CN115197052A - Method for synthesizing o-hydroxy phenetole by hydroxyapatite catalysis - Google Patents
Method for synthesizing o-hydroxy phenetole by hydroxyapatite catalysis Download PDFInfo
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- CN115197052A CN115197052A CN202210905507.6A CN202210905507A CN115197052A CN 115197052 A CN115197052 A CN 115197052A CN 202210905507 A CN202210905507 A CN 202210905507A CN 115197052 A CN115197052 A CN 115197052A
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- hydroxyapatite
- phenetole
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- catechol
- hydroxy
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- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 74
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 74
- MOEFFSWKSMRFRQ-UHFFFAOYSA-N 2-ethoxyphenol Chemical compound CCOC1=CC=CC=C1O MOEFFSWKSMRFRQ-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 55
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 8
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 116
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- VXHYVVAUHMGCEX-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)phenol Chemical compound OC1=CC=CC=C1OC1=CC=CC=C1O VXHYVVAUHMGCEX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 claims 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 150000001450 anions Chemical class 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 20
- 239000006227 byproduct Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 239000011575 calcium Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- ZQBZAOZWBKABNC-UHFFFAOYSA-N [P].[Ca] Chemical compound [P].[Ca] ZQBZAOZWBKABNC-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000003513 alkali Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MWKXCSMICWVRGW-UHFFFAOYSA-N calcium;phosphane Chemical compound P.[Ca] MWKXCSMICWVRGW-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical compound CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- OMONCKYJLBVWOQ-UHFFFAOYSA-N 1-ethoxy-2-methoxybenzene Chemical compound CCOC1=CC=CC=C1OC OMONCKYJLBVWOQ-UHFFFAOYSA-N 0.000 description 1
- QXACAUOGHQHJSV-UHFFFAOYSA-N 2-(oxiran-2-yl)aniline Chemical compound NC1=CC=CC=C1C1OC1 QXACAUOGHQHJSV-UHFFFAOYSA-N 0.000 description 1
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 229940073505 ethyl vanillin Drugs 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
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
- B01J27/18—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 with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
Abstract
The invention relates to a synthesis method of o-hydroxy phenetole, which takes catechol and diethyl carbonate as reactants; hydroxyapatite is used as a catalyst, the dosage of the hydroxyapatite is 0.5 to 1.5g, the particle size is 20 to 50 meshes, and the molar ratio of Ca to P is between 1.58 and 1.70; the reaction is carried out on a fixed bed reactor, the reaction is gas catalytic reaction, the reaction temperature is 250-450 ℃, and the space velocity is 4-8 h ‑1 . Ca in the catalyst of the invention 2+ 、PO 4 3‑ And OH ‑ The catalyst has strong ion exchange capacity, can be substituted by other cations or anions, and can regulate the number and the proportion of surface acid-base sites by regulating the molar ratio of Ca and P and the roasting temperature; meanwhile, the surface of the hydroxyapatite has rich hydroxyl groups, and reactants can be adsorbed in the reaction. Thus applying it toIn the reaction of synthesizing the o-hydroxy phenetole, the conversion rate of catechol and the selectivity of the o-hydroxy phenetole can be greatly improved, and meanwhile, the method also has the advantages of cheap and easily obtained raw materials, environmental friendliness and the like.
Description
Technical Field
The invention belongs to the technical field of chemical catalysis, and particularly relates to a method for synthesizing o-hydroxy phenetole by catalyzing catechol and diethyl carbonate by using hydroxyapatite as a catalyst and application thereof.
Background
O-hydroxy phenetole, also known as ethylguaiacol or o-ethoxyphenol, is one of the main raw materials for synthesizing the perfume ethyl vanillin, is widely applied to the fields of medicine, dye, cosmetics and dye synthesis, and can also be directly used as an analytical reagent.
At present, methods for producing o-hydroxy phenetole at home and abroad comprise an o-aminophenethylene ether method, an o-nitrochlorobenzene method, a catechol method and the like, and compared with other methods, the catechol method has the advantages of high yield, small pollution, low cost and the like, and is a more advanced process at home and abroad.
The catechol method is divided into a catechol/ethanol method, a catechol/diethyl carbonate method and a catechol/chloroethane method according to different alkylating reagents, the catechol/diethyl carbonate method is a main trend for developing and synthesizing the o-hydroxy phenetole at present, common catalysts comprise a silicon-aluminum molecular sieve, a transition metal oxide, a phosphate and the like, but the catalysts have lower activity, and an acidic site is easy to catalyze a reactant to generate side reactions such as alkylation, cyclization and the like on a benzene ring, so that the selectivity of the o-hydroxy phenetole is reduced.
