CN100588640C - Method for synthesizing o-hydroxy phenetole - Google Patents
Method for synthesizing o-hydroxy phenetole Download PDFInfo
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- CN100588640C CN100588640C CN200610165509A CN200610165509A CN100588640C CN 100588640 C CN100588640 C CN 100588640C CN 200610165509 A CN200610165509 A CN 200610165509A CN 200610165509 A CN200610165509 A CN 200610165509A CN 100588640 C CN100588640 C CN 100588640C
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Abstract
A method for synthesizing an O-hydroxy phenyl ether relates to a method for applying a novel catalyst to prepare the O-hydroxy phenyl ether, which is synthesized through a gas-phase alkylation betweenthe cathecol and the ethanol. The composition expirical formula of the active center of the catalysts is Al< 1 >P< a >X< b >; wherein, X is Cr, Mg, V or Zr, a is more than or equal to 0.9 and less than or equal to 1.5 and b is more than 0 and is less than or equal to 0.3; the aluminum nitrate is used as the aluminum source, the phosphoric acid, the ammonium dihydrogen phosphate and the ammonium phosphate or the ammonium phosphate are used as the phosphorous source and the nitrate, the zirconium oxychlorid and the ammonium metavanadate of Mg and Cr are used as the raw materials of X; the reaction between the catechol and the ethanol is carried out in a fixed bed reactor and the molar ratio of the ethanol to the catechol ranges from 2 to 7:1; the ratio of the mole number of the catechol tothat of the catalysts every hour ranges from 0.05 to 0.75 as Al, the reaction space velocity ranges from 0.1 to 1.5h<-1> as the volume of the liquid and the reaction temperature ranges from 533K to 593K. The catalysts adopted by the invention have simple compositions, the raw materials are simple and easy to be obtained and the specific surface area is larger; the invention delivers high yield andhigh stability for the target reaction.
Description
Technical field
The present invention relates to the method for a kind of pyrocatechol and ethanol gas solid phase alkylated reaction synthesizing 2-ethoxy-phenol, particularly a kind ofly use the method that new catalyst prepares 2-ethoxy-phenol.
Background technology
2-ethoxy-phenol (ethyl wood phenol) is important fine-chemical intermediate and an industrial chemicals in the industry such as spices, medicine, agricultural, and purposes is widely arranged.
2-ethoxy-phenol is as the raw material of synthetic perfume (vanillin food grade,1000.000000ine mesh), and demand is bigger, is in great demand very much in the international market.Vanillin food grade,1000.000000ine mesh is the high-grade spices of a kind of famous and precious broad spectrum type, is widely used in fixative, spoiled dose, seasonings, is applied in the production of industries such as makeup, perfumed soap, cake, candy, beverage, tobacco and bake; As spice additive, the few and exclusive aroma with its addition and the extremely favor of international fragrance, its demand has become well sold and in short supply chemical with annual 10% speed increase.At present, the vanirone of selling on the market is that raw material is synthetic greatly with the 2-ethoxy-phenol.Therefore, 2-ethoxy-phenol is as the critical materials of synthetic vanirone, and the production of whole vanillin food grade,1000.000000ine mesh is had fundamental influence.
At present, the method for industrialization synthesizing 2-ethoxy-phenol mainly contains two kinds both at home and abroad, i.e. o-phenetidine method and pyrocatechol-Ethanol Method.Two kinds of methods are compared, and pyrocatechol-Ethanol Method has the yield height, pollutes little, low cost and other advantages than the former, and this technology is present most advanced, the most competitive in the world operational path, and has realized industrialization in developed country.Multiple solid acid catalyst is used for this reaction, and as kaolin, oxide compound and mixed oxide, molecular sieve, phosphoric acid salt, loaded catalyst etc., but mostly there is the shortcoming of activity (selectivity or stability) difference in these catalyzer.
European patent (EP 0 509 927 A1) has been reported Al
aP
bTi
cSi
dX
eO
fThe reaction of the pure synthesizing guaiacol of pyrocatechol and second (first) has two embodiment on the catalyzer in the patent, under the reaction conditions of 553K, pyrocatechol/ethanol=1: 3.44 (mol), and Al
1P
1.1Ti
0.1Si
0.17O
4.79The transformation efficiency of pyrocatechol is 54.2% on the catalyzer, and the selectivity of 2-ethoxy-phenol is 97.2%; Al
1P
1.13Ti
0.1Si
0.17K
0.1O
4.97The pyrocatechol transformation efficiency is 40.1% on the catalyzer, the selectivity of 2-ethoxy-phenol is 98.6%, two kinds of selectivity of forming 2-ethoxy-phenol on the catalyzer are all than higher, but the transformation efficiency of pyrocatechol is lower, catalyzer has preparation method's complexity in this patent in addition, shortcomings such as component is many, and specific surface area is little.
