CN114789063B - Silicon-aluminum solid acid catalyst, preparation method and application - Google Patents
Silicon-aluminum solid acid catalyst, preparation method and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 239000011973 solid acid Substances 0.000 title claims abstract description 42
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 title abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 13
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 25
- 239000010703 silicon Substances 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- MOADXICVXMBHET-UHFFFAOYSA-N tricyclohexylmethylphosphane Chemical group C1CCCCC1C(C1CCCCC1)(P)C1CCCCC1 MOADXICVXMBHET-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 229910021419 crystalline silicon Inorganic materials 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000012670 alkaline solution Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 67
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 25
- 238000006555 catalytic reaction Methods 0.000 claims description 20
- 150000007524 organic acids Chemical class 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 150000001720 carbohydrates Chemical class 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 40
- 230000000052 comparative effect Effects 0.000 description 24
- 239000000047 product Substances 0.000 description 16
- 238000001914 filtration Methods 0.000 description 15
- 238000002791 soaking Methods 0.000 description 14
- 230000002378 acidificating effect Effects 0.000 description 13
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000008103 glucose Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000007171 acid catalysis Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- -1 citrate radical Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005406 washing Methods 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
- 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
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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Abstract
The invention discloses a preparation method of a silicon-aluminum solid acid catalyst, which comprises the following steps: step one, taking a silicon source, an aluminum source and an organic template agent and placing the silicon source, the aluminum source and the organic template agent in an alkaline solution; step two, placing the mixed material obtained in the step one in a reaction kettle for hydrothermal reaction; in the reaction process, the organic template agent provides reaction sites, the silicon-aluminum oxide grows on the organic template agent, and the organic template agent is broken along with the continuous growth of the silicon-aluminum oxide tissue crystal; cleaning and drying to obtain powdery crystalline silicon aluminum oxide; step three, immersing the silicon-aluminum oxide obtained in the step two into an acid solution to obtain a solid acid catalyst; the silicon in the solid acid catalyst is SiO 2 In the form of Al 2 O 3 Exists in the form of (1); wherein the organic template agent is tricyclohexylmethylphosphine, and the alkali source of the alkaline solution in the first step is tetrapropylammonium hydroxide; the solid acid catalyst prepared by the invention is applied to the preparation of biosaccharide, and has high catalytic efficiency and long catalytic life.
Description
Technical Field
The invention relates to the technical field of silicon-aluminum solid acid catalysts, in particular to a silicon-aluminum solid acid catalyst, a preparation method and application thereof.
Background
In the production process of the existing saccharide products, raw materials need to be catalyzed to obtain target products, the original catalyst is liquid acid, but after the catalyst is used reversely, the catalyst and the products are difficult to separate, the catalytic efficiency is low, and equipment is corroded to a certain extent.
Disclosure of Invention
The invention aims to provide a preparation method of a silicon-aluminum solid acid catalyst, which constructs a silicon-aluminum framework with stable acidification structure, improves the catalytic performance and prolongs the catalytic life.
In order to solve the technical problem, the technical scheme of the invention is as follows: a method of preparing a solid acid catalyst comprising the steps of:
step one, taking a silicon source, an aluminum source and an organic template agent and placing the silicon source, the aluminum source and the organic template agent in an alkaline solution;
step two, placing the mixed material obtained in the step one in a reaction kettle for hydrothermal reaction;
in the reaction process, the organic template agent provides reaction sites, the silicon-aluminum oxide grows on the organic template agent, and the organic template agent is broken along with the continuous growth of the silicon-aluminum oxide tissue crystal;
cleaning and drying to obtain powdery crystalline silicon aluminum oxide;
step three, immersing the silicon-aluminum oxide obtained in the step two into an acid solution to obtain a solid acid catalyst;
the silicon in the solid acid catalyst is SiO 2 In the form of Al 2 O 3 Exists in the form of (1);
wherein the organic template agent is tricyclohexylmethylphosphine, and the alkali source of the alkaline solution in the first step is tetrapropylammonium hydroxide.
