CN115197052B - Method for synthesizing o-hydroxyphenylethyl ether by catalyzing hydroxyapatite - Google Patents
Method for synthesizing o-hydroxyphenylethyl ether by catalyzing hydroxyapatite Download PDFInfo
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- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 71
- 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 71
- 238000000034 method Methods 0.000 title claims abstract description 45
- REINWLIFAPNZPI-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyphenyl)ethoxy]ethyl]phenol Chemical compound OC1=CC=CC=C1CCOCCC1=CC=CC=C1O REINWLIFAPNZPI-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 20
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 78
- 239000000243 solution Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000001035 drying Methods 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 20
- 239000006227 byproduct Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- 238000009834 vaporization Methods 0.000 description 19
- 230000008016 vaporization Effects 0.000 description 19
- 238000005070 sampling Methods 0.000 description 18
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 16
- ZQBZAOZWBKABNC-UHFFFAOYSA-N [P].[Ca] Chemical compound [P].[Ca] ZQBZAOZWBKABNC-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 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
- 230000008569 process Effects 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
- GOJFAKBEASOYNM-UHFFFAOYSA-N 2-(2-aminophenoxy)aniline Chemical compound NC1=CC=CC=C1OC1=CC=CC=C1N GOJFAKBEASOYNM-UHFFFAOYSA-N 0.000 description 1
- MOEFFSWKSMRFRQ-UHFFFAOYSA-N 2-ethoxyphenol Chemical compound CCOC1=CC=CC=C1O MOEFFSWKSMRFRQ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- 230000006978 adaptation Effects 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 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
- 238000004458 analytical method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 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
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 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
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 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
- 238000003746 solid phase reaction Methods 0.000 description 1
- 235000013599 spices Nutrition 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
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- 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 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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a synthesis method of o-hydroxyphenylethyl ether, 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 1.58 to 1.70; the reaction is carried out in a fixed bed reactor, the reaction is gas catalytic reaction, the reaction temperature is 250-450 ℃, and the airspeed is 4-8 h ‑1 . Ca in the catalyst of the invention 2+ 、PO 4 3‑ And OH (OH) ‑ The catalyst has strong ion exchange capacity, can be substituted by other cations or anions, and can regulate the quantity and proportion of acid-base sites on the surface by regulating the molar ratio of Ca and P and the roasting temperature; meanwhile, the surface of the hydroxyapatite has rich hydroxyl groups, and can adsorb reactants in the reaction. Therefore, the method is applied to the reaction for synthesizing the o-hydroxyphenylethyl ether, can greatly improve the conversion rate of catechol and the selectivity of the o-hydroxyphenylethyl ether, and has the advantages of low-cost 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-hydroxyphenylethyl ether by using hydroxyapatite as a catalyst to catalyze catechol and diethyl carbonate and application thereof.
Background
The o-hydroxyphenylethyl ether is also called ethyl guaiacol or o-ethoxyphenol, is one of the main raw materials of the synthetic spice ethyl vanillin, is widely applied to the fields of medicine, dye, cosmetics and dye synthesis, and can also be directly used as an analysis reagent.
At present, the method for producing the o-hydroxyphenylethyl ether at home and abroad has the advantages of high yield, small pollution, low cost and the like compared with other methods such as an o-aminophenylether method, an o-nitrochlorobenzene method, a catechol method and the like, and is an advanced process at home and abroad.
Catechol method is divided into catechol/ethanol method, catechol/diethyl carbonate method and catechol/chloroethane method according to alkylating agent, and catechol/diethyl carbonate method is the main trend of the synthesis of the o-hydroxyphenyldiethyl ether at present, and commonly used catalysts include silicon-aluminum molecular sieves, transition metal oxides, phosphates and the like, but the activity of the catalysts is lower, and the acid sites are easy to catalyze side reactions such as alkylation, cyclization and the like on benzene rings of reactants, so that the selectivity of the o-hydroxyphenyldiethyl ether is reduced.
Therefore, development of a catalyst with high activity and high selectivity for synthesizing o-hydroxyphenylethyl ether is urgently needed.