Though catalyzer such as Al-P-O, Al-P-Ti-O, Al-P-Ti-Si-O have better conversion rate and yield, stability can reach about 200h, still has the phenomenon of active decline and carbon deposit.
Summary of the invention
The objective of the invention is to develop the method that a kind of pyrocatechol and ethanol gas solid phase alkylated reaction prepare 2-ethoxy-phenol, use new catalyzer, make building-up reactions have higher transformation efficiency and yield, while has advantages of higher stability again, can solve the phenomenon that has active reduction in ground and carbon deposit in the prior art simultaneously.
Pyrocatechol and ethanol gas solid phase alkylated reaction reaction equation are:
Other by product mainly is the further alkylide of reactant and product
The device that reaction is used as shown in Figure 1,1 nitrogen steel cylinder among the figure, 2 flow stabilizing valves, 3 spinner-type flowmeters, 4 and 7 thermopairs, 5 and 8 reaction tubess, 6 and 10 process furnace, 9 beds, 11 receiving flasks, 12 cold-traps, 13 and 14 temperature programming temperature controllers, 15 SY-04 sampling pumps.
For realizing above purpose, technical scheme of the present invention is:
A kind of method of synthesizing 2-ethoxy-phenol, synthetic by pyrocatechol and ethanol vapor phase alkylation, the composition empirical formula at activity of such catalysts center is Al
1P
kX
hWherein X is Cr, Mg, V or Zr, 0.9≤a≤1.5,0＜b≤0.3, aluminum nitrate is as the aluminium source, phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate or ammonium phosphate are as the phosphorus source, the nitrate of Mg, Cr, zirconium oxychloride, ammonium meta-vanadate are as the raw material of above-mentioned X, pyrocatechol and alcoholic acid reaction are to carry out in fixed-bed reactor, the mol ratio of ethanol and pyrocatechol is 2～7: 1, per hour the mole number by pyrocatechol and catalyzer mole number are 0.05-0.75 by the ratio of Al, and reaction velocity is counted 0.1～1.5h with liquid volume
-1, temperature of reaction is that 533K is to 593K.
The composition empirical formula of the catalyzer that uses in the building-up reactions is Al
1P
aX
b, the wherein preferred Cr of X, Mg, V, Zr promptly the present invention includes the scheme of synthesizing 2-ethoxy-phenol of four kinds of catalyzer of use of optimization.
Scheme one, the preferred Al of catalyzer
1P
aCr
b0.9≤a≤1.5 wherein, 0＜b≤0.3, aluminum nitrate is as the aluminium source, and phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate or ammonium phosphate are as the phosphorus source, and the nitrate of Cr is as the raw material of catalyzer Cr, pyrocatechol and alcoholic acid reaction are to carry out in fixed-bed reactor, the mol ratio of ethanol and pyrocatechol is 2～7: 1, and per hour the mole number by pyrocatechol and catalyzer mole number are 0.05-0.75 by the ratio of Al, and reaction velocity is counted 0.1～1.5h with liquid volume
-1, temperature of reaction is that 533K is to 593K.