Therefore, the development of a high-activity and high-selectivity catalyst for synthesizing o-hydroxy phenetole is urgently needed.
Disclosure of Invention
The invention provides a method for efficiently catalytically synthesizing o-hydroxy phenetole by using a hydroxyapatite material as a catalyst, aiming at the problems of low catalyst activity, low product selectivity caused by a plurality of byproducts and the like in the synthesis of o-hydroxy phenetole in the prior art. The catalyst has adjustable acid and alkali sites, and the conversion rate and the selectivity of the catalyst are improved through the synergistic effect of the acid and alkali sites.
In order to solve the technical problem, the method is specifically carried out according to the following steps:
a method for synthesizing o-hydroxy phenetole by hydroxyapatite catalysis is characterized in that reactants are catechol and diethyl carbonate, wherein the molar ratio of catechol to diethyl carbonate is 1-2; the catalyst is hydroxyapatite, the reaction is carried out on a fixed bed and is gas catalytic reaction, the reaction temperature is 250-450 ℃, and the space velocity is 4-8 h -1 。
The dosage of the catalyst hydroxyapatite is 0.5-1.5 g, the particle size of the catalyst hydroxyapatite is 20-50 meshes, and the molar ratio of the catalyst hydroxyapatite Ca to the catalyst hydroxyapatite P is 1.58-1.70.
The hydroxyapatite provided by the invention is self-made hydroxyapatite, and the preparation method can be carried out according to the following method 1 or method 2, and comprises the following specific steps:
the method comprises the following steps: heating in water bath at 40 deg.C to obtain certain amount of (NH) 4 ) 2 HPO 4 Dropwise adding aqueous solution to Ca (NO) 3 ) 2 And (2) dropwise adding ammonia water into the aqueous solution to adjust the pH value to be 10 +/-0.1, stirring for 1h, aging for 12h at 40 ℃, carrying out suction filtration, stirring and washing with deionized water, drying overnight at 80 ℃, placing in a tubular furnace, roasting for 3-12 h in the air atmosphere at the roasting temperature of 300-850 ℃ to obtain the hydroxyapatite. Wherein, ca (NO) 3 ) 2 And (NH) 4 ) 2 HPO 4 The molar ratio of (a) to (b) is 0.9 to 1.1.
In the preparation method 1, the preferred roasting temperature is 360-700 ℃, and the roasting time is 5-10 h.
(2) The method 2 comprises the following steps: slowly adding phosphoric acid solution dropwise to Ca (OH) 2 In the glycol solution, the calcium-phosphorus ratio of the reaction system is 1.67, and ammonia is utilizedAdjusting pH to 10 + -0.1 with water, stirring for 10min, centrifuging the precipitated solution, washing, drying at 60 deg.C, and grinding to obtain hydroxyapatite.
The method for synthesizing the o-hydroxy phenetole by using the self-made hydroxyapatite in the gas-solid reaction specifically comprises the following steps: preparing pyrocatechol and diethyl carbonate into a reaction solution (1 2 ) Under protection, after the temperature reaches a set value, pumping the raw materials into a reactor through a trace constant flow pump, allowing the raw materials to flow through a bed layer for reaction, condensing to obtain a reaction solution, and quantitatively analyzing the conversion rate of catechol and the selectivity of o-hydroxy phenetole by using gas chromatography.
The invention provides a method for preparing o-hydroxy phenetole by using hydroxyapatite to catalyze the reaction of catechol and diethyl carbonate. Compared with the traditional catalyst, the method has the following advantages:
the hydroxyapatite has a stoichiometric formula of [ Ca 10 (PO 4 ) 6 (OH) 2 ]Wherein Ca is 2+ 、PO 4 3- And OH - Has strong ion exchange capacity, and can be substituted by other cations or anions. The number and the proportion of the acid-base sites on the surface can be adjusted by adjusting the molar ratio of Ca to P and the roasting temperature; meanwhile, the surface of the hydroxyapatite has abundant hydroxyl groups, and reactants can be adsorbed in the reaction. Therefore, when the method is applied to the reaction of preparing the o-hydroxy phenetole from the catechol and the diethyl carbonate, the conversion rate of the catechol can reach 100 percent at most, the selectivity of the o-hydroxy phenetole can reach 90 percent at most, the yield of the o-hydroxy phenetole is obviously improved, and meanwhile, the method also has the advantages of cheap and easily obtained raw materials, environmental friendliness and the like.
