CN113735086A - Aluminum phosphate, preparation method and application thereof, and preparation method of o-hydroxyanisole - Google Patents
Aluminum phosphate, preparation method and application thereof, and preparation method of o-hydroxyanisole Download PDFInfo
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- CN113735086A CN113735086A CN202111042097.9A CN202111042097A CN113735086A CN 113735086 A CN113735086 A CN 113735086A CN 202111042097 A CN202111042097 A CN 202111042097A CN 113735086 A CN113735086 A CN 113735086A
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- aluminum
- hydroxyanisole
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- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 52
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 43
- 239000011574 phosphorus Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 19
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000000017 hydrogel Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000002798 polar solvent Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000006266 etherification reaction Methods 0.000 claims description 6
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 5
- 238000005804 alkylation reaction Methods 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 238000006352 cycloaddition reaction Methods 0.000 claims description 3
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 3
- 238000006317 isomerization reaction Methods 0.000 claims description 3
- 238000006462 rearrangement reaction Methods 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000002808 molecular sieve Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000005696 Diammonium phosphate Substances 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/36—Aluminium phosphates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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Abstract
The invention belongs to the technical field of catalyst preparation, and particularly relates to aluminum phosphate and a preparation method thereof, and a preparation method of o-hydroxyanisole. The preparation method provided by the invention comprises the following steps: mixing pseudo-boehmite, a soluble phosphorus source, a polar solvent and strong acid to obtain aluminum phosphate hydrosol, wherein the atomic molar ratio of aluminum elements in the pseudo-boehmite to phosphorus elements in the phosphorus source is more than or equal to 1: 0.5; adjusting the pH value of the aluminum phosphate hydrosol to be more than or equal to 6 to obtain the aluminum phosphate hydrogel; drying the aluminum phosphate hydrogel to obtain an aluminum phosphate precursor; and calcining the aluminum phosphate precursor to obtain the aluminum phosphate. The aluminum phosphate provided by the invention has the advantages of high activity and stability, high catechol conversion rate and high selectivity of the target product o-hydroxyanisole when used for catalyzing the monoetherization reaction of catechol and dimethyl carbonate.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to aluminum phosphate, a preparation method and application thereof, and a preparation method of o-hydroxyanisole.
Background
O-hydroxyanisole, also known as methyl guaiacol, is a white or light yellow crystalline or transparent oily liquid with unique aromatic odor, is a fine chemical intermediate and chemical raw material in the industries of spice, agriculture, medicine, dye and the like, and has wide application.
The synthesis methods of o-hydroxyanisole are numerous, and can be divided into natural product extraction methods and industrial synthesis methods according to sources, the natural product extraction methods are limited by raw materials and extraction processes, the yield is limited, the yield requirements are difficult to meet, and the industrial synthesis methods become the main production modes at present.
The industrial synthesis method can be divided into a liquid phase method and a multiphase method according to the operation mode, the liquid phase method has the advantages of high reaction speed and the like, but the liquid phase method has high operation intensity and high labor cost and is eliminated, and the multiphase method becomes the mainstream process for producing the o-hydroxyanisole at present. The multiphase method is divided into a methanol method and a dimethyl carbonate method according to different raw materials, and the methanol method becomes a method with industrial prospect according to the price advantage of the raw materials, but easily causes pollution to the environment.
The synthesis route for synthesizing the o-hydroxyanisole by gas-solid phase catalysis with the catechol and the dimethyl carbonate as raw materials has the advantage of environmental friendliness and attracts more and more attention of people, but the yield of the target product o-hydroxyanisole is low under the influence of the performance of the catalyst.
Disclosure of Invention
In view of the above, the invention provides aluminum phosphate, a preparation method and application thereof, and a preparation method of o-hydroxyanisole.
The invention provides a preparation method of aluminum phosphate, which comprises the following steps:
mixing pseudo-boehmite, a soluble phosphorus source, a polar solvent and strong acid to obtain aluminum phosphate hydrosol, wherein the atomic molar ratio of aluminum elements in the pseudo-boehmite to phosphorus elements in the phosphorus source is more than or equal to 1: 0.5;
adjusting the pH value of the aluminum phosphate hydrosol to be more than or equal to 6 to obtain the aluminum phosphate hydrogel;
drying the aluminum phosphate hydrogel to obtain an aluminum phosphate precursor;
and calcining the aluminum phosphate precursor to obtain the aluminum phosphate.