Disclosure of Invention
The invention provides a method for efficiently catalyzing and synthesizing o-hydroxyphenylethyl ether 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 the o-hydroxyphenylethyl ether in the prior art. The catalyst has adjustable acid-base sites, and the conversion rate and selectivity of the catalyst are improved through the synergistic effect of the acid-base sites.
In order to solve the technical problems, the invention specifically comprises the following steps:
a method for synthesizing o-hydroxyphenylethyl ether by using hydroxyapatite as a catalyst is characterized in that reactants are catechol and diethyl carbonate, wherein the molar ratio of the catechol to the diethyl carbonate is 1:2-1:8; the catalyst is hydroxyapatite, the reaction is carried out on a fixed bed, the reaction is gas catalytic reaction, the reaction temperature is 250-450 ℃, and the airspeed is 4-8 h -1 。
As the limit of the invention, the dosage of the catalyst hydroxyapatite is 0.5 to 1.5g, the particle size of the catalyst hydroxyapatite is 20 to 50 meshes, and the molar ratio of the catalyst hydroxyapatite Ca to the catalyst P is 1.58 to 1.70.
As a limitation of the present invention, the self-made hydroxyapatite is adopted, and the preparation method of the self-made hydroxyapatite can be carried out according to the following method 1 or method 2, and the specific steps are as follows:
method 1: a certain amount of (NH) was heated in a water bath at 40 DEG C 4 ) 2 HPO 4 The aqueous solution was added dropwise to Ca (NO) 3 ) 2 Dropwise adding ammonia water into the aqueous solution, regulating 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 into a tube furnace, and roasting for 3-12 h in an air atmosphere at a roasting temperature of 300-850 ℃ to obtain the hydroxyapatite. Wherein Ca (NO) 3 ) 2 And (NH) 4 ) 2 HPO 4 The molar ratio of (2) is 0.9-1.1.
The preferred calcination temperature in preparation method 1 is 360-700 ℃ and the calcination time is 5-10 hours.
(2) Method 2: slowly dropping the phosphoric acid solution into Ca (OH) 2 In the glycol solution of (2), the calcium-phosphorus ratio of the reaction system is 1.67, the pH value is regulated to 10+/-0.1 by ammonia water, the solution is stirred for 10min, and the precipitated solution is centrifuged, washed, dried and ground at 60 ℃ to obtain the hydroxyapatite.
The self-made hydroxyapatite is used for synthesizing o-hydroxyphenylethyl ether by gas-solid phase reaction, and specifically comprises the following steps: preparing reaction liquid (1:2-1:8) of catechol and diethyl carbonate in molar ratio, placing a certain amount of hydroxyapatite into a fixed bed reactor, and the temperature of a vaporization chamber is250 ℃, the temperature of the reactor is 250-450 ℃, and the reactor is heated in inert gas (Ar or N) 2 ) Under protection, after the temperature reaches a set value, the raw materials are pumped into a reactor through a micro constant flow pump, flow through a bed layer for reaction, and are condensed to obtain a reaction liquid, and the conversion rate of catechol and the selectivity of the o-hydroxyphenylethyl ether are quantitatively analyzed by gas chromatography.
The invention provides a method for preparing o-hydroxyphenylethyl ether by catalyzing the reaction of catechol and diethyl carbonate by hydroxyapatite. Compared with the traditional catalyst, the method has the following advantages:
since the stoichiometric formula of hydroxyapatite is [ Ca ] 10 (PO 4 ) 6 (OH) 2 ]Wherein Ca is 2+ 、PO 4 3- And OH (OH) - Has strong ion exchange capacity and can be replaced by other cations or anions. The quantity and proportion of acid-base sites on the surface can be regulated by regulating the molar ratio of Ca to P and the roasting temperature; meanwhile, the surface of the hydroxyapatite has rich hydroxyl groups, and can adsorb reactants in the reaction. Therefore, the method is applied to the reaction of preparing the o-hydroxyphenylethyl ether from the catechol and the diethyl carbonate, the highest conversion rate of the catechol can reach 100 percent, the highest selectivity of the o-hydroxyphenylethyl ether can reach 90 percent, the yield of the o-hydroxyphenylethyl ether is obviously improved, and meanwhile, the method has the advantages of low cost and easiness in obtaining raw materials, environmental friendliness and the like.