Drawings
FIG. 1 is an XRD pattern of hydroxyapatite obtained in example 1; it can be seen from the figure that the self-made hydroxyapatite only shows the characteristic diffraction signal of the hydroxyapatite (JCPDS 01-086-074) and does not contain CaO and CaCO 3 Equal diffraction peaks indicate successful production of hydroxyphosphineAn apatite sample.
FIG. 2 shows different Ca/P hydroxyapatite surface acid-base densities; as can be seen from the figure, the surface acid strength and alkali strength of hydroxyapatite with different Ca/P have no obvious change, but the acid density decreases with the increase of Ca/P, the alkali density gradually increases, and the alkalinity is mainly Ca 2+ The acid site is H + Introduction of H for charge balance + Thus, the smaller the Ca/P ratio, the greater the acid density and the smaller the base density.
FIG. 3 is the surface acid-base density of hydroxyapatite samples at different calcination temperatures; it can be seen from the figure that the surface acid strength and alkali strength of the hydroxyapatite with different Ca/P have no obvious change, the alkali density has no obvious change, the acid density is increased and then reduced along with the roasting temperature, and the acid density reaches the maximum value at 500 ℃.
Detailed Description
The invention will be further described in the following examples, but it is to be understood that these examples are for illustrative purposes only and are not to be construed as limiting the practice of the invention.
The present invention synthesizes hydroxyapatite through two different methods, and different kinds of hydroxyapatite powder may be obtained through regulating the material amount and reaction condition.
Example 1
The hydroxyapatite is prepared by the method 1, added under heating in water bath at 40 ℃, and added with 150mL of (NH) with the concentration of 0.2500mol/L 4 ) 2 HPO 4 The aqueous solution was added dropwise to a solution containing 250mL of Ca (NO) at a concentration of 0.237mol/L 3 ) 2 Adding ammonia water dropwise into a three-neck flask of aqueous solution (used for adjusting the calcium-phosphorus ratio of the hydroxyapatite) to adjust the pH value to 10 +/-0.1, stirring for 1h, aging at 40 ℃ for 12h, performing suction filtration by using a sand mold funnel, stirring and washing by using deionized water, drying overnight at 80 ℃, placing in a tubular furnace, roasting for 5h in the air atmosphere at the roasting temperature of 500 ℃, and finally obtaining the hydroxyapatite with the calcium-phosphorus ratio of 1.58.
Example 2
Hydroxyapatite was prepared by method 1, added under heating in a water bath at 40 deg.C, and 150mL of (NH) solution with a concentration of 0.2500mol/L 4 ) 2 HPO 4 The aqueous solution was added dropwise to a solution containing 250mL of Ca (NO) at a concentration of 0.255mol/L 3 ) 2 Adding ammonia water dropwise into a three-neck flask of aqueous solution (used for adjusting the calcium-phosphorus ratio of hydroxyapatite) to adjust the pH value to 10 +/-0.1, stirring for 1h, aging for 12h at 40 ℃, performing suction filtration by using a sand mold funnel, stirring and washing by using deionized water, drying overnight at 80 ℃, placing in a tubular furnace, roasting for 10h in the air atmosphere at the roasting temperature of 700 ℃, and finally obtaining the hydroxyapatite with the calcium-phosphorus ratio of 1.70.
Example 3
The hydroxyapatite is prepared by the method 1, added under heating in water bath at 40 ℃, and added with 150mL of (NH) with the concentration of 0.2500mol/L 4 ) 2 HPO 4 The aqueous solution was added dropwise to a solution containing 250mL of Ca (NO) at a concentration of 0.250mol/L 3 ) 2 Adding ammonia water dropwise into a three-neck flask of an aqueous solution (used for adjusting the calcium-phosphorus ratio of the hydroxyapatite) to adjust the pH value to 10 +/-0.1, stirring for 1h, aging at 40 ℃ for 12h, performing suction filtration by using a sand mold funnel, stirring and washing by using deionized water, drying overnight at 80 ℃, placing in a tubular furnace, roasting for 5h in an air atmosphere at the roasting temperature of 500 ℃, and finally obtaining the hydroxyapatite with the calcium-phosphorus ratio of 1.67.
