NL2030281B1 - Aluminum phosphate and preparation method and use thereof, and preparation method of o-hydroxyanisole - Google Patents
Aluminum phosphate and preparation method and use thereof, and preparation method of o-hydroxyanisole Download PDFInfo
- Publication number
- NL2030281B1 NL2030281B1 NL2030281A NL2030281A NL2030281B1 NL 2030281 B1 NL2030281 B1 NL 2030281B1 NL 2030281 A NL2030281 A NL 2030281A NL 2030281 A NL2030281 A NL 2030281A NL 2030281 B1 NL2030281 B1 NL 2030281B1
- Authority
- NL
- Netherlands
- Prior art keywords
- aluminum phosphate
- reaction
- hydroxyanisole
- present disclosure
- preparation
- Prior art date
Links
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 34
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 32
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011574 phosphorus Substances 0.000 claims abstract description 28
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000000017 hydrogel Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002798 polar solvent Substances 0.000 claims abstract description 10
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005886 esterification reaction Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 17
- 238000006266 etherification reaction Methods 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 3
- 238000005804 alkylation reaction Methods 0.000 claims description 3
- 238000006482 condensation 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
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 6
- 229940009859 aluminum phosphate Drugs 0.000 description 83
- 235000014786 phosphorus Nutrition 0.000 description 22
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 230000002431 foraging effect Effects 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical class [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- NUMXHEUHHRTBQT-AATRIKPKSA-N 2,4-dimethoxy-1-[(e)-2-nitroethenyl]benzene Chemical compound COC1=CC=C(\C=C\[N+]([O-])=O)C(OC)=C1 NUMXHEUHHRTBQT-AATRIKPKSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001072332 Monia Species 0.000 description 1
- -1 agriculture Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000010210 aluminium Nutrition 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present disclosure relates to an aluminum phosphate and a preparation method thereof, and a preparation method of o— hydroxyanisole. The preparation method of aluminum phosphate includes the following steps: mixing pseudo—boehmite, a soluble phosphorus source, a polar solvent and a strong acid to obtain an aluminum phosphate hydrosol, with a mole ratio of aluminum atoms in the pseudo—boehmite to phosphorus atoms in the phosphorus source being Z l:0.5 ;adjusting a pH of the aluminum phosphate hydrosol to be Z 6, thereby obtaining an aluminum phosphate hydrogel; drying the aluminum phosphate hydrogel to obtain an aluminum phosphate precursor; andcalcining the aluminum phosphate precursor to obtain the aluminum phosphate. When used to catalyze an esterification reaction between o—dihydroxybenzene and dimethyl carbonate, the aluminum phosphate provided in the present disclosure has high activity and high stability, resulting in high conversion rate of the o—dihydroxybenzene and high selectivity of the target product o—hydroxyanisole.
Description
ALUMINUM PHOSPHATE AND PREPARATION METHOD AND USE THEREOF, AND
PREPARATION METHOD OF O-HYDROXYANISOLE
The present disclosure belongs to the technical field of cat- alyst preparation, and in particular, relates to an aluminum phos- phate and a preparation method and use thereof, and a preparation method of o-hydroxyanisole.
O-hydroxyanisole, also known as methyl guaiacol, is a white or light yellow crystal or transparent oily liquid with a unique aromatic odor. The o-hydroxyanisole has been widely used in indus- tries such as perfumes, agriculture, medicine and dyes as a fine chemical intermediate and a chemical raw material.
There are many synthesis methods for the o-hydroxyanisole, which can be divided into methods of extraction from natural prod- ucts and industrial synthesis methods according to source. The methods of extraction from natural products are restricted by raw materials and extraction techniques, and the yields thereof can hardly meet the production requirements. Thus, the industrial syn- thesis methods have been the main production methods at present.
The industrial synthesis methods can be divided into liquid- phase methods and multi-phase methods according to operation mode.
Despite rapid reaction rates, the liquid-phase methods have been phased out due to high operation intensity and high labor costs.