Preferably wherein the molar ratio of silicon to aluminum is from 25 to 100; wherein aluminum is the acid center. The silicon-aluminum solid acid catalyst obtained by the invention has stable catalytic performance by adjusting the silicon-aluminum molar ratio and considering both the structural stability and the acid center of the amount of combinable acid radical ions.
Preferably, the amount of the organic template material is 0.03 to 0.06 times the amount of the silicon material. The invention preferably selects the dosage of the organic template agent, and simultaneously promotes the formation of the mixed skeleton without the relatively independent action of the tricyclohexylmethylphosphine and the tetrapropylammonium hydroxide, and ensures that the particle size of the mixed skeleton is small and the specific surface area is large.
Preferably, the silicon source is orthosilicon acetate; the aluminum source is aluminum sulfate.
Preferably, the process conditions of the hydrothermal reaction in the second step are as follows:
the reaction temperature is 200 ℃ to 260 ℃; the reaction time is 2 to 3 hours. The invention utilizes hydrothermal reaction to lead the mixed structure skeleton to grow uniformly under relatively mild reaction conditions, and has small grain diameter and large specific surface area.
Preferably, the acid solution in the third step is a mixed acid solution of inorganic acid and organic acid; the organic acid has carboxylic acid groups in chain structures, and the organic acid adsorbs basic groups generated in the middle of carbohydrate catalysis through the carboxylic acid groups in a chain manner. The invention utilizes the carboxylic acid group of the organic acid to adsorb the catalytic intermediate product and combines the carboxylic acid group with the inorganic acid to effectively promote the catalysis, thereby improving the catalytic performance.
Preferably, the inorganic acid is sulfuric acid and the organic acid is citric acid. In the invention, the citric acid has a large amount of carboxylic acid groups and is in a chain structure, and in the sugar catalysis process, the organic molecular chain has a chain adsorption effect on alkaline groups such as intermediate products ribose, methylsulfonyl and the like which are catalyzed by the sugar, so that the continuity of the intermediate products is ensured; meanwhile, the sulfonic group helps the saccharides to be quickly dehydrated and deformed in the catalysis process, the saccharide molecular chains are easy to break, and citric acid is matched at the moment, so that the acidic group is provided to catalyze the saccharide deformation, the chain structure of the saccharides is stabilized to realize fixed-point catalysis, and the catalysis efficiency is improved.
Preferably, the mass ratio of the inorganic acid to the organic acid is 3:1. The invention controls the ratio of inorganic acid and organic acid, realizes dynamic fixed-point catalysis by matching with sulfonic acid group and citric acid group when the carboxyl group of citric acid continuously adsorbs the substance to be catalyzed to the periphery of the surface of solid acid, namely the invention utilizes the adsorption effect of the carboxyl group in the citric acid to transfer the substance in the preparation of biosaccharide from the pure concentration gradient drive, further combines the active adsorption of the carboxyl group, and matches with the basic acid catalysis effect of the sulfonic acid group and the citric acid group, thereby ensuring the dynamic continuous adsorption-catalysis and effectively promoting the catalysis. That is, the particulate matter obtained by the present invention utilizes the surface area and the surrounding liquid environment to construct an open and renewed catalytic reaction layer.
The invention aims to provide a silicon-aluminum solid acid catalyst which has small particles, large specific surface area and stable structure.
In order to solve the technical problem, the technical scheme of the invention is as follows: the solid acid catalyst prepared by the preparation method has the specific surface area of the silicon-aluminum oxide of 689 square meters/gram to 791 square meters/gram.
The invention aims to provide a silicon-aluminum solid acid catalyst applied to biosaccharide preparation, and the silicon-aluminum solid acid catalyst has the advantages of good catalytic effect, stable catalytic performance and long catalytic life.