Drawings
FIG. 1 is an XRD pattern of hydroxyapatite obtained in example 1; as can be seen from the figure, the self-made hydroxyapatite only shows the characteristic diffraction signal (JCPLDS 01-086-074) of the hydroxyapatite, and has no CaO or CaCO 3 The diffraction peaks, which indicate that the hydroxyapatite sample was successfully prepared.
FIG. 2 is a graph showing the acid-base densities of different Ca/P hydroxyapatite surfaces; as can be seen from the graph, the surface acid strength and the alkali strength of the hydroxyapatite with different Ca/P have no obvious change, but the acid density is reduced along with the increase of Ca/P, the alkali density is gradually increased, and the alkali is mainly Ca 2+ The acid position being H + Introduction of H for charge balance + Thus the smaller the Ca/P ratio, the more acid densityThe larger the alkali density, the smaller.
FIG. 3 shows the acid-base densities of the surfaces of hydroxyapatite samples at different roasting temperatures; from the graph, the surface acid strength and the alkali strength of the hydroxyapatite with different Ca/P are not obviously changed, the alkali density is not obviously changed, the acid density is firstly increased and then reduced along with the roasting temperature, and the maximum value is reached at 500 ℃.
Detailed Description
The invention will be further illustrated with reference to the following examples, but it should be understood that these examples are for illustrative purposes only and should not be construed as limiting the practice of the invention.
In the invention, two different methods are adopted to synthesize the hydroxyapatite, and the addition amount of raw materials and reaction conditions are regulated in the synthesis process, so that different hydroxyapatite powders can be obtained.
Example 1
Preparation of hydroxyapatite by method 1, addition with heating in a 40℃water bath, 150mL of (NH) at 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 0.237mol/L 3 ) 2 In a three-neck flask of aqueous solution (for adjusting the calcium-phosphorus ratio of hydroxyapatite), dropwise adding ammonia water to adjust the pH to 10+/-0.1, stirring for 1h, aging at 40 ℃ for 12h, filtering with a sand mold funnel, stirring and washing with deionized water, drying at 80 ℃ overnight, placing in a tubular furnace, roasting for 5h in an air atmosphere, wherein the roasting temperature is 500 ℃, and finally obtaining the hydroxyapatite with the calcium-phosphorus ratio of 1.58.
Example 2
Preparation of hydroxyapatite by method 1, addition with heating in a 40℃water bath, 150mL of (NH) at a concentration of 0.2500mol/L 4 ) 2 HPO 4 The aqueous solution was added dropwise to a solution containing 250mL of Ca (NO) having a concentration of 0.255mol/L 3 ) 2 Adding ammonia water dropwise into a three-neck flask (for adjusting calcium-phosphorus ratio of hydroxyapatite) of aqueous solution to adjust pH to 10+ -0.1, stirring for 1h, aging at 40deg.C for 12h, filtering with sand mold funnel, stirring and washing with deionized water, drying at 80deg.C overnight, placing into a tube furnace, roasting in air atmosphere for 10h at 700deg.C to obtain calcium-phosphorus ratio of 1.70Hydroxyapatite.
Example 3
Preparation of hydroxyapatite by method 1, addition with heating in a 40℃water bath, 150mL of (NH) at 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 In a three-neck flask of aqueous solution (for adjusting the calcium-phosphorus ratio of hydroxyapatite), dropwise adding ammonia water to adjust the pH to 10+/-0.1, stirring for 1h, aging at 40 ℃ for 12h, filtering with a sand mold funnel, stirring and washing with deionized water, drying at 80 ℃ overnight, placing in a tubular furnace, roasting for 5h in an air atmosphere, wherein the roasting temperature is 500 ℃, and finally obtaining the hydroxyapatite with the calcium-phosphorus ratio of 1.67.