The multi-phase methods have been mainstream processes for produc- ing the o-hydroxyanisole at present. The multi-phase methods are divided into a methanol method and a dimethyl carbonate method ac- cording to different raw materials. The methanol method has become an industrially promising method based on the advantage raw mate- rial price, but is prone to causing pollution to the environment.
A scheme of gas-solid phase catalyzed synthesis of o- hydroxyanisole from o-dihydroxybenzene and dimethyl carbonate as raw materials has the advantage of environmental friendliness and has attracted increasing attention. However, due to the influence of the performance of catalysts, the yield of the target product o-hydroxyanisole is low.
In view of the above problems, the present disclosure pro- vides an aluminum phosphate and a preparation method and use thereof, and a preparation method of o-hydroxyanisole. The alumi- num phosphate provided in the present disclosure has high activity and high reaction stability. When the aluminum phosphate is used to catalyze an esterification reaction between o-dihydroxybenzene and dimethyl carbonate to prepare o-hydroxyanisole, a high conver- sion rate of the o-dihydroxybenzene and high selectivity of the target product o-hydroxyanisole can be achieved.
The present disclosure provides a preparation method of alu- minum phosphate, including the following steps of: mixing pseudo-boehmite, a soluble phosphorus source, a polar solvent and a strong acid to obtain an aluminum phosphate hydro- sol, with a mole ratio of aluminum atoms in the pseudo-boehmite to phosphorus atoms in the phosphorus source being 2 1:0.5; adjusting a pH of the aluminum phosphate hydrosol to be 2 6, thereby obtaining an aluminum phosphate hydrogel; drying the aluminum phosphate hydrogel to obtain an aluminum phosphate precursor; and calcining the aluminum phosphate precursor to obtain the alu- minum phosphate.
Preferably, the mole ratio of the aluminum atom in the pseu- do-boehmite to the phosphorus atom in the phosphorus source may be 1:(0.5-1.5).
Preferably, a temperature for the calcining may range from 400°C to 800°C; a temperature holding time for the calcining may be 5-24 hours; and a rate of rise from room temperature to the temperature for the calcining may be 1-8°C/min.
Preferably, a temperature for the drying may range from 80°C to 120°C; and a rate of rise from room temperature to the tempera- ture for the drying may be 1-8°C/min.
Preferably, the soluble phosphorus source may be selected from the group consisting of phosphoric acid and ammonium phos- phate salts.
Preferably, the strong acid solution may be a nitric acid so- lution containing 65-68% by mass of nitric acid.
The present disclosure provides an aluminum phosphate ob- tained by the preparation method of the above-mentioned technical solutions. The aluminum phosphate has a weak acid site and a mod- erate acid site on surface thereof.
The present disclosure provides use of the aluminum phosphate obtained by the above-mentioned technical solutions as a catalyst in a dehydrogenation reaction, isomerization reaction, alkylation reaction, rearrangement reaction, condensation reaction, cycliza- tion addition reaction and etherification reaction.
The present disclosure further provides a preparation method of o-hydroxyanisole, including subjecting o-dihydroxybenzene and dimethyl carbonate to an etherification reaction catalyzed by the aluminum phosphate obtained by the above-mentioned technical solu- tions to obtain the o-hydroxyanisole.
Preferably, the esterification reaction may occur at a tem- perature ranging from 220°C to 320°C.
Preferably, a mole ratio of the o-dihydroxybenzene to the di- methyl carbonate may be 1:(3-8); and the esterification reaction may have a space velocity of 1-8 mL ght.