By adopting the technical scheme, the invention has the beneficial effects that:
compared with solid acid with a porous structure in the prior art, the crystalline silicon aluminum oxide prepared by the invention is used as a skeleton for forming an acid center, the main inventive concept of the invention is that tricyclohexylmethylphosphine used as an organic template is used for providing a reaction site, the particle size of the silicon aluminum oxide is controlled, the silicon aluminum oxide is a crystal, the crystal growth can be carried out on the organic template, when the crystal grows to a certain size, the organic template is broken, and the tissue crystal continues to grow; the dosage of tricyclohexylmethylphosphine is too small, the grain size of the silicon-aluminum oxide is large, the specific surface area is small, and the catalytic activity is low; too much tricyclohexylmethylphosphine is used to dilute the reaction solution, so that the product yield is influenced;
in the hydrothermal reaction process, a silicon source and an aluminum source generate SiO in a high-temperature alkaline environment 2 And Al 2 O 3 The Si and Al with similar particle sizes can be mutually doped and nested to form a mixed skeleton structure, and the more Si element in the mixed skeleton structure, the more stable the mixed skeleton structure; the Al element in the mixed skeleton structure is taken as an acid site and can be combined with an acid group, the more the Al element is, the more the acid group can be loaded, and the stronger the catalytic activity is; al is taken as an acidic active site and is combined with an acidic group through an ionic bond, the acidic group can ensure effective complexation and complete separation of a sugar-making intermediate product in the sugar-making process, an acidic environment is provided to promote the hydrolysis of saccharides, meanwhile, the stable structure of the acidic group is ensured, and the catalytic stability is improved; the invention utilizes substances and dosage to further combine hydrothermal reaction to construct a crystal structure and a mixed skeleton structure capable of being acidified, increases the specific surface area of the crystalline silicon aluminum oxide by reducing the particle size of the crystalline silicon aluminum oxide, is convenient to be matched with soaking acid liquor to connect acid groups to the surface of the mixed skeleton structure, and improves the catalytic efficiency of the invention applied to sugar catalysisWhile extending the catalytic life of the catalysts used in sugar catalysis.
Thereby achieving the above object of the present invention.
Drawings
FIG. 1 is an XRD pattern of a solid acid catalyst of silicon aluminum obtained in example 4 of the present invention;
FIG. 2 is a standard spectrum of the system with its own silica alumina.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
The embodiment discloses a preparation method of a solid acid catalyst, which comprises the following steps:
step one, taking a silicon source, an aluminum source and an organic template agent and placing the silicon source, the aluminum source and the organic template agent in an alkaline solution;
the silicon source is n-silicon acetate; the aluminum source is aluminum sulfate;
the proportion of the raw materials used in this example is as follows:
n(SiO 2 )：n(Al 2 O 3 )=50；
n (tetrapropylammonium hydroxide): n (SiO) 2 )=0.005；
n (tricyclohexylmethylphosphine): n (SiO) 2 )=0.03；
Step two, placing the mixed material obtained in the step one in a reaction kettle for hydrothermal reaction; fully stirring, then reacting for 2 hours at 200 ℃ to obtain silicon-aluminum oxide, cooling and filtering to obtain powdery silicon-aluminum oxide;
in the reaction process, the organic template agent provides reaction sites, the silicon-aluminum oxide grows on the organic template agent, and the organic template agent is broken along with the continuous growth of the silicon-aluminum oxide tissue crystal;
cleaning and drying to obtain powdery crystalline silicon aluminum oxide;
step three, immersing the silicon-aluminum oxide obtained in the step two into an acid solution to obtain a solid acid catalyst;
the silicon in the solid acid catalyst is SiO 2 In the form of Al 2 O 3 Exists in the form of (1);
wherein the organic template agent is tricyclohexylmethylphosphine, and the alkali source of the alkaline solution in the first step is tetrapropylammonium hydroxide.