Example 4
Preparation of hydroxyapatite by method 1, addition with heating in a 40℃water bath, 150mL of (NH) at a concentration of 0.2500mol/L 4 ) 2 HPO 4 The aqueous solution was added dropwise to a solution containing 250mL of Ca (NO) having a concentration of 0.255mol/L 3 ) 2 In a three-neck flask of aqueous solution (for adjusting the calcium-phosphorus ratio of hydroxyapatite), dropwise adding ammonia water to adjust the pH to 10+/-0.1, stirring for 1h, aging at 40 ℃ for 12h, filtering with a sand mold funnel, stirring and washing with deionized water, drying at 80 ℃ overnight, placing in a tubular furnace, roasting for 8h in an air atmosphere, wherein the roasting temperature is 360 ℃, and finally obtaining the hydroxyapatite with the calcium-phosphorus ratio of 1.70.
Example 5
Preparation of hydroxyapatite by method 1, addition with heating in a 40℃water bath, 150mL of (NH) at 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 In a three-neck flask of aqueous solution (for adjusting the calcium-phosphorus ratio of hydroxyapatite), dropwise adding ammonia water to adjust the pH to 10+/-0.1, stirring for 1h, aging at 40 ℃ for 12h, filtering with a sand mold funnel, stirring and washing with deionized water, drying at 80 ℃ overnight, placing in a tubular furnace, roasting for 8h in an air atmosphere, wherein the roasting temperature is 500 ℃, and finally obtaining the hydroxyapatite with the calcium-phosphorus ratio of 1.67.
Example 6
Preparation of hydroxyapatite by method 2, the1.8g of Ca (OH) 2 Adding into 100ml of ethylene glycol, stirring strongly until the solution is completely dissolved, then slowly dripping 1.4g of phosphoric acid solution into the solution by using a separating funnel, washing the separating funnel by using deionized water, adjusting the pH value of the separating funnel to 10+/-0.1 by using ammonia water, centrifuging the precipitated solution after stirring for 10min, washing the solution by using deionized water for 3 times, removing impurities, and drying and grinding at 60 ℃ to obtain hydroxyapatite powder.
Example 7
The hydroxyapatite prepared in example 1 was used as a catalyst, catechol and diethyl carbonate were mixed in a molar ratio of 1:2, 1.5g of the catalyst was placed in a fixed bed reactor, the catalyst particle size was 30 mesh, the temperature of a vaporization chamber was increased to 230 ℃, the temperature of the reactor was increased to 250 ℃, and the weight hourly space velocity was 4h -1 And (3) sampling by using a constant flow pump, and collecting the main product, namely the o-hydroxyphenyldiethyl ether and the by-product, namely the o-phenylphthaldiethyl ether after the reaction is condensed. In this example, the conversion of catechol was 56% and the selectivity of the phenetole was 80%.
Example 8
The hydroxyapatite prepared in example 3 was used as a catalyst, catechol and diethyl carbonate were mixed in a molar ratio of 1:2, 1.5g of the catalyst was placed in a fixed bed reactor, the catalyst particle size was 30 mesh, the temperature of the vaporization chamber was increased to 230 ℃, the reactor was increased to 250 ℃, and the weight hourly space velocity was 4h -1 And (3) sampling by using a constant flow pump, and collecting the main product, namely the o-hydroxyphenyldiethyl ether and the by-product, namely the o-phenylphthaldiethyl ether after the reaction is condensed. In this example, the conversion of catechol was 68% and the selectivity to phenetole was 83%.
Example 9
Using the hydroxyapatite prepared in example 4, catechol and diethyl carbonate were mixed at a molar ratio of 1:8, 0.5g of catalyst was placed in a fixed bed reactor, the catalyst particle size was 30 mesh, the vaporization chamber temperature was increased to 230 ℃, the reactor was warmed to 450 ℃, and the weight hourly space velocity was 8h -1 And (3) sampling by using a constant flow pump, and collecting the main product, namely the o-hydroxyphenyldiethyl ether and the by-product, namely the o-phenylphthaldiethyl ether after the reaction is condensed. The book is provided withIn the examples, the conversion of catechol was 85% and the selectivity to o-hydroxyphenylethyl ether was 80%.