The present disclosure provides a preparation method of alu- minum phosphate, including the following steps: mixing pseudo- boehmite, a soluble phosphorus source, a polar solvent and a strong acid to obtain an aluminum phosphate hydrosol, with a mole ratio of aluminum atom in the pseudo-boehmite to phosphorus atom in the phosphorus source being 2 1:0.5 ;adjusting a pH of the alu- minum phosphate hydrosol to be 2 6, thereby obtaining an aluminum phosphate hydrogel; drying the aluminum phosphate hydrogel to ob- tain an aluminum phosphate precursor; and calcining the aluminum phosphate precursor to obtain the aluminum phosphate. According to the preparation method provided in the present disclosure, the pseudo-boehmite and the soluble phosphorus source are dissolved in a strong acid solution to form the aluminum phosphate hydrosol, and the pH of the aluminum phosphate hydrosol is then adjusted to be 2 6, so that the aluminum phosphate hydrogel is obtained. Fi- nally, the aluminum phosphate hydrogel is orderly dried and cal- cined to obtain the aluminum phosphate. According to the present disclosure, during the sol-gel process, the mole ratio of the alu- minum atoms in the pseudo-boehmite to the phosphorus atoms in the phosphorus source is controlled to be 2 1:0.5 and a pH of the gel is controlled to be 26, so that basic sites and Lewis acid sites are uniformly distributed on the surface of the finally formed aluminum phosphate. In addition, molecular sieves exhibit highly weak acidic property on surface thereof. When used as a catalyst to catalyze the etherification reaction of o-dihydroxybenzene, high catalytic activity is achieved under the synergistic action of the basic sites and the Lewis acid sites on the surface of the aluminum phosphate. Moreover, the surface of the aluminum phos- phate prepared herein has high weak acidic property and is weak in adsorption capability to o-dihydroxybenzene molecules, and there- fore, when used to catalyze a reaction, the reactants and product can be rapidly separated from the surface of the molecular sieves, resulting in not easy carbon deposition. In short, the aluminum phosphate has high stability.
The present disclosure further provides a preparation method of o-hydroxyaniscle, including subjecting o-dihydroxybenzene and dimethyl carbonate to an etherification reaction catalyzed by the aluminum phosphate obtained by the above-mentioned technical solu- tions to obtain the o-hydroxyanisole. According to the present disclosure, when the aluminum phosphate obtained by the above technical solutions, is used as a catalyst to catalyze gas-solid phase mono-etherification of o-dihydroxybenzene and dimethyl car- bonate to obtain the o-hydroxyanisole, few by-products may be ob- tained and the selectivity of the by-products is low. The results of examples show that: when the aluminum phosphate provided in the present disclosure is used to catalyze a reaction, the conversion rate of o-dihydroxybenzene is 93.0%; and the selectivity of the o- hydroxyanisole is 71.1%, while the selectivity of the o-dimethoxy benzene is 27.0% and the selectivity of other by-product is 1.9%.
In addition, the aluminum phosphate provided in the present dis- closure has good stability and exhibits no obvious reduction in activity when used to catalyze a reaction for 200 hours. The con- version rate of the o-dihydroxybenzene can be maintained at above 92%; and the selectivity of the o-hydroxyanisole is above 70%, while the selectivity of the o-dimethoxy benzene is 28% and the 5 selectivity of other by-product is 2%.
Furthermore, the aluminum phosphate provided in the present disclosure is simple in preparation process, low in raw material costs, and the preparation process is green and free from pollu- tion.
FIG. 1 is a diagram showing results of activity stability of aluminum phosphate prepared in Example 1 of the present disclo- sure.
FIG 2 is a diagram showing results of activity stability of a product prepared in Comparative Example 2 of the present disclo- sure.
The present disclosure provides a preparation method of alu- minum phosphate, including the following steps of: mix pseudo-boehmite, a soluble phosphorus source, a polar solvent and a strong acid to obtain an aluminum phosphate hydro- sol, with a mole ratio of aluminum atoms in the pseudo-boehmite to phosphorus atoms in the phosphorus source being 2 1:0.5; adjust a pH of the aluminum phosphate hydrosol to be 2 6, thereby obtaining an aluminum phosphate hydrogel; dry the aluminum phosphate hydrogel to obtain an aluminum phosphate precursor; and calcine the aluminum phosphate precursor to obtain the alumi- num phosphate.