Soaking the silicon-aluminum oxide prepared in the embodiment into a mixture of silicon-aluminum oxide and aluminum oxide according to the mass ratio of 3:1, soaking the mixed acid sulfuric acid and citric acid for 3 hours, filtering and drying to obtain the target product, namely the silicon-aluminum type solid acid catalyst.
The concentration of concentrated sulfuric acid and citric acid in this example may range from 70% to 85%.
Example 2
The main differences between this embodiment and embodiment 1 are:
n(SiO 2 )：n(Al 2 O 3 )=100；
n (tetrapropylammonium hydroxide): n (SiO) 2 )=0.007；
n (tricyclohexylmethylphosphine): n (SiO) 2 )=0.04；
Putting the reaction raw materials into a reaction kettle, fully stirring, then reacting for 2.3 hours at 220 ℃ to obtain silicon-aluminum oxide, cooling, and filtering to obtain powdery silicon-aluminum oxide;
soaking the silicon-aluminum oxide prepared in the embodiment into a solution prepared by mixing the following components in a mass ratio of 3:1, soaking the mixed acid sulfuric acid and citric acid for 3 hours, filtering and drying to obtain the target product, namely the silicon-aluminum type solid acid catalyst.
Example 3
The main differences between this embodiment and embodiment 1 are:
n(SiO 2 )：n(Al 2 O 3 )=150；
n (tetrapropylammonium hydroxide): n (SiO) 2 )=0.009；
n (tricyclohexylmethylphosphine): n (SiO) 2 )=0.05；
Putting the reaction raw materials into a reaction kettle, fully stirring, then reacting for 2.6 hours at 240 ℃ to obtain silicon-aluminum oxide, cooling, and filtering to obtain powdery silicon-aluminum oxide;
soaking the silicon-aluminum oxide prepared in the embodiment into a mixture of silicon-aluminum oxide and aluminum oxide according to the mass ratio of 3:1, soaking the mixed acid sulfuric acid and citric acid for 3 hours, filtering and drying to obtain the target product, namely the silicon-aluminum type solid acid catalyst.
Example 4
The main differences between this embodiment and embodiment 1 are:
n(SiO 2 )：n(Al 2 O 3 )= 200；
n (tetrapropylammonium hydroxide): n (SiO) 2 )=0.01；
n (tricyclohexylmethylphosphine): n (SiO) 2 )= 0.06；
Putting the reaction raw materials into a reaction kettle, fully stirring, then reacting at 260 ℃ for 2.8 hours to obtain silicon-aluminum oxide, cooling, and filtering to obtain powdery silicon-aluminum oxide;
soaking the silicon-aluminum oxide prepared in the embodiment into a solution prepared by mixing the following components in a mass ratio of 3:1, soaking the mixed acid sulfuric acid and citric acid for 3 hours, filtering and drying to obtain the target product, namely the silicon-aluminum type solid acid catalyst.
Example 5
The main differences between this embodiment and embodiment 1 are:
n(SiO 2 )：n(Al 2 O 3 )= 200；
n (tetrapropylammonium hydroxide): n (SiO) 2 )= 0.01；
n (tricyclohexylmethylphosphine): n (SiO) 2 )= 0.05；
Putting the reaction raw materials into a reaction kettle, fully stirring, then reacting for 3 hours at 260 ℃ to obtain silicon-aluminum oxide, cooling, and filtering to obtain powdery silicon-aluminum oxide;
soaking the silicon-aluminum oxide prepared in the embodiment into a mixture of silicon-aluminum oxide and aluminum oxide according to the mass ratio of 3:1, soaking the mixed acid sulfuric acid and citric acid for 3 hours, filtering and drying to obtain the target product, namely the silicon-aluminum type solid acid catalyst.
Comparative example 1
This example uses the liquid catalyst sulfuric acid as the catalyst for biosaccharide production.