Example 10
Using the hydroxyapatite prepared in example 5, catechol and diethyl carbonate were mixed at a molar ratio of 1:8, 0.5g of catalyst was placed in a fixed bed reactor, the catalyst particle size was 30 mesh, the vaporization chamber temperature was increased to 230 ℃, the reactor was warmed to 450 ℃, and the weight hourly space velocity was 8h -1 And (3) sampling by using a constant flow pump, and collecting the main product, namely the o-hydroxyphenyldiethyl ether and the by-product, namely the o-phenylphthaldiethyl ether after the reaction is condensed. In this example, the conversion of catechol was 78% and the selectivity to phenetole was 88%.
Example 11
Using the hydroxyapatite prepared in example 3, catechol and diethyl carbonate were mixed in a molar ratio of 1:4, 1g of catalyst was placed in a fixed bed reactor, the catalyst particle size was 30 mesh, the vaporization chamber temperature was increased to 230 ℃, the reactor was warmed to 330 ℃, and the weight hourly space velocity was 6h -1 And (3) sampling by using a constant flow pump, and collecting the main product, namely the o-hydroxyphenyldiethyl ether and the by-product, namely the o-phenylphthaldiethyl ether after the reaction is condensed. In this example, the conversion of catechol was 98% and the selectivity to phenetole was 90%.
Example 12
Using the hydroxyapatite prepared in example 5, catechol and diethyl carbonate were mixed in a molar ratio of 1:4, 1g of catalyst was placed in a fixed bed reactor, the catalyst particle size was 30 mesh, the vaporization chamber temperature was increased to 230 ℃, the reactor was warmed to 330 ℃, and the weight hourly space velocity was 6h -1 And (3) sampling by using a constant flow pump, and collecting the main product, namely the o-hydroxyphenyldiethyl ether and the by-product, namely the o-phenylphthaldiethyl ether after the reaction is condensed. In this example, the conversion of catechol was 99% and the selectivity to phenetole was 90%.
Example 13
With the hydroxyapatite prepared in example 2, catechol and diethyl carbonate were mixed in a molar ratio of 1:4, and 1g of catalyst was placed in a fixed bed reactor, the catalystThe particle size is 30 meshes, the temperature of the vaporization chamber is increased to 230 ℃, the temperature of the reactor is increased to 300 ℃, and the weight hourly space velocity is 6h -1 And (3) sampling by using a constant flow pump, and collecting the main product, namely the o-hydroxyphenyldiethyl ether and the by-product, namely the o-phenylphthaldiethyl ether after the reaction is condensed. In this example, the conversion of catechol was 70% and the selectivity to phenetole was 84%.
Example 14
Using the hydroxyapatite prepared in example 6, catechol and diethyl carbonate were mixed in a molar ratio of 1:4, 1g of catalyst was placed in a fixed bed reactor, the catalyst particle size was 30 mesh, the vaporization chamber temperature was increased to 230 ℃, the reactor was warmed to 300 ℃, and the weight hourly space velocity was 6h -1 And (3) sampling by using a constant flow pump, and collecting the main product, namely the o-hydroxyphenyldiethyl ether and the by-product, namely the o-phenylphthaldiethyl ether after the reaction is condensed. In this example, the conversion of catechol was 60% and the selectivity of the phenetole was 85%.
Example 15
Using the hydroxyapatite prepared in example 3, catechol and diethyl carbonate were mixed in a molar ratio of 1:2, 1g of catalyst was placed in a fixed bed reactor, the catalyst particle size was 30 mesh, the vaporization chamber temperature was increased to 230 ℃, the reactor was warmed to 330 ℃, and the weight hourly space velocity was 6h -1 And (3) sampling by using a constant flow pump, and collecting the main product, namely the o-hydroxyphenyldiethyl ether and the by-product, namely the o-phenylphthaldiethyl ether after the reaction is condensed. In this example, the conversion of catechol was 80% and the selectivity of the phenetole was 85%.