In the present disclosure, unless otherwise specified, the raw materials used are all commercially-available products well known to those skilled in the art.
According to the present disclosure, pseudo-boehmite, a solu- ble phosphorus source, a polar solvent and a strong acid are mixed to obtain an aluminum phosphate hydrosol, and a mole ratio of alu-
minum atoms in the pseudo-boehmite to phosphorus atoms in the phosphorus source is 2 1:0.5.
In the present disclosure, the pseudo-boehmite has a specific surface area of 200-300 m°/g, more preferably 250 m°/g. The pseudo- boehmite has a pore volume of 0.7-1 mL/g, more preferably 0.8 mL/g. The pseudo-boehmite preferably has a pore size of 8-9 nm.
In the present disclosure, the soluble phosphorus source is preferably selected from the group consisting of phosphoric acid and ammonium phosphate salts, more preferably one or more selected from the group consisting of phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and triammonium phos- phate, and most preferably triammonium phosphate.
In the present disclosure, the mole ratio of the aluminum at- oms in the pseudo-boehmite to the phosphorus atoms in the phospho- rus source is 2 1:0.5, preferably 1:(0.5-1.5), more preferably 1:(0.6-1.3), and most preferably 1:(0.8-1). In specific implemen- tation of the present disclosure, the mole ratio of the aluminum atoms in the pseudo-boehmite to the phosphorus atoms in the phos- phorus source is selected from the group consisting of 1:0.85, 1:0.75, 1:0.85, and 1:0.5.
In the present disclosure, the polar solvent is preferably selected from the group consisting of water and low alcohols, more preferably water and ethyl alcohol, and most preferably water.
In the present disclosure, a solid-to-liquid ratio of the pseudo-boehmite 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 present disclosure, the strong acid is preferably a nitric acid solution containing 65-68% by mass of nitric acid.
In the present disclosure, a ratio of the volume of the strong acid to the mass of the pseudo-boehmite is preferably (0.1- 0.5) mL:1 g, more preferably (0.2-0.45) mL:1 g.
In the present disclosure, the mixing preferably includes the following steps: first mix the pseudo-boehmite, the soluble phosphorus source and the polar solvent to obtain a first mixture; and second mix the first mixture with the strong acid to obtain the aluminum phosphate hydrosol.
The pseudo-boehmite, the soluble phosphorus source and the polar solvent are mixed first to obtain the first mixture. In the present disclosure, the first mixing is preferably carried out at a temperature of 20°C to 28°C. The first mixing is preferably car- ried out for 1 to 3 hours. The first mixing is carried out under stirring. The present disclosure has no specific requirement on the specific implementation process of the stirring.
In the present disclosure, after the first the mixture is ob- tained, the second mixing is performed on the first mixture and the strong acid to obtain the aluminum phosphate hydrosol. In the present disclosure, the second mixing is preferably carried out at a temperature of 20°C to 28°C. The second mixing is preferably carried out for 1 to 3 hours. The second mixing is carried out un- der stirring. The present disclosure has no specific requirement on the specific implementation process of the stirring.
In the present disclosure, after the aluminum phosphate hy- drosol is obtained, a pH of the aluminum phosphate hydrosol is ad-
Justed to be 2 6, preferably 7-10, so that an aluminum phosphate hydrogel is obtained. In specific embodiments of the present dis- closure, the pH is selected from the group consisting of 7, 8 and 9.
In the present disclosure, a pH of the aluminum phosphate hy- drosol is preferably adjusted by using a pH regulator which is preferably ammonium hydroxide. The present disclosure has no spe- cific requirement on the mass concentration of the ammonium hy- droxide. In the present disclosure, the pH is preferably adjusted under stirring. The present disclosure has no specific requirement on the specific implementation process of the stirring.
In the present disclosure, after a pH of the aluminum phos- phate hydrosol is adjusted to be 26, the aluminum phosphate hydro- sol system having the pH 2 6 is preferably allowed to stand for aging, thereby obtaining the aluminum phosphate hydrogel. In the present disclosure, the time for standing for aging is preferably 1-24 hours, more preferably 5-20 hours. A temperature for standing for aging is preferably room temperature.