Comparative example 2
In the example, the silicon-aluminum solid catalyst ZMS-5 is used as a catalyst for preparing the biosaccharide, and the silicon-aluminum solid catalyst ZMS-5 is an existing product on sale, does not load an acidic group and has a specific surface area of 220 square meters per gram.
Comparative example 3
The main difference between this example and example 1 is that:
n(SiO 2 )：n(Al 2 O 3 )=50；
n (tetrapropylammonium hydroxide): n (SiO) 2 )=0.005；
n (tricyclohexylmethylphosphine): n (SiO) 2 )=0.03；
Putting the reaction raw materials into a reaction kettle, fully stirring, then reacting for 2 hours at 200 ℃ to obtain silicon-aluminum oxide, cooling, and filtering to obtain powdery silicon-aluminum oxide;
soaking the silicon-aluminum oxide into a sulfuric acid solution for 3 hours, filtering and drying to obtain a target product silicon-aluminum type solid acid catalyst, wherein the use amount of sulfuric acid in the example is the same as that of mixed acid in the example 1; the concentration of sulfuric acid was the same as that of sulfuric acid in example 1.
Comparative example 4
The main difference between this example and example 1 is that:
n(SiO 2 )：n(Al 2 O 3 )=50；
n (tetrapropylammonium hydroxide): n (SiO) 2 )=0.005；
n (tricyclohexylmethylphosphine): n (SiO) 2 )=0.03；
Putting the reaction raw materials into a reaction kettle, fully stirring, then reacting for 2 hours at 200 ℃ to obtain silicon-aluminum oxide, cooling, and filtering to obtain powdery silicon-aluminum oxide;
soaking the silicon-aluminum oxide into a citric acid solution for 3 hours, filtering and drying to obtain a target product silicon-aluminum type solid acid catalyst, wherein the using amount of citric acid in the example is the same as that of the mixed acid in the example 1; the concentration of citric acid was the same as that of citric acid in example 1.
The specific surface area of the solid acid catalysts obtained in comparative examples 2 to 4 and examples 1 to 5 was measured by a specific surface area meter, and the specific data are shown in table 1.
TABLE 1 comparison of specific surface area data of the solid acid catalysts obtained in comparative examples 2 to 4 and examples 1 to 5
| Group of | Specific surface area (square meter/gram) |
| Comparative example 2 | 220 |
| Comparative example 3 | 687 |
| Comparative example 4 | 691 |
| Example 1 | 689 |
| Example 2 | 743 |
| Example 3 | 769 |
| Example 4 | 791 |
| Example 5 | 785 |
As can be seen from Table 1, compared with the existing products, the specific surface area of the silicon-aluminum oxide prepared by the catalyst synthesis method provided by the invention is improved by 3 to 4 times, the product with high specific surface area is effectively prepared, and meanwhile, the specific surface area of the product is increased along with the increase of the dosage of the organic template, namely tricyclohexylmethylphosphine, wherein the specific surface area of the product in example 4 is as high as 791 square meters per gram. The chemical analysis is carried out on the silicon aluminum oxide obtained in the example 4, the XRD is tested, and the comparison between the figure 1 and the figure 2 shows that the synthesized sample of the invention has characteristic peaks at 9.35 degrees, 18.49 degrees, 20.38 degrees, 27.76 degrees and 50.31 degrees, which correspond to the standard spectrum at the characteristic peaks; further combining the comparison between fig. 1 and fig. 2, it can be seen that the silicon aluminum oxide prepared by the present invention has a large specific surface area and a smaller corresponding crystal form, so that the peak intensity value of the characteristic peak at 27.76 ° is decreased, and the data in this case is consistent with the above specific surface area test results, which indicates that the present invention successfully synthesizes silicon aluminum oxide in which silicon and aluminum are mutually doped and nested.