Scheme two, the preferred Al of catalyzer
1P
aMg
b0.9≤a≤1.5 wherein, 0＜b≤0.3, aluminum nitrate is as the aluminium source, and phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate or ammonium phosphate are as the phosphorus source, and the nitrate of Mg is as the raw material of catalyzer Mg, pyrocatechol and alcoholic acid reaction are to carry out in fixed-bed reactor, the mol ratio of ethanol and pyrocatechol is 2～7: 1, and per hour the mole number by pyrocatechol and catalyzer mole number are 0.05-0.75 by the ratio of Al, and reaction velocity is counted 0.1～1.5h with liquid volume
-1, temperature of reaction is that 533K is to 593K.。
Scheme three, the preferred Al of catalyzer
1P
aZr
b0.9≤a≤1.5 wherein, 0＜b≤0.3, aluminum nitrate is as the aluminium source, and phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate or ammonium phosphate are as the phosphorus source, and zirconium oxychloride is as the raw material of catalyzer Zr, pyrocatechol and alcoholic acid reaction are carried out in fixed-bed reactor, the mol ratio of ethanol and pyrocatechol is 2～7: 1, and per hour the mole number by pyrocatechol and catalyzer mole number are 0.05-0.75 by the ratio of Al, and reaction velocity is counted 0.1～1.5h with liquid volume
-1, temperature of reaction is that 533K is to 593K.。
Scheme four, the preferred Al of catalyzer
1P
aV
b0.9≤a≤1.5 wherein, 0＜b≤0.3, aluminum nitrate is as the aluminium source, and phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate or ammonium phosphate are as the phosphorus source, and ammonium meta-vanadate is as the raw material of catalyst V, pyrocatechol and alcoholic acid reaction are carried out in fixed-bed reactor, the mol ratio of ethanol and pyrocatechol is 2～7: 1, and per hour the mole number by pyrocatechol and catalyzer mole number are 0.05-0.75 by the ratio of Al, and reaction velocity is counted 0.1～1.5h with liquid volume
-1, temperature of reaction is that 533K is to 593K.
Above-mentioned method for preparing catalyst is as follows among the present invention:
One of the nitrate of aluminum nitrate and Mg, Cr, zirconium oxychloride, ammonium meta-vanadate (wherein ammonium meta-vanadate is dissolved in the water earlier) are dissolved in ethanol, drip in the aqueous solution of phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate or ammonium phosphate, stirred for several hour; The 363K water bath method, 673K is to 1073K roasting 5h.
The catalyzer that the present invention adopts forms simple, and raw material is simple and easy to, and specific surface area is bigger; The characteristics that have high yield, high stability for goal response.
Description of drawings
Fig. 1: reaction unit figure
Embodiment
Embodiment 1:
Preparation of catalysts: catalyzer adopts precipitator method preparation, one of the nitrate of aluminum nitrate and Mg, Cr, zirconium oxychloride, ammonium meta-vanadate (wherein ammonium meta-vanadate is dissolved in the water earlier) are dissolved in ethanol, drip in the aqueous solution of phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate or ammonium phosphate stirred for several hour; The 363K water bath method, 673K is to 1073K roasting 5h.
Embodiment 2
Catalyst A l of the present invention
1P
aX
b(Zr V) is used for the reaction of pyrocatechol and ethanol gas solid phase alkylation synthesizing 2-ethoxy-phenol for X=Mg, Cr.
The device that reaction is used as shown in Figure 1,1 nitrogen steel cylinder among the figure, 2 flow stabilizing valves, 3 spinner-type flowmeters, 4 and 7 thermopairs, 5 and 8 reaction tubess, 6 and 10 process furnace, 9 beds, 11 receiving flasks, 12 cold-traps, 13 and 14 temperature programming temperature controllers, 15 SY-04 sampling pumps.
Temperature of reaction is 533-593K in the reaction, volume space velocity=0.1-1.5h
-1, per hour mole number and the catalyzer mole ratio by pyrocatechol is 0.05-0.75, pyrocatechol is 1/2-1/7 (mol) with the alcoholic acid ratio.
Test result analysis example 1
Table 1,2 and 3 has been listed Al respectively
1P
aX
bPerformance on the catalyzer in the synthesizing 2-ethoxy-phenol reaction.
