material, and the composite acidic material with a stepped pore structure is finally obtained through high-temperature activation, phosphoric acid dealumination, crystallization and high-temperature carbonization of the kaolin, and the composite acidic material has the advantages of mesoporous structure and adjustable proportion.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the activated carbon@SAPO-11/kaolin composite acidic material comprises the following steps:
(1) Roasting kaolin at a certain temperature to obtain metakaolin, then adding a phosphoric acid solution with a certain concentration, and carrying out water bath at a certain temperature to obtain a dealuminated and activated kaolin acidic solution;
(2) Taking the kaolin acidic solution, sequentially adding deionized water, a silicon source, an aluminum source and a template agent, uniformly stirring, putting the obtained mixed solution into a ball mill for ball milling, transferring the ball mill into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal crystallization in a homogeneous phase reactor, and cooling, centrifuging and washing to obtain an SAPO-11/kaolin intermediate product;
(3) Mechanically stirring a certain amount of high molecular polymer and the SAPO-11/kaolin intermediate product, and heating at a certain temperature until the high molecular polymer and the SAPO-11/kaolin intermediate product form a gel structure to obtain a high molecular gel containing SAPO-11/kaolin;
(4) Carbonizing the obtained polymer gel containing the SAPO-11/kaolin at a certain temperature to obtain the activated carbon@SAPO-11/kaolin composite acidic material with the stepped holes.
Further, the concentration of the phosphoric acid solution in the step (1) is 1-4 mol/L, and the adding amount of the phosphoric acid solution is 5-mL per gram of kaolin.
Further, the roasting temperature is 600-1000 ℃ and the roasting time is 4-6 hours; the temperature of the water bath is 50-90 ℃ and the time is 1-2 h.
Further, the addition amount of the aluminum source in the step (2) is converted according to the mole ratio of phosphorus to aluminum in the obtained mixed solution of 0.7-1.5:1; the addition amount of the silicon source is converted according to the mole ratio of silicon to aluminum in the obtained mixed solution of 0.3-0.5:1; the molar ratio of the template agent to aluminum in the mixed solution is 0.4-1.5:1, and the addition amount of deionized water is converted according to the molar ratio of the aluminum in the obtained mixed solution of 30-120:1.
The silicon source comprises one or more of metakaolin, tetraethyl orthosilicate, silica sol and white carbon black; the aluminum source comprises one or more of metakaolin, pseudo-boehmite and aluminum isopropoxide; the template agent comprises one or more of di-n-propylamine, diisopropylamine and di-n-butylamine.
Further, the rotational speed of the ball milling in the step (2) is 1000-15000 r/min, and the time is 1-2 h; the temperature of the hydrothermal crystallization is 140-200 ℃, the rotating speed is 50-480 r/min, and the time is 2-72 h.
Further, the mass ratio of the high molecular polymer used in the step (3) to the intermediate product of the SAPO-11+ kaolin is 0.5-1.5:1; the high molecular polymer comprises one or more of starch and cellulose. Wherein the starch can be one or more of corn starch, sweet potato starch, wheat starch and pea starch. The cellulose may be one or more of carboxymethyl cellulose, hydroxypropyl methylcellulose, and hydroxyethyl cellulose.
Further, the heating temperature in the step (3) is 150-200 ℃.
Further, the carbonization temperature in the step (4) is 500-800 ℃ and the carbonization time is 3-4 hours.
The invention provides a preparation method of a mesoporous structure and proportion-adjustable stepped pore acid carrier material, which is characterized in that activated and dealuminated kaolin and phosphoric acid solution are respectively used as a silicon source and a phosphorus source in the preparation process, so that a raw material for forming a SAPO-11 molecular sieve is provided, a mesoporous structure is also provided, and the SAPO-11/kaolin polymer gel is carbonized to generate the mesoporous structure, and the mesoporous structure can be flexibly modulated through the dealumination and carbonization processes of the kaolin.
Compared with the existing step hole molecular sieve, the invention has the advantages that: the synthesized activated carbon@SAPO-11/kaolin composite acidic material has micropores mainly provided by SAPO-11, mesopores provided by activated carbon and kaolin, and the mesoporous structure can be flexibly modulated through the processes of dealumination and carbonization of the kaolin.