The catalysts corresponding to examples 1 to 5 and comparative examples 1 to 5 were subjected to a catalytic activity test, which was specifically as follows:
taking a certain amount of glucose, and mixing the glucose: the molar mass ratio of the catalyst is 1:0.1 adding a catalyst, adding a solution DMF (N-N-dimethylformamide), reacting for 1h at 130 ℃, ending the reaction, testing the glucose content before and after the reaction by using a traditional glucose enzymatic method, and calculating the catalytic rate, wherein the specific algorithm of the catalytic rate is that the catalytic rate = (the glucose amount before the reaction-the glucose amount after the reaction)/the glucose amount before the reaction is 100%, and the test data of the catalytic rate is shown in Table 2.
Table 2 catalytic activity of catalysts corresponding to examples 1 to 5 and comparative examples 1 to 5
| Group of | Catalytic ratio (%) |
| Comparative example 1 | 90 |
| Comparative example 2 | 65 |
| Comparative example 3 | 86 |
| Comparative example 4 | 79 |
| Example 1 | 91 |
| Example 2 | 93 |
| Example 3 | 94 |
| Example 4 | 96 |
| Example 5 | 95 |
As can be seen from the catalytic data in Table 2, the catalytic rate of the solid acid catalyst provided by the invention is better than that of the traditional liquid catalyst, and compared with the existing silicon-aluminum type solid catalyst, the catalytic rate is improved by nearly 50%, and the catalytic performance is obviously improved; comparative example 4 is used for loading citric acid alone, and because the citric acid has a large molecular chain, the loaded citric acid has poor effect and is difficult to form dynamic fixed-point catalysis, and the catalytic rate is only 79%; comparative example 3 is carried with sulfonic group alone, and the specific surface area of the silicon-aluminum oxide is large, the sulfonic group is rich, and the catalytic rate is 86%; after the mixed acid is loaded in the embodiments 1 to 5, the catalytic rate is 91 to 96 percent, and the catalytic performance is obviously improved.
The catalytic rate of examples 1 to 5 is higher than that of comparative examples 2 to 4, mainly the carboxyl group of citric acid in the mixed acid continuously adsorbs a substance to be catalyzed to the periphery of the surface of the solid acid, and dynamic fixed-point catalysis is realized by matching with the sulfonic acid group and the citric acid group, namely the invention utilizes the adsorption effect of the carboxyl group in the citric acid to transfer the substance in the preparation of biosaccharide from the pure concentration gradient drive, further combines the active adsorption of the carboxyl group, and matches with the basic acid catalysis effect of the sulfonic acid group and the citric acid group, so that the dynamic continuous adsorption-catalysis is ensured, and the catalysis is effectively promoted. That is, the particulate matter obtained by the present invention utilizes the surface area and the surrounding liquid environment to construct an open and renewed catalytic reaction layer.
The solid acid catalysts obtained in examples 1 to 5 and comparative examples 2 to 4 were subjected to a reuse effect test, and the specific operation method was as follows:
and (3) filtering and separating the solid acid catalyst, washing with ethanol, drying, catalyzing glucose again according to the steps, and calculating the catalytic efficiency of repeated use for five times.