Example 16
Using the hydroxyapatite prepared in example 3, catechol and diethyl carbonate were mixed in a molar ratio of 1:8, 1g of catalyst was placed in a fixed bed reactor, the catalyst particle size was 30 mesh, the vaporization chamber temperature was increased to 230 ℃, the reactor was warmed to 330 ℃, and the weight hourly space velocity was 6h -1 And (3) sampling by using a constant flow pump, and collecting the main product, namely the o-hydroxyphenyldiethyl ether and the by-product, namely the o-phenylphthaldiethyl ether after the reaction is condensed. In this example, the catechol conversion was 85% and the selectivity to the phenetole was 78%.
Example 17
Using the hydroxyapatite prepared in example 3, catechol and diethyl carbonate were mixed in a molar ratio of 1:4, 1g of catalyst was placed in a fixed bed reactor, the catalyst particle size was 30 mesh, the vaporization chamber temperature was increased to 230 ℃, the reactor was warmed to 250 ℃, and the weight hourly space velocity was 6h -1 And (3) sampling by using a constant flow pump, and collecting the main product, namely the o-hydroxyphenyldiethyl ether and the by-product, namely the o-phenylphthaldiethyl ether after the reaction is condensed. In this example, the conversion of catechol was 60% and the selectivity of the phenetole was 85%.
Example 18
Using the hydroxyapatite prepared in example 3, catechol and diethyl carbonate were mixed at a molar ratio of 1:4, 1g of the catalyst was placed in a fixed bed reactor, the vaporization temperature was increased to 230 ℃, the reactor was heated to 450 ℃, and the weight hourly space velocity was 6h -1 And (3) sampling by using a constant flow pump, and collecting the main product, namely the o-hydroxyphenyldiethyl ether and the by-product, namely the o-phenylphthaldiethyl ether after the reaction is condensed. In this example, the conversion of catechol was 100% and the selectivity to phenetole was 75%.
Example 19
Using the hydroxyapatite prepared in example 3, catechol and diethyl carbonate were mixed in a molar ratio of 1:4, 1g of catalyst was placed in a fixed bed reactor, the catalyst particle size was 30 mesh, the vaporization chamber temperature was increased to 230 ℃, the reactor was warmed to 330 ℃, and the weight hourly space velocity was 4h -1 And (3) sampling by using a constant flow pump, and collecting the main product, namely the o-hydroxyphenyldiethyl ether and the by-product, namely the o-phenylphthaldiethyl ether after the reaction is condensed. In this example, the conversion of catechol was 88% and the selectivity to phenetole was 80%.
Example 20
Using the hydroxyapatite prepared in example 3, catechol and diethyl carbonate were mixed in a molar ratio of 1:4, 1g of catalyst was placed in a fixed bed reactor, the catalyst particle size was 30 mesh, the vaporization chamber temperature was increased to 230 ℃, the reactor was warmed to 330 ℃, and the weight hourly space velocity was 8h -1 By constant-flow pumpsAnd (3) sampling, and collecting the main product, namely the o-hydroxyphenyldiethyl ether and the by-product, namely the o-phenylphthaldiethyl ether after the reaction is finished and condensed. In this example, the catechol conversion was 79% and the selectivity to the phenetole was 85%.
Example 21
Using the hydroxyapatite prepared in example 3, catechol and diethyl carbonate were mixed in a molar ratio of 1:4, 1.5g of catalyst was placed in a fixed bed reactor, the catalyst particle size was 30 mesh, the vaporization chamber temperature was increased to 230 ℃, the reactor was warmed to 330 ℃, and the weight hourly space velocity was 4h -1 And (3) sampling by using a constant flow pump, and collecting the main product, namely the o-hydroxyphenyldiethyl ether and the by-product, namely the o-phenylphthaldiethyl ether after the reaction is condensed. In this example, the conversion of catechol was 92% and the selectivity to phenetole was 90%.
