CN1057481C - Compound oxide catalyst for synthesizing benzene diphenol by phenol-hydrogen peroxide hydroxylation - Google Patents
Compound oxide catalyst for synthesizing benzene diphenol by phenol-hydrogen peroxide hydroxylation Download PDFInfo
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- CN1057481C CN1057481C CN95119700A CN95119700A CN1057481C CN 1057481 C CN1057481 C CN 1057481C CN 95119700 A CN95119700 A CN 95119700A CN 95119700 A CN95119700 A CN 95119700A CN 1057481 C CN1057481 C CN 1057481C
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- phenol
- hydrogen peroxide
- composite oxide
- oxide catalysts
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Abstract
The present invention belongs to a catalyst for synthesizing dihydroxybenzene by the hydroxylation of phenol-hydrogen peroxide, which is a composite oxide with the structure of AxByOx, wherein A represents metal, rare earth, etc., B represents metal, nonmetal, etc., and O is oxygen; x is from 0 to 3, y is from 0 to 12, and z is a positive number meeting the requirement of valence. A preparation method comprises: mixing the salt or the oxide of relative elements according to mole ratio, roasting at high temperature or adding a complexing agent, a precipitating agent, etc., decomposing at high temperature, grinding and calcining. When the molar ratio of phenol to hydrogen peroxide is 0.5, the conversion rate of phenol can reach 67%. The catalyst has the advantages of simple reaction process, good catalytic performance, low price and practicality.
Description
The present invention relates to composite oxide catalysts, the Preparation of catalysts of synthesizing benzene diphenol by phenol-hydrogen peroxide hydroxylation and used the method for this catalyst synthesizing benzene diphenol.
Pyrocatechol and Resorcinol are the important chemical products, and Application Areas is very extensive.Traditional Process of Hydroquinone Production method has the aniline oxidation style, to diisopropyl benzene method etc.Pyrocatechol is except that from timber tar and useless sulfite solution obtain, also can be by ortho position sulfonation phenol or halogenated phenol obtain.Because the needs of economic aspect and environmental protection aspect, after the seventies, successively released Rhone-Poulenc method, Ube method, Brichima method and Enichem method etc. again, these methods all are raw material with phenol, and hydrogen peroxide is that oxygenant is produced Resorcinol and pyrocatechol simultaneously.Most in the world at present pyrocatechols and 1/3rd above Resorcinol are produced by these 4 kinds of methods, be that the Enichem method of catalyzer is the most advanced wherein with the TS-1 molecular sieve, and caused the great attention of international petroleum chemical circles, some famous major companies are all actively being studied, in the hope of developing the technology of oneself.
More domestic major companies have set about the device of rule scale operation dihydroxy-benzene.But at present domestic still do not have a sophisticated advanced technologies, and introducing advanced is that the Enichem technology possibility of catalyzer is little with the Ts-1 molecular sieve, and its process detail still holds in close confidence in addition, and the introduction expense is surprising.
Because the synthesis technique complexity of molecular sieve usually need be through High Temperature High Pressure, the crystallization cycle needs a couple of days and even tens of days, and necessary template costs an arm and a leg in its building-up process in addition, thereby the catalyzer cost is high; Again because the proportion of molecular sieve is generally less, the industrial separation difficulty, only higher in the rate of recovery, repeating utilization factor just has using value under the situation preferably.Therefore, the cheap practical catalyzer of exploitation is characteristics of the present invention.
The purpose of this invention is to provide and a kind ofly on catalytic performance, can compare favourably, and be better than the practical catalyzer of Enichem technology at aspects such as price, reaction process and catalyst separating with Enichem technology.
The general formula of composite oxide catalysts involved in the present invention is: A
xB
yO
z
In the formula, A can be the metallic element that transition metal (as titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc etc.), basic metal (as sodium, potassium, rubidium etc.), alkaline-earth metal (as beryllium, magnesium, calcium, strontium, barium etc.), rare earth (as lanthanum, cerium, lutetium, yttrium, scandium etc.), heavy metal and other ionic radius are suitable for the corresponding construction requirement, the B position can be metal that transition metal, basic metal, alkaline-earth metal, heavy metal and other ionic radius be suitable for structural requirement, non-metallic element etc., and O is an oxygen.X=0～3, y=0～12, z is the positive number that satisfies each valency requirement, and wherein the element of A position can replace with one or more different element, and also available one or more the different element in B position replaces, as La
2CuO
4, LaCrO
3, LaFeO
3, La
0.8Sr
0.2FeO
3Deng, the mol ratio of its composition should satisfy valent requirement.