Preferably, the atomic molar ratio of the aluminum element in the pseudo-boehmite to the phosphorus element in the phosphorus source is 1 (0.5-1.5).
Preferably, the calcining temperature is 400-800 ℃, the calcining heat preservation time is 5-24 h, and the temperature rising rate from the room temperature to the calcining temperature is 1-8 ℃/min.
Preferably, the drying temperature is 80-120 ℃, and the heating rate of heating from room temperature to the drying temperature is 1-8 ℃/min.
Preferably, the soluble source of phosphorus comprises phosphoric acid and/or an ammonium phosphate salt.
Preferably, the strong acid solution is a nitric acid solution, and the mass content of the nitric acid solution is 65-68%.
The invention provides the aluminum phosphate prepared by the preparation method in the technical scheme, and the surface of the aluminum phosphate is provided with a weak acid center and a medium-strength acid center.
The invention provides application of the aluminum phosphate serving as the catalyst in dehydrogenation reaction, isomerization reaction, alkylation reaction, rearrangement reaction, condensation reaction, cycloaddition reaction and etherification reaction.
The invention provides a preparation method of o-hydroxyanisole, which is characterized in that the o-hydroxyanisole is obtained by adopting aluminum phosphate to catalyze catechol and dimethyl carbonate to carry out monoetherification reaction.
Preferably, the temperature of the monoetherification reaction is 220-320 ℃.
Preferably, the molar ratio of the catechol to the dimethyl carbonate is 1 (3-8); the reaction space velocity in the mono-etherification reaction is 1-8 mL/g-1·h-1。
The invention provides a preparation method of aluminum phosphate, which comprises the following steps: mixing pseudo-boehmite, a soluble phosphorus source, a polar solvent and strong acid to obtain aluminum phosphate hydrosol, wherein the atomic molar ratio of aluminum elements in the pseudo-boehmite to phosphorus elements in the phosphorus source is more than or equal to 1: 0.5; adjusting the pH value of the aluminum phosphate hydrosol to be more than or equal to 6 to obtain an aluminum phosphate hydrogel, and drying the aluminum phosphate hydrogel to obtain an aluminum phosphate precursor; and calcining the aluminum phosphate precursor to obtain the aluminum phosphate. The preparation method provided by the invention is characterized in that pseudo-boehmite and a soluble phosphorus source are dissolved in a strong acid solution to form an aluminum phosphate hydrosol, the pH value of the aluminum phosphate hydrosol is more than or equal to 6 to obtain an aluminum phosphate hydrogel, and finally, the aluminum phosphate is obtained by sequentially drying and calcining. In the sol-gel process, the atomic molar ratio of aluminum element in pseudo-boehmite to phosphorus element in a phosphorus source is controlled to be more than or equal to 1:0.5, the pH value during gel formation is controlled to be more than or equal to 6, the surface of the finally formed aluminum phosphate presents a uniform distribution of a basic center and a Lewis acid center, the whole surface of the molecular sieve presents higher faintly acid, the aluminum phosphate is used as a catalyst to catalyze the synergistic effect of the basic center and the Lewis acid center on the surface of the aluminum phosphate during catechol etherification reaction, the catalytic activity is high, the surface of the prepared aluminum phosphate has higher faintly acid and weak adsorption capacity on catechol molecules, and reactants and products can be quickly separated from the surface of the molecular sieve during catalytic reaction, are not easy to deposit carbon and have higher stability.
The invention provides a preparation method of o-hydroxyanisole, which is characterized in that the o-hydroxyanisole is obtained by adopting aluminum phosphate to catalyze catechol and dimethyl carbonate to carry out monoetherification reaction. According to the technical scheme, the aluminum phosphate is used as the catalyst to catalyze the gas-solid phase monoetherification of catechol and dimethyl carbonate to prepare the o-hydroxyanisole, so that few byproducts are generated and the selectivity of the byproducts is low. The results of the examples show that when the aluminum phosphate provided by the invention is used for catalyzing the reaction, the conversion rate of catechol is 93.0%, the selectivity of o-hydroxyanisole is 71.1%, the selectivity of o-dimethyl ether is 27.0%, and the selectivity of other byproducts is 1.9%. The aluminum phosphate provided by the invention has good stability, the activity of the catalytic reaction is not obviously reduced within 200 hours, the conversion rate of catechol can be maintained to be more than 92%, the selectivity of o-hydroxyanisole is maintained to be more than 70%, the selectivity of dimethyl phthalate is 28%, and the selectivity of other byproducts is 2%.