In the present disclosure, after the aluminum phosphate hy- drogel is obtained, the aluminum phosphate hydrogel is dried to obtain an aluminum phosphate precursor.
In the present disclosure, a temperature for the drying is preferably 80°C to 120°C, more preferably 90°C to 100°C. In the present disclosure, the time for the drying is preferably 24 to 48 hours, more preferably 30-35 hours. A rate of rise from room tem- perature to the temperature for the drying is preferably 1- 8°C/min, more preferably 2.5-5°C/min. In specific implementation of the present disclosure, the drying is preferably performed in a drying oven.
In the present disclosure, a solvent and impurities (includ- ing the acid radicals of the strong acid, the pH regulator, etc.) in the aluminum phosphate hydrogel are removed by drying, so that a solid Al-P initial gel network is obtained.
In the present disclosure, after the aluminum phosphate pre- cursor is obtained, the aluminum phosphate precursor is calcined to obtain the aluminum phosphate.
In the present disclosure, a temperature for the calcining is preferably 400°C to 800°C, more preferably 450°C to 780°C, and most preferably 500°C to 750°C. In the present disclosure, a tem- perature holding time for the calcining is preferably 5 to 24 hours, more preferably 10 to 12 hours. A rate of rise from room temperature to the temperature for the calcining is preferably 1- 8°C/min, more preferably 5-7°C/min.
In the present disclosure, the aluminum phosphate is formed by calcining, so that the network structure of molecular sieves is reinforced and residual impurities in the molecular sieves are further removed.
The present disclosure provides an aluminum phosphate ob- tained by the preparation method of the above-mentioned technical solutions. The aluminum phosphate has a weak acid site and a mod- erate acid site on surface thereof.
In the present disclosure, the aluminum phosphate has a spe- cific surface area of 60-90 m’/g, more preferably 65-80 m°/g. The aluminum phosphate preferably has a pore volume of 0.1-0.2 cm’/g, more preferably 0.15 cm’/g. The aluminum phosphate preferably has a pore size of 8-9 nm.
In the present disclosure, when the aluminum phosphate is an-
alyzed by temperature-programmed desorption of ammonia (NH;-TPD), a desorption temperature of ammonia is preferably 100°C to 300°C.
The present disclosure provides use of the aluminum phosphate obtained by the above-mentioned technical solutions as a catalyst in a dehydrogenation reaction, isomerization reaction, alkylation reaction, rearrangement reaction, condensation reaction, cycliza- tion addition reaction and etherification reaction.
The present disclosure further provides a preparation method of o-hydroxyanisole, including subjecting o-dihydroxybenzene and dimethyl carbonate to an etherification reaction catalyzed by the aluminum phosphate obtained by the above-mentioned technical solu- tions to obtain the o-hydroxyanisole.
When the aluminum phosphate provided in the present disclo- sure is used as a catalyst to catalyze an etherification reaction between o-dihydroxybenzene and dimethyl carbonate, basic sites on the surface of the aluminum phosphate can activate H atoms on hy- droxyl groups of the o-dihydroxybenzene, and the Lewis acid on the surface of the aluminum phosphate has the function of absorbing electrons and is capable of adsorbing oxygen atoms on carbonyl groups of the dimethyl carbonate to adjacent acid sites. The H at- oms on the hydroxyl groups of the activated o-dihydroxybenzene are bonded to the oxygen atoms and then attack carbon atoms on methyl groups of the dimethyl carbonate to obtain the o-hydroxyanisole.
In the present disclosure, the etherification reaction occurs preferably at a temperature of 220°C to 320°C, more preferably 230°C to 300°C, and most preferably 250°C to 280°C.
In the present disclosure, the mole ratio of the o- dihydroxybenzene to the dimethyl carbonate is preferably 1: (3-8), more preferably 1:(3.5-6).