Example 4
Hydroxyapatite was prepared by method 1, added under heating in a water bath at 40 deg.C, and 150mL of (NH) solution with a concentration of 0.2500mol/L 4 ) 2 HPO 4 The aqueous solution was added dropwise to a solution containing 250mL of Ca (NO) at a concentration of 0.255mol/L 3 ) 2 Adding ammonia water dropwise into a three-neck flask of aqueous solution (used for adjusting the calcium-phosphorus ratio of hydroxyapatite) to adjust the pH value to 10 +/-0.1, stirring for 1h, aging for 12h at 40 ℃, performing suction filtration by using a sand mold funnel, stirring and washing by using deionized water, drying overnight at 80 ℃, placing in a tubular furnace, roasting for 8h in the air atmosphere at the roasting temperature of 360 ℃, and finally obtaining the hydroxyapatite with the calcium-phosphorus ratio of 1.70.
Example 5
Hydroxyapatite was prepared by method 1, added under heating in a water bath at 40 deg.C, and 150mL of (NH) solution with a concentration of 0.2500mol/L 4 ) 2 HPO 4 The aqueous solution was added dropwise to a solution containing 250mL of Ca (NO) at a concentration of 0.250mol/L 3 ) 2 Three-neck flask of aqueous solution (for adjusting hydroxyl group)Calcium phosphorus ratio of apatite), ammonia water is added dropwise to adjust the pH value to 10 +/-0.1, stirring is carried out for 1h, aging is carried out for 12h at 40 ℃, suction filtration is carried out by a sand mold funnel, deionized water is used for stirring and washing, drying is carried out overnight at 80 ℃, then the obtained product is placed in a tubular furnace, roasting is carried out for 8h under the air atmosphere, the roasting temperature is 500 ℃, and finally hydroxyapatite with the calcium phosphorus ratio of 1.67 is obtained.
Example 6
Preparation of hydroxyapatite by method 2, 1.8g of Ca (OH) 2 Adding the mixture into 100ml of ethylene glycol, stirring the mixture strongly until the mixture is dissolved completely, then slowly dropwise adding 1.4g of phosphoric acid solution into the solution by using a separating funnel, wherein the calcium-phosphorus ratio of a reaction system is 1.67, washing the separating funnel by using deionized water, adjusting the pH to 10 +/-0.1 by using ammonia water, stirring the solution for 10min, centrifuging the precipitated solution, washing the solution for 3 times by using the deionized water, removing impurities, drying and grinding the solution at 60 ℃ to obtain hydroxyapatite powder.
Example 7
The hydroxyapatite prepared in example 1 is used as a catalyst, catechol and diethyl carbonate are mixed according to a molar ratio of 1 -1 Injecting the mixture by a constant flow pump, and collecting main products of o-hydroxy phenetole and a byproduct o-phenetole after the reaction is finished and condensed. In this example, the conversion of catechol was 56% and the selectivity of o-hydroxy phenetole was 80%.
Example 8
The hydroxyapatite prepared in example 3 is used as a catalyst, pyrocatechol and diethyl carbonate are mixed according to a molar ratio of 1 -1 Injecting the mixture by a constant flow pump, and collecting main products of o-hydroxy phenetole and a byproduct o-phenetole after the reaction is finished and condensed. In this example, the conversion of catechol was 68% and the selectivity of o-hydroxy phenetole was 83%.
Example 9
Using the hydroxyapatite prepared in example 4, catechol and diethyl carbonate were mixed in a molar ratio of 1 -1 Injecting the mixture by a constant flow pump, and collecting main products of o-hydroxy phenetole and a byproduct o-phenetole after the reaction is finished and condensed. In this example, the conversion of catechol was 85% and the selectivity of o-hydroxy phenetole was 80%.
Example 10
Using the hydroxyapatite prepared in example 5, catechol and diethyl carbonate were mixed in a molar ratio of 1 -1 Injecting sample by a constant flow pump, and collecting main products of o-hydroxyphenyl ether and a byproduct of o-phenyl diethyl ether after the reaction is finished and condensed. In this example, the conversion of catechol was 78% and the selectivity of o-hydroxy phenetole was 88%.
Example 11
Adopting the hydroxyapatite prepared in example 3, mixing pyrocatechol and diethyl carbonate according to a molar ratio of 1 -1 Injecting the mixture by a constant flow pump, and collecting main products of o-hydroxy phenetole and a byproduct o-phenetole after the reaction is finished and condensed. In this example, the conversion of catechol was 98% and the selectivity of o-hydroxy phenetole was 90%.