The aluminum phosphate provided by the invention has the advantages of simple preparation process, low raw material cost and green and pollution-free preparation process.
Drawings
FIG. 1 is a graph showing the results of activity stability of aluminum phosphate prepared in example 1 of the present invention.
FIG. 2 is a graph showing the results of the activity stability of the product of comparative example 2 of the present invention.
Detailed Description
The invention provides a preparation method of aluminum phosphate, which comprises the following steps:
mixing pseudo-boehmite, a soluble phosphorus source, a polar solvent and strong acid to obtain aluminum phosphate hydrosol, wherein the atomic molar ratio of aluminum elements in the pseudo-boehmite to phosphorus elements in the phosphorus source is more than or equal to 1: 0.5;
adjusting the pH value of the aluminum phosphate hydrosol to be more than or equal to 6 to obtain the aluminum phosphate hydrogel;
drying the aluminum phosphate hydrogel to obtain an aluminum phosphate precursor;
and calcining the aluminum phosphate precursor to obtain the aluminum phosphate.
In the present invention, the starting materials are all commercially available products well known to those skilled in the art unless otherwise specified.
The preparation method comprises the step of mixing pseudo-boehmite, a soluble phosphorus source, a polar solvent and strong acid to obtain the aluminum phosphate hydrosol, wherein the atomic molar ratio of aluminum elements in the pseudo-boehmite to phosphorus elements in the phosphorus source is more than or equal to 1: 0.5.
In the invention, the specific surface area of the pseudo-boehmite is preferably 200-300 m2(iv)/g, more preferably 250m2/g. The pore volume of the pseudo-boehmite is preferably 0.7-1 mL/g, and more preferably 0.8 mL/g. The preferred pore diameter of the pseudo-boehmite is 8-9 nm.
In the present invention, the soluble source of phosphorus is preferably phosphoric acid and/or an ammonium phosphate salt, more preferably one or more of phosphoric acid, diammonium phosphate, monoammonium phosphate and triammonium phosphate, and most preferably triammonium phosphate.
In the invention, the atomic molar ratio of the aluminum element in the pseudo-boehmite to the phosphorus element in the phosphorus source is more than or equal to 1:0.5, preferably 1 (0.5-1.5), more preferably 1 (0.6-1.3), and most preferably 1 (0.8-1). in the specific implementation of the invention, the atomic molar ratio of the aluminum element in the pseudo-boehmite to the phosphorus element in the phosphorus source is 1:0.85, 1:0.75, 1:0.95, and 1: 0.5.
In the present invention, the polar solvent is preferably water and/or a lower alcohol, more preferably water and/or ethanol, and most preferably water.
In the invention, the solid-to-liquid ratio of the pseudoboehmite to the polar solvent is preferably 1 (2.5-4.5), more preferably 1 (2.8-4), and most preferably 1 (3-3.5).
In the invention, the strong acid is preferably a nitric acid solution, and the mass content of the nitric acid solution is 65-68%.
In the present invention, the volume ratio of the strong acid to the pseudoboehmite is preferably (0.1 to 0.5) mL:1g, and more preferably (0.2 to 0.45) mL:1 g.
In the present invention, the mixing preferably comprises the steps of:
the pseudo-boehmite, the soluble phosphorus source and the polar solvent are subjected to first mixing to obtain a first mixed material,
and carrying out second mixing on the first mixed material and strong acid to obtain the aluminum phosphate hydrosol.
And carrying out first mixing on the pseudo-boehmite, the soluble phosphorus source and the polar solvent to obtain a first mixed material. In the present invention, the temperature of the first mixing is preferably 20 to 28 ℃. The time for the first mixing is preferably 1-3 h. The first mixing is carried out under the condition of stirring, and the invention has no special requirements on the specific implementation process of the stirring.