Composite oxides involved in the present invention are carried out structural analysis think that related structure should comprise: simple metal oxide compound, spinelle type composite oxides, scheelite type composite oxides, perovskite composite oxide and their analogue thereof etc.Also can be by the impregnating means with on such composite oxide supported or carrier that the aperture is bigger big, as La in certain specific surface area
2O
3/ γ-Al
2O
3Deng.
The basic preparation method of composite oxides involved in the present invention is: the accurate corresponding soluble salt of each element of weighing or can not dissolved salt or oxide compound in molar ratio, and through high-temperature roasting or add complexing agent, precipitation agent after pyrolytic decomposition, grinding, roasting form.Such catalyzer also can be synthetic by artificial power such as High Temperature High Pressure or natural power.
Controlling suitable roasting time and maturing temperature is to guarantee that catalyzer has highly active key; When needs satisfy certain intermediate valence attitude, should be taken into account roasting in inert atmosphere, reducing atmosphere or vacuum.
High temperature range was 100～200 ℃ when High Temperature High Pressure was synthetic, and high pressure is the autogenous pressure after airtight.
The method of catalysis of phenol hydroxylation with hydrogen peroxide synthesizing benzene diphenol involved in the present invention is that to be that catalyzer carries out catalytic with composite oxides.Catalytic process is a liquid and solid phase reaction, is solvent with organism or water, is oxygenant with 30% hydrogen peroxide.Oxygenant can inject reaction system disposable or gradually.30～80 ℃, synthesis under normal pressure 1～10 hour.Said solvent should comprise acetonitrile, acetate, ethanol, acetone, methyl alcohol, formic acid, dimethyl formamide, trichloromethane, ethylene dichloride, dioxane, tetrahydrofuran (THF), water etc.
It is rather important to the generation that reduces tar to inject hydrogen peroxide gradually by micro pump.
The oxygenant of catalysis of phenol hydroxylation with hydrogen peroxide synthesizing benzene diphenol is 30% a commercially available hydrogen peroxide, and injection length is 0～10 hour, and reaction system is controlled by super constant temperature trough, and its temperature error is less than ± 0.2 ℃.
The present invention finds through repeatedly adopting differing temps, differential responses time, different catalysts amount and different phenol/hydrogen peroxide mol ratios etc. to carry out condition experiment, at phenol: during hydrogen peroxide (30%)=2 (mol ratio), the peak rate of conversion of its phenol (calculating by the phenol amount that drops into) can reach 30%, and the dihydroxy-benzene selectivity surpasses 90% (wherein pyrocatechol is 1: 1～1.5: 1 with the ratio of Resorcinol); If when reducing the mol ratio (as phenol/hydrogen peroxide=0.5) of phenol and hydrogen peroxide, then phenol conversion can reach 67%.
Product analysis of the present invention is finished on the temperature programming capillary gas chromatograph, separates with 14.5 meters～0.23 millimeter XE-60 elasticity glass capillary column.Sample size during analysis is 0.2 μ L, and the correction factor of corresponding product is: pyrocatechol 1.8809, Resorcinol 2.1088, benzoquinones 1.3840 (all with respect to phenol).Do not contain Resorcinol in the product of the present invention.
Example 1: lanthanum nitrate, strontium nitrate and the iron nitrate of getting metering, its water-soluble back is added the oxalic acid that measures, behind evaporate to dryness in the water-bath, put into baking oven, in 120 ℃ of oven dry, grind the back and decompose, after fully grinding, put into 850 ℃ of roastings of retort furnace 5 hours again in 400 ℃ of blowing airs.
Get 50 milligrams of the catalyzer made, add that to be warming up to reaction behind the solvent temperature required, treat to add in molar ratio after the homo(io)thermism phenol and the hydrogen peroxide of metering, the sealing eudiometer.Read the decomposition amount of hydrogen peroxide after the reaction some time, and carry out product analysis.
Example 2. is got 50 milligrams of La
2O
3, be warming up to 70 ℃ behind the adding solvent, the phenol of adding metering and hydrogen peroxide (mol ratio of phenol and hydrogen peroxide is 2: 1) afterreaction 5 hours.Find that through the product analysis phenol conversion is 19.91%, pyrocatechol and Resorcinol selectivity are respectively 62.44%, 34.69%.
Example 3. is got 50 milligrams of La
2O
3/ γ-Al
2O
3, be warming up to 70 ℃ behind the adding solvent, the phenol of adding metering and hydrogen peroxide (mol ratio of phenol and hydrogen peroxide is 2: 1) afterreaction 5 hours.Find that through the product analysis phenol conversion is 22.03%, pyrocatechol and Resorcinol selectivity are respectively 60.69%, 36.63%.