Example 12
Using the hydroxyapatite prepared in example 5, catechol and diethyl carbonate were mixed in a molar ratio of 1 -1 Feeding the sample by a constant flow pump, and condensing after the reaction is completedThe main products were then collected as o-hydroxy phenetole and as a by-product o-phenetole. In this example, the conversion of catechol was 99% and the selectivity to o-hydroxy phenetole was 90%.
Example 13
Using the hydroxyapatite prepared in example 2, catechol and diethyl carbonate were mixed in a molar ratio of 1 -1 Injecting the mixture by a constant flow pump, and collecting main products of o-hydroxy phenetole and a byproduct o-phenetole after the reaction is finished and condensed. In this example, the conversion of catechol was 70% and the selectivity of o-hydroxy phenetole was 84%.
Example 14
Using the hydroxyapatite prepared in example 6, catechol and diethyl carbonate were mixed in a molar ratio of 1 -1 Injecting the mixture by a constant flow pump, and collecting main products of o-hydroxy phenetole and a byproduct o-phenetole after the reaction is finished and condensed. In this example, the conversion of catechol was 60% and the selectivity of o-hydroxy phenetole was 85%.
Example 15
Adopting the hydroxyapatite prepared in example 3, mixing pyrocatechol and diethyl carbonate according to a molar ratio of 1 -1 Injecting the mixture by a constant flow pump, and collecting main products of o-hydroxy phenetole and a byproduct o-phenetole after the reaction is finished and condensed. In this example, the conversion of catechol was 80% and the selectivity of o-hydroxy phenetole was 85%.
Example 16
Using the hydroxyapatite prepared in example 3, catechol and diethyl carbonate were addedMixing according to a molar ratio of 1 -1 Injecting the mixture by a constant flow pump, and collecting main products of o-hydroxy phenetole and a byproduct o-phenetole after the reaction is finished and condensed. In this example, the conversion of catechol was 85% and the selectivity to hydroxyphenyl ether was 78%.
Example 17
Using the hydroxyapatite prepared in example 3, catechol and diethyl carbonate were mixed in a molar ratio of 1 -1 Injecting the mixture by a constant flow pump, and collecting main products of o-hydroxy phenetole and a byproduct o-phenetole after the reaction is finished and condensed. In this example, the conversion of catechol was 60% and the selectivity of o-hydroxy phenetole was 85%.
Example 18
Using the hydroxyapatite prepared in example 3, catechol and diethyl carbonate were mixed according to a molar ratio of 1 -1 Injecting the mixture by a constant flow pump, and collecting main products of o-hydroxy phenetole and a byproduct o-phenetole after the reaction is finished and condensed. In this example, the conversion of catechol was 100%, and the selectivity of phenetole was 75%.
Example 19
Using the hydroxyapatite prepared in example 3, catechol and diethyl carbonate were mixed in a molar ratio of 1 -1 Injecting the mixture by a constant flow pump, and collecting main products of o-hydroxy phenetole and a byproduct o-phenetole after the reaction is finished and condensed. In this example, the conversion of catechol was 88% selectivity to o-hydroxyphenyl ether was 80%.
Example 20
Using the hydroxyapatite prepared in example 3, catechol and diethyl carbonate were mixed in a molar ratio of 1 -1 Injecting the mixture by a constant flow pump, and collecting main products of o-hydroxy phenetole and a byproduct o-phenetole after the reaction is finished and condensed. In this example, the conversion of catechol was 79% and the selectivity of o-hydroxy phenetole was 85%.
Example 21
Using the hydroxyapatite prepared in example 3, catechol and diethyl carbonate were mixed in a molar ratio of 1 -1 Injecting the mixture by a constant flow pump, and collecting main products of o-hydroxy phenetole and a byproduct o-phenetole after the reaction is finished and condensed. In this example, the conversion of catechol was 92% and the selectivity to o-hydroxy phenetole was 90%.
Example 22
Using the hydroxyapatite prepared in example 3, catechol and diethyl carbonate were mixed in a molar ratio of 1 -1 Injecting the mixture by a constant flow pump, and collecting main products of o-hydroxy phenetole and a byproduct o-phenetole after the reaction is finished and condensed. In this example, the conversion of catechol was 90%, and the selectivity of o-hydroxy phenetole was 91%.