In the present disclosure, the etherification reaction pref- erably has a space velocity of 1-8 mL-g +h’, more preferably 1.5-7 mL -g™* -h™*, and most preferably 2-5 mL-g*-h™.
In the present disclosure, the etherification reaction pref- erably occurs in a fixed-bed reactor, and the reaction is a gas- solid phase reaction.
The technical solutions in the present disclosure will be clearly and completely described below in conjunction with exam-
ples of the present disclosure. Apparently, the described examples are merely some rather than all of the embodiments of the present disclosure. All other examples obtained by a person of ordinary skill in the art based on the examples of the present disclosure without creative efforts shall fall within the protection scope of the present disclosure.
Example 1
Pseudo-boehmite (having a surface area of 250 m?/g, a pore volume of 0.8 mL/g and a pore size of 8-9 nm), phosphoric acid and deionized water were mixed at 40°C, where a mole ratio of phospho- rus atom in the phosphoric acid to aluminum atom in the pseudo- boehmite was 0.85:1; a solid-to-liquid ratio of the pseudo- boehmite to water was 1:2.5. The fully mixed mixture was then add- ed with 65% by mass of nitric acid to obtain an aluminum phosphate hydrosol, where a ratio of the used nitric acid (mL) to the pseu- do-boehmite (g) was 0.3:1. Ammonium hydroxide was added to the aluminum phosphate hydrosol to adjust the pH to 8, and mixed for 2 hours to obtain an aluminum phosphate hydrogel. The aluminum phos- phate hydrogel was allowed to stand for aging for 2 hours. The mixture was heated until water evaporated completely, and then dried in a drying oven at 120°C for 24 hours to obtain a solid precursor. The solid precursor was warmed from room temperature to 500°C at a rate of 8°C/min and calcinated for 24 hours to obtain aluminum phosphate (having a specific surface area of 65-80 m‘/g, a pore volume of 0.15 cm’/g, and a pore size of 8-9 nm). During anal- ysis by temperature-programmed desorption of ammonia (NH;-TPD), a desorption temperature of ammonia was preferably 300°C.
Example 2
The preparation method in this example was basically the same as that in Example 1 except that the phosphorus source was ammoni- um dihydrogen phosphate.
Example 3
The preparation method in this example was basically the same as that in Example 1 except that the phosphorus source was diammo- nium hydrogen phosphate.
Example 4
The preparation method in this example was basically the same as that in Example 1 except that the pH was adjusted to 7 by using ammonium hydroxide.
Example 5
The preparation method in this example was basically the same as that in Example 1 except that the pH was adjusted to 2 by using ammonium hydroxide.
Example 6
The preparation method in this example was basically the same as that in Example 1 except that the mole ratio of the phosphorus atom in the phosphorus source to the aluminum atom in the pseudo- boehmite was 0.75:1.
Example 7
The preparation method in this example was basically the same as that in Example 1 except that the mole ratio of the phosphorus atom in the phosphorus source to the aluminum atom in the pseudo- boehmite was 0.95:1.
Example 8
The preparation method in this example was basically the same as that in Example 1 except that the mole ratio of the phosphorus atom in the phosphorus source to the aluminum atom in the pseudo- boehmite was 0.5:1.
Comparative Example 1
The preparation method in this example was basically the same as that in Example 1 except that the ratio of the used nitric acid (mL) to the pseudo-boehmite (g) was 0.
Comparative Example 2
The preparation method in this example was basically the same as that in Example 1 except that the pH was adjusted not using am- monia hydroxide.
Example 9
The molecular sieves prepared in Examples 1 to 8 and the mo- lecular sieves prepared in Comparative Examples 1 and 2 were used to catalyze a gas-solid phase mono-etherification reaction between o-dihydroxybenzene and dimethyl carbonate to prepare the o- hydroxyanisole. The reaction occured on a fixed-bed apparatus un- der the conditions of: a mole ratio of o-dihydroxybenzene to dime- thyl carbonate of 1:6, a reaction temperature of 250°C, and a space velocity of 4 mL-g-1-h-1.