Example 22
Using the hydroxyapatite prepared in example 3, catechol and diethyl carbonate were mixed in a molar ratio of 1:4, 1.5g of catalyst was placed in a fixed bed reactor, the catalyst particle size was 50 mesh, the vaporization chamber temperature was increased to 230 ℃, the reactor was warmed to 330 ℃, and the weight hourly space velocity was 4h -1 And (3) sampling by using a constant flow pump, and collecting the main product, namely the o-hydroxyphenyldiethyl ether and the by-product, namely the o-phenylphthaldiethyl ether after the reaction is condensed. In this example, the conversion of catechol was 90% and the selectivity of the phenetole was 91%.
Comparative example 1
The self-made activated carbon supported heteropolyacid is used as a catalyst, catechol and diethyl carbonate are mixed according to a molar ratio of 1:4, 1g of catalyst is placed in a fixed bed reactor, the particle size of the catalyst is 30 meshes, the temperature of a vaporization chamber is increased to 230 ℃, the temperature of the reactor is increased to 300 ℃, and the weight hourly space velocity is 6h -1 And (3) sampling by using a constant flow pump, and collecting the main product, namely the o-hydroxyphenyldiethyl ether and the by-product o-phenylphthaldiethyl ether, after the reaction is completed and condensed. In this example, the catechol conversion was 40% and the selectivity to the phenetole was 61%.
Comparative example 2
Homemade KOH/NaY is adopted as catalystThe catalyst is prepared by mixing catechol and diethyl carbonate according to a molar ratio of 1:4, placing 1g of catalyst in a fixed bed reactor, wherein the particle size of the catalyst is 30 meshes, the temperature of a vaporization chamber is increased to 230 ℃, the temperature of the reactor is increased to 300 ℃, and the weight hourly space velocity is 6h -1 And (3) sampling by using a constant flow pump, and collecting the main product, namely the o-hydroxyphenyldiethyl ether and the by-product o-phenylphthaldiethyl ether, after the reaction is completed and condensed. In this example, the catechol conversion was 52% and the selection of the o-hydroxyphenylethyl ether was 63%.
Table 1 hydroxyapatite obtained by different preparation methods
| Examples | Preparation method | Ratio of calcium to phosphorus | Firing temperature/. Degree.C | Roasting 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
From tables 1 and 2, it can be seen that the invention adopts self-made hydroxyapatite as the catalyst to catalyze the reaction of catechol and diethyl carbonate to generate the o-hydroxyphenylethyl ether, and compared with the existing catalyst, the conversion rate of catechol and the selectivity of the o-hydroxyphenylethyl ether are greatly improved, wherein the conversion rate of catechol can reach 98%, the selectivity of the o-hydroxyphenylethyl ether can reach 90%, and the yield of the o-hydroxyphenylethyl ether is remarkably improved.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (2)
1. A method for synthesizing o-hydroxyphenyldiethyl ether by using hydroxyapatite as a catalyst is characterized in that reactants are catechol and diethyl carbonate, wherein the molar ratio of the catechol to the diethyl carbonate is 1:2-1:8, the catalyst is hydroxyapatite, the reaction is catalytic reaction carried out on a fixed bed, the reaction temperature is 250-450 ℃, and the weight hourly space velocity is 4-8 h -1 ；
The catalyst hydroxyapatite is used in an amount of 0.5-1.5 g, the particle size is 30-50 meshes, the molar ratio of Ca to P in the hydroxyapatite is 1.58-1.70, and the preparation method is carried out according to the method 1 or the method 2:
(1) Method 1: a certain amount (NH) 4 ) 2 HPO 4 The aqueous solution was added dropwise to Ca (NO) 3 ) 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 ℃, and carrying out suction filtration, washing, drying and roasting to obtain hydroxyapatite, wherein the roasting temperature is 300-850 ℃, and the roasting time is 3-12 hours;
(2) Method 2: slowly dropping the phosphoric acid solution into Ca (OH) 2 In the glycol solution of (2), ammonia water is utilized to adjust the pH value to 10+/-0.1, the solution which is precipitated is centrifugated after stirring for 10min, and the hydroxyapatite is obtained after washing, drying and grinding.
2. The method for synthesizing o-hydroxyphenylethyl ether by using hydroxyapatite as set forth in claim 1, wherein the roasting temperature in the method 1 is 360-700 ℃ and the roasting time is 5-10 h.
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