Comparative example 1
The method comprises the steps of adopting self-made active carbon-loaded heteropoly acid as a catalyst, mixing pyrocatechol and diethyl carbonate according to a molar ratio of 1The room temperature is raised to 230 ℃, the temperature of the reactor is raised to 300 ℃, and the weight hourly space velocity is 6h -1 Injecting the mixture by a constant flow pump, and collecting main products of o-hydroxy phenetole and a byproduct o-phenetole after the reaction is finished and condensed. In this example, the conversion of catechol was 40% and the selectivity of o-hydroxy phenetole was 61%.
Comparative example 2
The method comprises the steps of adopting self-made KOH/NaY as a catalyst, mixing pyrocatechol and diethyl carbonate according to a molar ratio of 1 -1 Injecting the mixture by a constant flow pump, and collecting main products of o-hydroxy phenetole and a byproduct o-phenetole after the reaction is finished and condensed. In this example, the conversion of catechol was 52% and the selection of o-hydroxy phenetole was 63%.
TABLE 1 hydroxyapatite obtained by different preparation methods
| Examples | Preparation method | Calcium to phosphorus ratio | Roasting temperature/. Degree.C | Calcination time/h |
| Example 1 | Method 1 | 1.58 | 500 | 5 |
| Example 2 | Method 1 | 1.70 | 700 | 8 |
| Example 3 | Method 1 | 1.67 | 500 | 5 |
| Example 4 | Method 1 | 1.70 | 360 | 8 |
| Example 5 | Method 1 | 1.67 | 500 | 10 |
| Example 6 | Method 2 | 1.67 | _ | _ |
TABLE 2 comparison of catalytic Activity of examples and comparative examples
It can be seen from tables 1 and 2 that the method provided by the invention uses self-made hydroxyapatite as a catalyst to catalyze the reaction of catechol and diethyl carbonate to generate o-hydroxy phenetole, and compared with the existing catalyst, the conversion rate of catechol and the selectivity of o-hydroxy phenetole are both greatly improved, wherein the conversion rate of catechol can reach 98%, the selectivity of o-hydroxy phenetole can reach 90%, and the yield of o-hydroxy phenetole is significantly improved.
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 (5)
1. A method for synthesizing o-hydroxy phenetole by hydroxyapatite catalysis is characterized in that reactants are catechol and diethyl carbonate, wherein the molar ratio of catechol to diethyl carbonate is 1-2; the catalyst is hydroxyapatite, the reaction is gas catalytic reaction carried out on a fixed bed, the reaction temperature is 250-450 ℃, and the space velocity is 4-8 h -1 。
2. The method for catalytically synthesizing o-hydroxyphenyl ether by hydroxyapatite according to claim 1, wherein the dosage of the catalyst hydroxyapatite is 0.5 to 1.5g, the size of the catalyst particle is 30 to 50 meshes, and the molar ratio of Ca to P in the catalyst hydroxyapatite is 1.58 to 1.70.
3. The method for the catalytic synthesis of o-hydroxyphenyl ether with hydroxyapatite according to claim 1, wherein the hydroxyapatite is prepared by self-made hydroxyapatite according to the following method 1 or method 2:
(1) The method comprises the following steps: a certain amount of (NH) 4 ) 2 HPO 4 Dropwise addition of an aqueous solution to Ca (NO) 3 ) 2 Adding ammonia water dropwise into the aqueous solution to adjust the pH value to be 10 +/-0.1, stirring for 1h, aging for 12h at 40 ℃, performing suction filtration, washing, drying and roasting to obtain hydroxyapatite;
(2) The method 2 comprises the following steps: slowly adding phosphoric acid solution to Ca (OH) 2 Adjusting the pH value to 10 +/-0.1 by using ammonia water in the glycol solution, stirring for 10min, centrifuging the precipitated solution, washing, drying and grinding to obtain the hydroxyapatite.
4. The method for the catalytic synthesis of o-hydroxy phenetole with hydroxyapatite according to claim 3, wherein Ca (NO) is used in the method 1 3 ) 2 And (NH) 4 ) 2 HPO 4 The molar ratio of the raw materials is 0.9-1.1, the roasting temperature is 300-850 ℃, and the roasting time is 3-12 h.
5. The method for the catalytic synthesis of o-hydroxy phenetole by hydroxyapatite according to claim 3, wherein the calcination temperature in the method 1 is 360-700 ℃ and the calcination time is 5-10 h.
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