After the first mixed material is obtained, the first mixed material and strong acid are subjected to second mixing to obtain the aluminum phosphate hydrosol. In the present invention, the temperature of the second mixing is preferably 20 to 28 ℃. The second mixing time is preferably 1-3 h. The second mixing is carried out under the condition of stirring, and the invention has no special requirements on the specific implementation process of the stirring.
After the aluminum phosphate hydrosol is obtained, the pH value of the aluminum phosphate hydrosol is adjusted to be more than or equal to 6, the aluminum phosphate hydrogel is obtained, the pH value is preferably 7-10, and in the specific embodiment of the invention, the pH values are 7, 8 and 9.
The pH value of the aluminum phosphate hydrosol is preferably adjusted by using a pH regulator, the pH regulator is preferably ammonia water, and the invention has no special requirement on the mass concentration of the ammonia water. The pH value is preferably adjusted under the condition of stirring, and the invention has no special requirement on the specific implementation process of the stirring.
After the pH value of the aluminum phosphate hydrosol is more than or equal to 6, the aluminum phosphate hydrosol system with the pH value more than or equal to 6 is preferably subjected to standing aging to obtain the aluminum phosphate hydrogel, and the standing aging time is preferably 1-24 hours, and more preferably 5-20 hours. The temperature of the standing aging is preferably room temperature.
After the aluminum phosphate hydrogel is obtained, the aluminum phosphate hydrogel is dried to obtain the aluminum phosphate precursor.
In the invention, the drying temperature is preferably 80-120 ℃, and more preferably 90-100 ℃. In the invention, the drying time is preferably 24-48 h, and more preferably 30-35 h. The heating rate from room temperature to the drying temperature is preferably 1 to 8 ℃/min, and more preferably 2.5 to 5 ℃/min. In the practice of the present invention, the drying is preferably carried out in a drying oven.
According to the invention, the solvent and impurities (including acid radicals of strong acid, pH regulator and the like) in the aluminum phosphate hydrogel are removed by drying, so that a solid Al-P initial gel network is obtained.
After the aluminum phosphate precursor is obtained, the aluminum phosphate precursor is calcined to obtain the aluminum phosphate.
In the invention, the calcination temperature is preferably 400-800 ℃, more preferably 450-780 ℃, and most preferably 500-750 ℃. In the invention, the calcination heat preservation time is preferably 5-24 h, and more preferably 10-12 h. The heating rate from room temperature to the calcination temperature is preferably 1 to 8 ℃/min, and more preferably 5 to 7 ℃/min.
According to the invention, aluminum phosphate is formed by calcination, the network structure of the molecular sieve is strengthened, and residual impurities in the molecular sieve are further removed.
The invention provides the aluminum phosphate prepared by the preparation method in the technical scheme, and the surface of the aluminum phosphate is provided with a weak acid center and a medium-strength acid center.
In the present invention, in the case of the present invention,the specific surface area of the aluminum phosphate is preferably 60-90 m2A concentration of 65 to 80m is more preferable2/g. The pore volume of the aluminum phosphate is preferably 0.1-0.2 cm3G, more preferably 0.15cm3(ii) in terms of/g. The preferred pore diameter of the aluminum phosphate is 8-9 nm.
In the present invention, the aluminum phosphate employs NH3In the TPD analysis, the desorption temperature of ammonia is preferably 100 to 300 ℃.
The invention provides application of the aluminum phosphate serving as the catalyst in dehydrogenation reaction, isomerization reaction, alkylation reaction, rearrangement reaction, condensation reaction, cycloaddition reaction and etherification reaction.
The invention provides a preparation method of o-hydroxyanisole, which is characterized in that the o-hydroxyanisole is obtained by adopting aluminum phosphate to catalyze catechol and dimethyl carbonate to carry out monoetherification reaction.
When the aluminum phosphate provided by the invention is used as a catalyst to catalyze the monoetherification reaction of catechol and dimethyl carbonate, the alkaline center on the surface of the aluminum phosphate can activate the H atom on the hydroxyl group of the catechol, the electron-withdrawing action of the Lewis acid on the surface of the aluminum phosphate can adsorb the carbonyl oxygen atom of the dimethyl carbonate on the adjacent acid site, and the activated H on the hydroxyl group of the catechol can attack the carbon atom on the methyl group of the dimethyl carbonate to obtain the o-hydroxyanisole.