Drawings
FIG. 1 is an XRD spectrum of the material obtained in examples 1 to 4 and comparative example 1;
FIG. 2 is N of the materials obtained in examples 1 to 4 and comparative example 1 2 Adsorption-desorption isotherms;
FIG. 3 is a graph showing pore size distribution of the materials obtained in examples 1 to 4 and comparative example 1.
Detailed Description
The preparation method of the activated carbon@SAPO-11/kaolin composite acidic material comprises the following steps:
(1) Roasting kaolin at 600-1000 ℃ for 4-6 hours to obtain metakaolin, adding 1-4 mol/L phosphoric acid solution according to the amount of 5mL/g, and carrying out water bath at 50-90 ℃ for 1-2 hours to obtain a dealuminated and activated kaolin acidic solution;
(2) Taking the kaolin acidic solution, sequentially adding deionized water, a silicon source, an aluminum source and a template agent, stirring uniformly, putting the obtained mixed solution into a ball mill, ball milling for 1-2 hours at 1000-15000 r/min, transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal crystallization for 2-72 hours at the rotating speed of 50-480 r/min in a homogeneous reactor at 140-200 ℃, and cooling, centrifuging and washing to obtain an SAPO-11/kaolin intermediate product;
(3) Mixing a high polymer and the SAPO-11/kaolin intermediate product according to a mass ratio of 0.5-1.5:1, mechanically stirring, and heating at 150-200 ℃ until the high polymer and the SAPO-11/kaolin intermediate product form a gel structure to obtain a high polymer gel containing SAPO-11/kaolin;
(4) Carbonizing the obtained polymer gel containing the SAPO-11/kaolin for 3-4 hours at the temperature of 500-800 ℃ under the condition of nitrogen or argon sweeping, so as to obtain the activated carbon@SAPO-11/kaolin composite acidic material with the stepped holes.
The addition amount of the aluminum source in the step (2) is converted according to the mole ratio of phosphorus to aluminum in the obtained mixed solution of 0.7-1.5:1; the addition amount of the silicon source is converted according to the mole ratio of silicon to aluminum in the obtained mixed solution of 0.3-0.5:1; the molar ratio of the template agent to aluminum in the mixed solution is 0.4-1.5:1, and the addition amount of deionized water is converted according to the molar ratio of the aluminum in the obtained mixed solution of 30-120:1.
The silicon source comprises one or more of metakaolin, tetraethyl orthosilicate, silica sol and white carbon black; the aluminum source comprises one or more of metakaolin, pseudo-boehmite and aluminum isopropoxide; the template agent comprises one or more of di-n-propylamine, diisopropylamine and di-n-butylamine.
The high molecular polymer in the step (3) comprises one or more of starch and cellulose. Wherein the starch can be one or more of corn starch, sweet potato starch, wheat starch and pea starch. The cellulose may be one or more of carboxymethyl cellulose, hydroxypropyl methylcellulose, and hydroxyethyl cellulose.
In order to solve the problems of the restriction of the pore canal of the traditional microporous molecular sieve carrier, large dosage of commercial template agent and high cost, the invention prepares a carrier material with a stepped pore structure and adjustable micro-mesoporous proportion by taking natural kaolin as a raw material and utilizing the pore canal structure of the kaolin, so as to improve the connectivity of the pore canal of the acidic carrier material and provide a new thought for developing ideal pore canal materials required by natural mineral preparation.
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1
(1) Activating and dealuminating kaolin: roasting kaolin at 850 ℃ for 4 h to obtain metakaolin, adding phosphoric acid solution with the concentration of 4 mol/L according to the amount of 5mL/g under stirring, and treating 1 h in a 70 ℃ water bath to obtain a dealuminated and activated kaolin acidic solution;
(2) Synthesis of SAPO-11/Kaolin intermediate: weighing the dealuminated and activated kaolin acidic solution 12.8 and g obtained in the step (1), and sequentially adding 28.31 and g of water, 2.28g of pseudo-boehmite, 1.26 and g of tetraethyl orthosilicate and 3.06 and g of di-n-propylamine under the stirring condition to form a gel precursor, wherein the molar ratio of the precursor is as follows: 1Al 2 O 3 :0.9P 2 O 5 :0.3SiO 2 :1.5DPA:100H 2 O; then adding the precursor into a ball mill, ball milling for 30 min at 12000 r/min, finally transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing for 24 h at 180 ℃ at 480 r/min in a homogeneous reactor, cooling, centrifuging and washing to obtain an SAPO-11/kaolin intermediate product;
(3) Preparation of SAPO-11/kaolin-containing polymer gel: adding 70 g deionized water into the SAPO-11/kaolin intermediate product obtained in the step (2) of 6 g, stirring uniformly, then adding 5 g carboxymethyl cellulose and 3 g corn starch, stirring uniformly, and heating at 160 ℃ until a gel structure is formed, thus obtaining polymer gel containing SAPO-11/kaolin;
(4) Preparation of activated carbon @ SAPO-11/kaolin composite material: and (3) carbonizing the polymer gel containing the SAPO-11/kaolin obtained in the step (3) at high temperature for 3 hours under the condition of 600 ℃ and nitrogen purging to obtain the activated carbon@SAPO-11/kaolin composite acidic material, which is named as C-1.