The conversion rate of the o-dihydroxybenzene, the selectivi- ty of the o-hydroxyaniscle, the selectivity of the o-dimethoxy benzene and the selectivity of other by-product were calculated, and the results were shown in Table 1.
Table 1 Results of Example 9
Selectivity (%) benzene
Catalyst Conversion o-dimethoxy ben- =
Other
Rate (%) anisole zene
Example 8 | 45.8 22.7
Compara- tive Ex- 1.3 66.3 33.7 0 ample 1
Compara- tive Ex- 45.9 94.9 15.0 ample 2
As shown in Table 9, when the aluminum phosphate prepared in the present disclosure was used as a catalyst to catalyze gas- solid phase mono-etherification of o-dihydroxybenzene and dimethyl carbonate to prepare the o-hydroxyanisole, the reaction activity of the catalyst was high and few by-products were obtained with low selectivity of the by-products. The conversion rate of the o- dihydroxybenzene was greater than 45%; and the selectivity of the o-hydroxyanisole was 2 64%, while the selectivity of the o- dimethoxy benzene was 20-30% and the selectivity of other by- product was less than 5%.
Test Example
The stability of the molecular sieve products prepared in Ex- ample 1 and Comparative Example 2 used as catalysts was tested,
where the molecular sieves prepared in Example 1 and Comparative
Example 2 were used to catalyze a gas-solid phase mono- etherification reaction between o-dihydroxybenzene and dimethyl carbonate to prepare the o-hydroxyanisole. The reaction occurred on a fixed-bed apparatus under the conditions of: a mole ratio of o-dihydroxybenzene to dimethyl carbonate of 1:6, a reaction tem- perature of 250°C, and a space velocity of 4 mL-g ht.
The conversion rate of the o-dihydroxybenzene, the selectivi- ty of the o-hydroxyanisole, the selectivity of the o-dimethoxy benzene and the selectivity of by-product were calculated, and the results of Example 1 were shown in FIG 1. It could be clearly ob- served that the catalyst exhibited no obvious reduction in activi- ty when used to catalyze the reaction for 200 hours, and the se- lectivity of the o-hydroxyanisole was above 70%, while the selec- tivity of the o-dimethoxy benzene was around 28% and the selectiv- ity of other by-product was around 2%. It showed that the catalyst prepared by the preparation method provided in Example 1 of the present disclosure had good stability. After reacting for 30 hours, the conversion rate and the selectivity of the catalyst of
Comparative Example 2 shown in FIG. 2 were reduced from 45.9% and 94.9% to 30.2% and 70.3%, with poor stability.
The foregoing are merely descriptions of preferred embodi- ments of the present disclosure. It should be noted that several improvements and modifications can be made by a person of ordinary skill in the art without departing from the principle of the pre- sent disclosure, and these improvements and modifications shall also be deemed as falling within the protection scope of the pre- sent disclosure.