In the invention, the temperature of the monoetherification reaction is preferably 220-320 ℃, more preferably 230-300 ℃, and most preferably 250-280 ℃.
In the invention, the molar ratio of the catechol to the dimethyl carbonate is preferably 1 (3-8), and more preferably 1 (3.5-6).
In the invention, the reaction space velocity in the mono-etherification reaction is preferably 1-8 mL-g-1·h-1More preferably 1.5 to 7 mL/g-1·h-1Most preferably 2 to 5 mL/g-1·h-1。
In the present invention, the monoetherification reaction is preferably carried out in a fixed bed reactor, and the reaction is a gas-solid reaction.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Pseudo-boehmite (surface area of 250 m)2Perg, the pore volume is 0.8mL/g, the pore diameter is 8-9 nm), and phosphoric acid and deionized water are stirred and mixed at 40 ℃, wherein the atomic molar ratio of phosphorus element in the phosphoric acid to pseudo-boehmite aluminum element is 0.85: 1, the solid-to-liquid ratio of the pseudo-boehmite to the water is 1: 2.5; uniformly stirring the mixture, and adding 65% by mass of nitric acid, wherein the ratio of the amount of nitric acid (mL) to the pseudoboehmite (g) is 0.3: 1, obtaining an aluminum phosphate hydrosol, adjusting the pH value of the aluminum phosphate hydrosol to 8 by using ammonia water, and stirring and mixing for 2 hours to obtain the aluminum phosphate hydrogel; standing and deepening for 2 hours; heating the mixture until water is evaporated to dryness, and drying the mixture in a drying oven at 120 ℃ for 24 hours to obtain a precursor solid material; heating the solid material of the precursor from room temperature at 8 ℃/min to 500 ℃ and roasting for 24 hours to obtain the aluminum phosphate (the specific surface area is 65-80 m)2/g, pore volume 0.15cm3(g) the pore diameter is 8-9 nm), NH is adopted3The desorption temperature of ammonia for the TPD analysis is preferably 300 ℃.
Example 2
The procedure was substantially the same as in example 1 except that the phosphorus source was ammonium dihydrogen phosphate.
Example 3
The process was essentially the same as that of example 1, except that the phosphorus source was diammonium phosphate.
Example 4
The procedure was substantially the same as in example 1, except that aqueous ammonia was used to adjust the pH to 7.
Example 5
Substantially the same as in example 1 except that aqueous ammonia was used to adjust the pH to 9.
Example 6
Substantially the same as in example 1 except that the atomic molar ratio of the phosphorus element in the phosphorus source to the aluminum element of the pseudo-boehmite was 0.75: 1.
example 7
Substantially the same as in example 1 except that the atomic molar ratio of the phosphorus element in the phosphorus source to the aluminum element of the pseudo-boehmite was 0.95: 1.
example 8
Substantially the same as in example 1 except that the atomic molar ratio of the phosphorus element in the phosphorus source to the aluminum element of the pseudo-boehmite was 0.5: 1.
comparative example 1
The preparation method was substantially the same as that of example 1, except that the ratio of the amount of nitric acid (mL) to the amount of pseudoboehmite (g) was 0.
Comparative example 2
The procedure was substantially the same as in example 1, except that ammonia was not used for adjusting the pH.
Example 9
The molecular sieves prepared in examples 1-8 and the molecular sieves prepared in comparative examples 1 and 2 are used for catalyzing the reaction of catechol and dimethyl carbonate for preparing o-hydroxyanisole through gas-solid phase monoetherification, the reaction is carried out on a fixed bed device, and the reaction conditions are as follows: the molar ratio of catechol to dimethyl carbonate is 1:6, the reaction temperature is 250 ℃, and the reaction space velocity is 4 mL/g-1·h-1。
The conversion of catechol, the selectivity to o-hydroxyanisole, the selectivity to o-dimethylether, and the selectivity to other by-products were calculated, and the results are shown in table 1.