Example 4. is got 50 milligrams of La
2CuO
4, be warming up to 70 ℃ behind the adding solvent, the phenol of adding metering and hydrogen peroxide (mol ratio of phenol and hydrogen peroxide is 2: 1) afterreaction 5 hours.Find that through the product analysis phenol conversion is 24.08%, pyrocatechol and Resorcinol selectivity are respectively 57.46%, 40.04%.
Example 5. is got 50 milligrams of La
2CrO
3, be warming up to 70 ℃ behind the adding solvent, the phenol of adding metering and hydrogen peroxide (mol ratio of phenol and hydrogen peroxide is 2: 1) afterreaction 5 hours.Find that through the product analysis phenol conversion is 18.13%, pyrocatechol and Resorcinol selectivity are respectively 58.86%, 37.00%.
Example 6. is got 50 milligrams of La
2FeO
3, be warming up to 70 ℃ behind the adding solvent, the phenol of adding metering and hydrogen peroxide (mol ratio of phenol and hydrogen peroxide is 2: 1) afterreaction 5 hours.Find that through the product analysis phenol conversion is 10.43%, pyrocatechol and Resorcinol selectivity are respectively 54.63%, 39.99%.
Example 7. is got 50 milligrams of La
0.8Sr
0.2FeO
3, be warming up to 70 ℃ behind the adding solvent, the phenol of adding metering and hydrogen peroxide (mol ratio of phenol and hydrogen peroxide is 2: 1) afterreaction 5 hours.Find that through the product analysis phenol conversion is 9.70%, pyrocatechol and Resorcinol selectivity are respectively 53.06%, 41.78%.
Example 8: press the preparation method in the example 1, the preparation catalyst series, getting wherein, catalytic activity the higher person carries out condition experiment.Catalytic result when table 1 is different phenol/hydrogen peroxide mol ratio.
Hydroxylation activity when different phenol of table 1 and hydrogen peroxide mol ratio
*
1: 21: 12: 13: 14: 1 phenol conversions (%) of mol ratio, 66.69 47.03 29.95 16.53 10.88 pyrocatechol selectivity (%), 61.58 59.22 57.63 56.87 59.78 Resorcinol selectivity (%) 37.37 37.96 37.58 38.42 33.82
* temperature of reaction is 70 ℃, 5 hours reaction times.
By table 1 as seen, during the mol ratio at phenol and hydrogen peroxide among the present invention lower (1: 2), the transformation efficiency of phenol can reach 67%, and is 2: 1 o'clock in the mol ratio of phenol and hydrogen peroxide, and phenol conversion can reach 30%; Even in lower mol ratio, still can reach 16% as 3: 1 o'clock phenol conversions.
Example 9: adopting the catalyzer described in the example 8, is 2: 1 o'clock in the mol ratio of phenol and hydrogen peroxide, and other condition is constant, only changes temperature of reaction, the results are shown in table 2.
The hydroxylation active reaction temperature of phenol under table 2 differing temps/℃ 30 40 50 60 70 phenol conversions (%) 23.32 24.96 25.73 27.61 29.95 pyrocatechol selectivity (%) 63.11 62.34 60.56 59.97 57.63 Resorcinol selectivity (%) 28.83 34.38 36.14 36.30 37.58
Example 10: adopting the catalyzer in the example 8, is 2: 1 (other condition is with table 1) in the mol ratio of phenol and hydrogen peroxide, the change catalytic amount, and reaction result is shown in table 3.
The hydroxylation active catalyst of phenol during table 3 different catalysts amount/phenol wt% 1.0 2.5 5.0 7.5 10.0 phenol conversions (%) 28.18 29.88 29.95 29.83 30.05 pyrocatechol selectivity (%) 59.59 57.78 57.63 57.29 55.28 Resorcinol selectivity (%) 37.31 39.44 37.58 39.24 40.08
Example 11: keep the condition in the example 8, investigate the differential responses time, the results are shown in table 4 to the active influence of hydroxylation.
The table 4 differential responses time is to the active influence of hydroxylation
Reaction times/h 1234568
Phenol conversion (%) 25.90 27.31 28.13 28.88 29.95 29.11 30.30 pyrocatechol selectivity (%) 60.02 59.37 60.17 58.19 57.63 59.16 60.52 Resorcinol selectivity (%) 35.00 36.13 35.17 38.35 37.58 35.87 35.21
Claims (7)
1. the reoxygenation joint compound catalyzer of a catalysis of phenol hydroxylation with hydrogen peroxide synthesizing benzene diphenol, its essentially consist is:
A
xB
yO
z
In the formula, A is transition metal La, and B is Cu, Cr, Sr, Fe element or two kinds of different elements in them, and O is an oxygen, x=0～3, and y=0～12, z is the positive integer that satisfies the valency requirement.