Claims (10)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111042097.9A CN113735086A (en) | 2021-09-07 | 2021-09-07 | Aluminum phosphate, preparation method and application thereof, and preparation method of o-hydroxyanisole |
Publications (1)
Publication Number | Publication Date |
---|---|
NL2030281B1 true NL2030281B1 (en) | 2023-03-21 |
Family
ID=78736361
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NL2030281A NL2030281B1 (en) | 2021-09-07 | 2021-12-23 | Aluminum phosphate and preparation method and use thereof, and preparation method of o-hydroxyanisole |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN113735086A (en) |
NL (1) | NL2030281B1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5292701A (en) * | 1985-08-29 | 1994-03-08 | W. R. Grace & Co.-Conn. | High pore volume and pore diameter aluminum phosphate and method of making the same |
US5801277A (en) * | 1996-05-23 | 1998-09-01 | Nippon Shokubai Co., Ltd. | Solid catalyst for etherification reaction and production process for ether compound using this catalyst |
CN103706383B (en) * | 2013-12-10 | 2016-08-17 | 南京工业大学 | Catalyst for catechol guaiacol and preparation method thereof |
CN104174417B (en) * | 2014-09-02 | 2016-08-17 | 西华师范大学 | Aluminium phosphate catalyst and preparation thereof and application |
EP3661902A1 (en) * | 2017-08-03 | 2020-06-10 | Universiteit Antwerpen | Method for the deacylation and/or dealkylation of compounds |
CN110002966B (en) * | 2019-02-21 | 2022-04-19 | 宝鸡文理学院 | Method for synthesizing o-hydroxyanisole from catechol and methanol |
CN111187148B (en) * | 2020-02-24 | 2022-08-09 | 上海大学 | Method for simultaneously preparing o-hydroxy phenetole and 1, 3-benzodioxole-2-one |
-
2021
- 2021-09-07 CN CN202111042097.9A patent/CN113735086A/en active Pending
- 2021-12-23 NL NL2030281A patent/NL2030281B1/en active
Also Published As
Publication number | Publication date |
---|---|
CN113735086A (en) | 2021-12-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5625108A (en) | Process for preparing amorphous, catalytically active silicoaluminas | |
AU2008274582B2 (en) | Process for preparing silicoaluminoposphate (SAPO) molecular sieves, catalysts containing said sieves and catalytic dehydration processes using said catalysts | |
EP2898948B1 (en) | Glycerin dehydration catalyst, preparation method therefor, and method for producing acrolein | |
NL2030281B1 (en) | Aluminum phosphate and preparation method and use thereof, and preparation method of o-hydroxyanisole | |
AU2017336262B2 (en) | Catalyst comprising small 10-ring zeolite crystallites and a method for producing hydrocarbons by reaction of oxygenates over said catalyst. | |
US3781222A (en) | Dehydration catalysts,particularly for the dehydration of diols | |
ES2819698T3 (en) | Monoalcohols dehydration process using a modified crystalline aluminosilicate | |
Nesterenko et al. | Dehydrogenation of ethylbenzene and isobutane over Ga-and Fe-containing mesoporous silicas | |
CN1246223C (en) | Method of synthesizing silicon phosphorus aluminium molecular sieve | |
Vlasenko et al. | Insight into the active site nature of zeolite H-BEA for liquid phase etherification of isobutylene with ethanol | |
Buniazet et al. | Unexpected selectivity of ferrierite for the conversion of isobutanol to linear butenes and water effects | |
CN104971768B (en) | A kind of SAPO-34/ natural clay composite material and preparation method and application | |
CN109395772B (en) | Isomerization catalyst and preparation method and application thereof | |
Chen et al. | Effect of coprecipitation method on Mg–Al hydrotalcite properties: application in the synthesis of diethylene glycol di-(methyl carbonate) | |
CN1704390A (en) | Method for preparing olefin by conversion of methanol | |
CN105111044A (en) | Method for synthesizing isopentenol from butenol | |
US9259718B1 (en) | Method for preparing catalyst for glycerin dehydration, and method for preparing acrolein | |
CN1076219C (en) | Silicon phosphorus aluminium molecular sieve containing alkaline earth metal and its synthesis | |
Schmidtmeyer et al. | Stoichiometric and nonstoichiometric Al P O catalysts: Studies with the probe molecule 2-methylcyclohexanol | |
RU2421441C1 (en) | Single-step method of producing isoprene | |
CN112973778B (en) | Iron-zirconium bimetal supported catalyst and preparation method and application thereof | |
El-Hakam et al. | Surface properties and catalytic activity of Ni/Al2O3–AlPO4 catalysts | |
US4619907A (en) | Chromium phosphate catalyst | |
CN115140749A (en) | Micro-mesoporous SAPO-34 molecular sieve and preparation method using carbon deposition species as template agent | |
US4543436A (en) | Chromium phosphate as an alkylation catalyst |