TABLE 1 results of example 9
From table 9, when the aluminum phosphate prepared by the invention is used for catalyzing gas-solid phase monoetherification of catechol and dimethyl carbonate to prepare o-hydroxyanisole, the catalyst has high reaction activity, few byproducts and low selectivity of the byproducts. Wherein the conversion rate of catechol is more than 45%, the selectivity of o-hydroxyanisole is more than or equal to 64%, the selectivity of o-dimethyl ether is 20-30%, and the selectivity of other byproducts is less than 5%.
Test example
The molecular sieve products prepared in example 1 and comparative example 2 were tested for stability when used as catalysts, wherein: the molecular sieves prepared in example 1 and comparative example 2 are applied to the reaction of preparing o-hydroxyanisole by gas-solid phase monoetherification of catechol and dimethyl carbonate, and the reaction is carried out on a fixed bed device, and the reaction conditions are as follows: the mol ratio of the catechol to the dimethyl carbonate is 1:6, the reaction temperature is 250 ℃, and the reaction space velocity is 4mL g-1·h-1。
The conversion rate of catechol, the selectivity of o-hydroxyanisole, the selectivity of o-dimethyl ether and the selectivity of byproducts are calculated, and the results obtained in example 1 are shown in fig. 1, so that it can be clearly observed that the conversion rate is not obviously reduced after the catalyst participates in the reaction for 200 hours, the o-hydroxyanisole selectivity is maintained above 70%, the selectivity of o-dimethyl ether is around 28%, and the selectivity of other byproducts is around 2%. The catalyst prepared by the preparation method provided by the embodiment 1 of the invention has good stability. While the catalyst of comparative example 2 shown in fig. 2 had poor stability after 30h of reaction when the conversion and selectivity were reduced from the initial 45.9% and 94.9% to 30.2% and 70.3%, respectively.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of aluminum phosphate is characterized by comprising the following steps:
mixing pseudo-boehmite, a soluble phosphorus source, a polar solvent and strong acid to obtain aluminum phosphate hydrosol, wherein the atomic molar ratio of aluminum elements in the pseudo-boehmite to phosphorus elements in the phosphorus source is more than or equal to 1: 0.5;
adjusting the pH value of the aluminum phosphate hydrosol to be more than or equal to 6 to obtain the aluminum phosphate hydrogel;
drying the aluminum phosphate hydrogel to obtain an aluminum phosphate precursor;
and calcining the aluminum phosphate precursor to obtain the aluminum phosphate.
2. The preparation method according to claim 1, wherein the atomic molar ratio of the aluminum element in the pseudoboehmite to the phosphorus element in the phosphorus source is 1 (0.5-1.5).
3. The preparation method according to claim 1, wherein the calcination temperature is 400 to 800 ℃, the calcination holding time is 5 to 24 hours, and the temperature rise rate from room temperature to the calcination temperature is 1 to 8 ℃/min.
4. The method according to claim 1, wherein the drying temperature is 80 to 120 ℃, and the rate of temperature increase from room temperature to the drying temperature is 1 to 8 ℃/min.
5. The method of claim 1, wherein the soluble source of phosphorus comprises phosphoric acid and/or an ammonium phosphate salt.
6. An aluminum phosphate obtained by the method as recited in any one of claims 1 to 5, wherein the aluminum phosphate has weak acid centers and medium-strength acid centers on the surface.
7. Use of the aluminum phosphate of claim 6 as a catalyst in dehydrogenation reactions, isomerization reactions, alkylation reactions, rearrangement reactions, condensation reactions, cycloaddition reactions, and etherification reactions.
8. A preparation method of o-hydroxyanisole, characterized in that o-hydroxyanisole is obtained by using the aluminum phosphate of claim 6 to catalyze catechol and dimethyl carbonate to carry out monoetherification reaction.
9. The preparation method according to claim 8, wherein the temperature of the monoetherification reaction is 220-320 ℃.
10. The preparation method of claim 8, wherein the molar ratio of the catechol to the dimethyl carbonate is 1 (3-8); the reaction space velocity of the monoetherification reaction is 1-8 mL-g-1·h-1。
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| CN114477117A (en) * | 2021-12-17 | 2022-05-13 | 中建材蚌埠玻璃工业设计研究院有限公司 | Aluminum phosphate-based powder for heat insulation and preparation method thereof |
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