Example 2
In the step (3), no more carboxymethyl cellulose was added, and the addition amount of corn starch was increased from 3 g to 6 g, and the obtained material was designated as C-2 in the same manner as in example 1.
Example 3
The crystallization temperature in the step (2) was adjusted to 170℃and the crystallization time was adjusted to 48 h, and the obtained material was designated as C-3 in the same manner as in example 1.
Example 4
The molar ratio of the gel component in the step (2) is adjusted as follows: 1Al 2 O 3 :1.2P 2 O 5 :0.3SiO 2 :1.5DPA:100H 2 O, namely, 14.4. 14.4 g of the dealuminated and activated kaolin acidic solution obtained in the step (1) is weighed, 27.35 g of water, 1.94g of pseudo-boehmite, 1.26 g of tetraethyl orthosilicate and 3.06 g of di-n-propylamine are sequentially added under stirring to form a precursor, and the crystallization time and crystallization temperature in the example 3 are used, and the other operations are the same as those in the example 1, so that the obtained material is named as C-4.
Comparative example
SAPO-11 purchased from university of Nanking was used as a control, and the crystallinity was 100 and designated as D-1.
The physical properties of the obtained materials were measured as shown in FIGS. 1 to 3 and Table 1.
TABLE 1 physical Properties parameters of the products
As can be seen from FIG. 1, the materials prepared in examples 1-4 all have AEL topology structures, and the relative crystallinity of the materials is 64%, 67%, 84% and 91% respectively, which indicates that the synthetic products are the activated carbon@SAPO-11/kaolin composite acidic material, wherein the composite material obtained in example 4 has a relatively high SAPO-11 content.
As can be seen from fig. 2, all the materials have micro-mesoporous structures, and belong to the step hole materials. As is clear from Table 1, the specific surface area of C-1 was 217 m 2 /g, mesoporous volume of 0.23 and 0.23 m 2 Specific surface area of C-2 per gram is 214 m 2 /g, mesoporous volume of 0.23 and 0.23 m 2 Specific surface area of C-3/g is 150 m 2 /g, mesoporous volume of 0.15 m 2 Specific surface area of C-4 per gram is 145 m 2 Per g, mesoporous volume of 0.07 m 2 Per g, and D-1 has a specific surface area of 125 m 2 Per g, mesoporous volume of 0.21 m 2 /g。
As can be seen from FIG. 3, when no carboxymethyl cellulose is added to the synthesis system and the addition amount of corn starch is increased, the pore structure property of the obtained material C-2 is not greatly changed compared with that of C-1; when the crystallization temperature of the synthesis system is adjusted to 170 ℃ and the crystallization time is adjusted to 48 h, the content of the SAPO-11 molecular sieve in the obtained material C-3 is increased, thereby reducing the number of large mesopores of the kaolinLess, which is consistent with the results of table 1; when the molar ratio of the gel component in the synthesis system is adjusted to be 1Al 2 O 3 :1.2P 2 O 5 :0.3SiO 2 :1.5DPA:100H 2 In the O process, the content of the SAPO-11 molecular sieve in the obtained material C-4 is further increased, and the number of the large mesopores of the kaolin is further reduced.