Table 1Al
1P
1.15X
0.02Performance on the catalyzer in the synthesizing 2-ethoxy-phenol reaction
*
*Reaction conditions: pyrocatechol/ethanol=1/4 (mol), volume space velocity=0.2h
-1, per hour mole number by pyrocatechol and catalyzer mole number (by Al) be than being 0.2, temperature of reaction=553K, reaction times=6h
Table 2Al
1P
0.9X
0.3Performance on the catalyzer in the synthesizing 2-ethoxy-phenol reaction
*
*Reaction conditions: pyrocatechol/ethanol=1/4 (mol), volume space velocity=0.2h
-1, per hour mole number by pyrocatechol and catalyzer mole number (by Al) be than being 0.2, temperature of reaction=553K, reaction times=6h
Table 3Al
1P
1X
0.1Performance on the catalyzer in the synthesizing 2-ethoxy-phenol reaction
*
*Reaction conditions: pyrocatechol/ethanol=1/4 (mol), volume space velocity=0.2h
-1, per hour mole number by pyrocatechol and catalyzer mole number (by Al) be than being 0.2, temperature of reaction=553K, reaction times=6h
Test result analysis example 2
Al when table 4 has provided the different volumes air speed
1P
1.15V
0.02Performance in the synthesizing 2-ethoxy-phenol reaction on the catalyzer:
Table 4 volume space velocity is to Al
1P
1.15V
0.02Effect on Performance in the synthesizing 2-ethoxy-phenol reaction on the catalyzer
*
*Reaction conditions: pyrocatechol/ethanol=1/4 (mol), temperature of reaction=553K, reaction times=6h
Test result analysis example 3
Al when table 5 has provided the differential responses temperature
1P
1.15V
0.02Performance in the synthesizing 2-ethoxy-phenol reaction on the catalyzer:
Table 5 temperature of reaction is to Al
1P
1.15V
0.02Effect on Performance in the synthesizing 2-ethoxy-phenol reaction on the catalyzer
*
*Reaction conditions: pyrocatechol/ethanol=1/4 (mol), volume space velocity=0.2h
-1, per hour mole number by pyrocatechol and catalyzer mole number (by Al) be than being 0.2, reaction times=6h
Test result analysis example 4
Al
1P
aZr
bThe study on the stability of sample in pyrocatechol and the reaction of ethanol synthesizing 2-ethoxy-phenol finds that catalyst stability can reach about 700h, and the accumulation life-span can reach more than the 2000h after regenerating.
Claims (1)
1. the method for a synthesizing 2-ethoxy-phenol is synthetic by pyrocatechol and ethanol vapor phase alkylation, it is characterized in that:
The composition empirical formula at the activity of such catalysts center of using is Al
1P
aX
b, wherein X is Zr, 0.9≤a≤1.5,0＜b≤0.3; The Preparation of catalysts method drips in the aqueous solution of phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate or ammonium phosphate for aluminum nitrate and zirconium oxychloride are dissolved in the ethanolic soln, and stirred for several hour is then through the 363K water bath method, at 673K-1073K roasting 5h;
Pyrocatechol and alcoholic acid reaction are to carry out in fixed-bed reactor, the mol ratio of ethanol and pyrocatechol is 2～7: 1, per hour the mole number by pyrocatechol and catalyzer mole number are 0.05-0.75 by the ratio of Al, and reaction velocity is counted 0.1～1.5h with liquid volume
-1, temperature of reaction is that 533K is to 593K.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110002965B (en) * | 2019-02-21 | 2022-04-19 | 宝鸡文理学院 | Production method of o-hydroxyanisole |
| CN110002966B (en) * | 2019-02-21 | 2022-04-19 | 宝鸡文理学院 | Method for synthesizing o-hydroxyanisole from catechol and methanol |
| CN110002964B (en) * | 2019-02-21 | 2022-04-19 | 宝鸡文理学院 | Method for synthesizing o-hydroxyanisole by catalyzing catechol and methanol |
| CN109879729B (en) * | 2019-02-21 | 2022-04-19 | 宝鸡文理学院 | Method for producing o-hydroxyanisole |
| 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 |
| CN113582820A (en) * | 2021-09-07 | 2021-11-02 | 宁夏沪惠药化科技有限公司 | Synthesis method of m-hydroxyanisole |
| CN115197052B (en) * | 2022-07-29 | 2023-11-03 | 常州大学 | Method for synthesizing o-hydroxyphenylethyl ether by catalyzing hydroxyapatite |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4533758A (en) * | 1982-11-08 | 1985-08-06 | Air Products And Chemicals, Inc. | Alkylation of phenols to alkyl aryl ethers using phosphate catalysts |
-
2006
- 2006-12-21 CN CN200610165509A patent/CN100588640C/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4533758A (en) * | 1982-11-08 | 1985-08-06 | Air Products And Chemicals, Inc. | Alkylation of phenols to alkyl aryl ethers using phosphate catalysts |
Non-Patent Citations (2)
| Title |
|---|
| Al-P-Ti-Si-O体系催化剂上乙醇和邻苯二酚的O－乙基化反应. 李雪梅，张文祥等.高等学校化学学报，第23卷第8期. 2002 |
| Al-P-Ti-Si-O体系催化剂上乙醇和邻苯二酚的O－乙基化反应. 李雪梅，张文祥等.高等学校化学学报，第23卷第8期. 2002 * |
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