2. according to the described composite oxide catalysts of claim 1, it is characterized in that said B position is Fe, it basic composition is La
0.8Sr
0.2FeO
3
3. according to claim 1 or 2 described composite oxide catalysts, it is characterized in that, composite oxides consist of La
2O
3, i.e. x=2, y=0, z=3, and load on γ-Al
2O
3On the carrier.
4. the preparation method of the composite oxide catalysts of a claim 1 is, the soluble salt of weighing La and Cu, Cr, Sr, Fe or insolubility salt or oxide compound are raw material in molar ratio, mix the back and add complexing agent or precipitation agent, make product through pyrolytic decomposition, grinding, roasting.
5. according to the preparation method of the described composite oxide catalysts of claim 4, it is characterized in that, said raw material is lanthanum nitrate, strontium nitrate, iron nitrate, their water-soluble backs are added oxalic acid, solvent evaporated after the generation co-precipitation, put into baking oven in 120 ℃ of oven dry, grind the back and decompose, after grinding, put into retort furnace again in 850 ℃ of roastings 5 hours in 400 ℃ of blowing airs.
6. the method for a phenol hydroxylation synthesizing benzene diphenol is, in liquid-solid phase system, finish reaction, with organism or water is solvent, with the hydrogen peroxide is that oxygenant is produced dihydroxy-benzene, it is characterized in that having used composite oxide catalysts, put it in the solvent, stir fast behind adding phenol and the hydrogen peroxide; Oxygenant can be injected or disposable adding reaction system gradually by micro pump, and at 30～80 ℃, normal pressure reacted 1～10 hour down.
7. by the method for the phenol hydroxylation synthesizing benzene diphenol described in the claim 6, it is characterized in that said concentration of hydrogen peroxide is 30%, the temperature error by super constant temperature trough control reaction system is in 0.2 ℃, and the injection length of oxygenant is 0～10 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95119700A CN1057481C (en) | 1995-12-16 | 1995-12-16 | Compound oxide catalyst for synthesizing benzene diphenol by phenol-hydrogen peroxide hydroxylation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95119700A CN1057481C (en) | 1995-12-16 | 1995-12-16 | Compound oxide catalyst for synthesizing benzene diphenol by phenol-hydrogen peroxide hydroxylation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1134313A CN1134313A (en) | 1996-10-30 |
| CN1057481C true CN1057481C (en) | 2000-10-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95119700A Expired - Fee Related CN1057481C (en) | 1995-12-16 | 1995-12-16 | Compound oxide catalyst for synthesizing benzene diphenol by phenol-hydrogen peroxide hydroxylation |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085115C (en) * | 1998-03-10 | 2002-05-22 | 北京燕山石油化工公司研究院 | Compound oxide catalyst for phenol hydroxylation and its preparing method |
| CN1064647C (en) * | 1998-03-18 | 2001-04-18 | 吉林大学 | Catalyst for clean catalytic oxidation of arene and its preparation |
| CN1096293C (en) * | 2000-05-24 | 2002-12-18 | 中国石油化工集团公司 | Phenyl hydroxylating catalyst |
| CN1130258C (en) * | 2000-06-15 | 2003-12-10 | 中国石油化工集团公司 | Catalyst for preparing benzene diphenol by means of oxidation of phenol |
| CN1130259C (en) * | 2000-06-15 | 2003-12-10 | 中国石油化工集团公司 | Catalyst for preparing benzene diphenol by means of direct oxidation of phenol |
| DE202008017277U1 (en) * | 2008-11-30 | 2009-04-30 | Süd-Chemie AG | catalyst support |
| CN102924485A (en) * | 2011-08-12 | 2013-02-13 | 合肥师范学院 | 1,10-phenanthroline metal complex of different scales, and preparation method and use thereof |
| CN103028411B (en) * | 2013-01-07 | 2014-06-25 | 南京尊龙化工有限公司 | Novel N-methyl aniline catalyst synthesized through chromium-free gas phase method |
| CN107597173B (en) * | 2017-10-11 | 2020-07-21 | 中国天辰工程有限公司 | Catalyst for synthesizing benzenediol by phenol hydroxylation and preparation method thereof |
| CN112237935B (en) * | 2020-09-10 | 2022-07-12 | 万华化学集团股份有限公司 | Catalyst for treating peroxide-containing wastewater and preparation and application methods thereof |
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1995
- 1995-12-16 CN CN95119700A patent/CN1057481C/en not_active Expired - Fee Related
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