The analysis result shows that the activated carbon@SAPO-11/kaolin composite acid material with a stepped pore structure is successfully synthesized by taking kaolin as a raw material, wherein the SAPO-11 molecular sieve provides micropores, the activated carbon and the kaolin provide mesopores, and the mesoporous structure and the proportion of the activated carbon@SAPO-11/kaolin composite acid material can be flexibly modulated, so that a new way is provided for the development of the macromolecular catalyst acid material.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. The preparation method of the activated carbon@SAPO-11/kaolin composite acidic material is characterized by comprising the following steps of:
(1) Roasting kaolin at a certain temperature to obtain metakaolin, then adding a phosphoric acid solution with a certain concentration, and carrying out water bath at a certain temperature to obtain a dealuminated and activated kaolin acidic solution;
(2) Taking the kaolin acidic solution, sequentially adding deionized water, a silicon source, an aluminum source and a template agent, uniformly stirring, ball-milling the obtained mixed solution, transferring the ball-milled mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal crystallization in a homogeneous phase reactor, and cooling, centrifuging and washing to obtain an SAPO-11/kaolin intermediate product;
(3) Mechanically stirring a certain amount of high molecular polymer and the SAPO-11/kaolin intermediate product, and heating at a certain temperature until the high molecular polymer and the SAPO-11/kaolin intermediate product form a gel structure to obtain a high molecular gel containing SAPO-11/kaolin;
(4) Carbonizing the obtained polymer gel containing the SAPO-11/kaolin at a certain temperature to obtain the activated carbon@SAPO-11/kaolin composite acidic material with the stepped holes.
2. The method for preparing the activated carbon@SAPO-11/kaolin composite acidic material according to claim 1, wherein the concentration of the phosphoric acid solution in the step (1) is 1-4 mol/L, and the adding amount of the phosphoric acid solution is 5mL per gram of kaolin.
3. The preparation method of the activated carbon@SAPO-11/kaolin composite acidic material according to claim 1, wherein the roasting temperature in the step (1) is 600-1000 ℃ and the time is 4-6 hours; the temperature of the water bath is 50-90 ℃ and the time is 1-2 h.
4. The method for preparing the activated carbon@SAPO-11/kaolin composite acidic material according to claim 1, wherein the addition amount of the aluminum source in the step (2) is converted according to the mole ratio of phosphorus to aluminum in the obtained mixed solution being 0.7-1.5:1; the addition amount of the silicon source is converted according to the mole ratio of silicon to aluminum in the obtained mixed solution of 0.3-0.5:1; the molar ratio of the template agent to aluminum in the mixed solution is 0.4-1.5:1, and the addition amount of deionized water is converted according to the molar ratio of the aluminum in the obtained mixed solution of 30-120:1.
5. The method for preparing an activated carbon @ SAPO 11/kaolin composite acidic material of claim 1 or 4, wherein the silicon source comprises one or more of metakaolin, tetraethyl orthosilicate, silica sol and white carbon black; the aluminum source comprises one or more of metakaolin, pseudo-boehmite and aluminum isopropoxide; the template agent comprises one or more of di-n-propylamine, diisopropylamine and di-n-butylamine.
6. The preparation method of the activated carbon@SAPO-11/kaolin composite acid material according to claim 1, wherein the rotational speed of the ball mill in the step (2) is 1000-15000 r/min, and the time is 1-2 h; the temperature of the hydrothermal crystallization is 140-200 ℃, the rotating speed is 50-480 r/min, and the time is 2-72 h.
7. The method for preparing the activated carbon@SAPO-11/kaolin composite acidic material according to claim 1, wherein the mass ratio of the high molecular polymer used in the step (3) to the intermediate product of SAPO-11+kaolin is 0.5-1.5:1; the high molecular polymer comprises one or more of starch and cellulose.
8. The method for preparing the activated carbon@SAPO-11/kaolin composite acidic material according to claim 1, wherein the heating temperature in the step (3) is 150-200 ℃.
9. The preparation method of the activated carbon@SAPO-11/kaolin composite acidic material according to claim 1, wherein the carbonization temperature in the step (4) is 500-800 ℃ and the carbonization time is 3-4 hours.
10. An activated carbon @ SAPO-11/kaolin composite acidic material prepared by the method of claim 1.
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| CN103663493A (en) * | 2013-12-04 | 2014-03-26 | 中国科学院山西煤炭化学研究所 | Preparation method of silicoaluminophosphate molecular sieve with mesoporous-microporous hierarchical structure |
| CN106582804A (en) * | 2015-10-20 | 2017-04-26 | 中国石油大学(北京) | Hierarchical porous SAPO-34/kaolin composite material and preparation method thereof |
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| US20190224652A1 (en) * | 2018-01-23 | 2019-07-25 | China University Of Petroleum-Beijing | Sapo-34/zsm-5@kaolin microsphere composite catalytic material and its preparation and use |
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