Table 3 stability testing of solid acid catalysts corresponding to examples 1 to 5 and comparative examples 2 to 4
| Item | First catalytic ratio (%) | Second catalytic ratio (%) | Third catalytic ratio (%) | Fourth catalytic ratio (%) | Fifth catalytic ratio (%) |
| Comparative example 2 | 65 | 59 | 46 | 37 | 34 |
| Comparative example 3 | 86 | 80 | 76 | 70 | 64 |
| Comparative example 4 | 79 | 70 | 61 | 55 | 51 |
| Example 1 | 91 | 89 | 85 | 78 | 72 |
| Example 2 | 93 | 90 | 84 | 77 | 73 |
| Example 3 | 94 | 92 | 89 | 85 | 79 |
| Example 4 | 96 | 95 | 90 | 86 | 81 |
| Example 5 | 95 | 93 | 90 | 84 | 79 |
As can be seen from Table 3, the crystalline silicon aluminum oxide prepared by the method serves as a framework for forming an acid center, and compared with the solid acid with a porous structure in the prior art, the silicon source and the aluminum source generate SiO under a high-temperature alkaline environment 2 And Al 2 O 3 The grain sizes of Si and Al are similar, and the Si and Al can be mutually doped and nested to form a mixed framework structure, and the more Si elements in the mixed framework structure, the more stable the mixed framework structure; the Al element in the mixed skeleton structure is taken as an acid site and can be combined with an acid group, the more the Al element is, the more the acid group can be loaded, and the stronger the catalytic activity is; the Al is taken as an acidic active site and is combined with an acidic group through an ionic bond, the acidic group can ensure effective complexation and complete separation of a sugar-making intermediate product in the sugar-making process, an acidic environment is provided to promote the hydrolysis of the sugar, the stable structure of the acidic group is ensured, and the catalytic stability is improved; according to the invention, a crystal structure and an acidifiable mixed skeleton structure are constructed by further combining hydrothermal reaction with substances and dosage, the specific surface area of the crystalline silicon aluminum oxide is increased by reducing the particle size of the crystalline silicon aluminum oxide, and acidic groups are conveniently connected to the surface of the mixed skeleton structure by matching with soaking acid liquor; the mixed framework of the invention has stable structure and good matching effectThe carboxyl groups are used for adsorption to realize dynamic fixed-point catalysis, and simultaneously, the basic acid catalysis of the sulfonic acid group and the citrate radical is ensured, so compared with comparative examples 2 to 4, the solid acid catalyst prepared by the invention has good repeated use effect, the invention improves the catalysis efficiency of biological sugar preparation, has long catalysis life, and is beneficial to efficient and continuous preparation of biological sugar.
Claims (6)
1. The application of a solid acid catalyst in biological sugar hydrolysis is characterized in that:
the method comprises the following steps:
step one, taking a silicon source, an aluminum source and an organic template agent and placing the silicon source, the aluminum source and the organic template agent in an alkaline solution;
the molar ratio of silicon to aluminum is 25 to 100;
the amount of the organic template substance is 0.03 to 0.06 times the amount of the silicon substance;
step two, placing the mixed material obtained in the step one in a reaction kettle for hydrothermal reaction;
the technological conditions of the hydrothermal reaction are as follows:
the reaction temperature is 200 ℃ to 260 ℃; the reaction time is 2 to 3 hours;
in the reaction process, the organic template agent provides reaction sites, the silicon-aluminum oxide grows on the organic template agent, and the organic template agent is broken along with the continuous growth of the silicon-aluminum oxide tissue crystal;
cleaning and drying to obtain powdery crystalline silicon aluminum oxide;
step three, immersing the silicon-aluminum oxide obtained in the step two into an acid solution to obtain a solid acid catalyst;
the acid solution in the third step is a mixed acid solution of inorganic acid and organic acid; the organic acid has carboxylic acid groups in chain structures, and basic groups generated in the catalysis of saccharides are adsorbed by the organic acid through the carboxylic acid groups in a chain manner; the silicon in the solid acid catalyst is SiO 2 In the form of Al 2 O 3 Exists in the form of (1);
wherein the organic template agent is tricyclohexylmethylphosphine, and the alkali source of the alkaline solution in the first step is tetrapropylammonium hydroxide.
2. Use according to claim 1, characterized in that: the aluminum in the silicon aluminum oxide is an acid center.
3. Use according to claim 1, characterized in that: the silicon source is orthosilicon acetate; the aluminum source is aluminum sulfate.
4. Use according to claim 1, characterized in that: the inorganic acid is sulfuric acid, and the organic acid is citric acid.
5. Use according to claim 4, characterized in that: the mass ratio of the inorganic acid to the organic acid is 3:1.
6. Use according to claim 1, characterized in that: the specific surface area of the silicon aluminum oxide is 689 square meter/gram to 791 square meter/gram.
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