CN1481935A - Accelerating agent and its application in synthesizing carbolic acid using benzene and hydrogen dioxide - Google Patents

Accelerating agent and its application in synthesizing carbolic acid using benzene and hydrogen dioxide Download PDF

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Publication number
CN1481935A
CN1481935A CNA021329087A CN02132908A CN1481935A CN 1481935 A CN1481935 A CN 1481935A CN A021329087 A CNA021329087 A CN A021329087A CN 02132908 A CN02132908 A CN 02132908A CN 1481935 A CN1481935 A CN 1481935A
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catalyst
benzene
carrier
hydrogen peroxide
reaction
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CN100443172C (en
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杰 徐
徐杰
高肖汉
冯美宽
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Inner Mongolia Hangjinqi Hengyi Construction Co ltd
Dalian Institute of Chemical Physics of CAS
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Inner Mongolia Hangjinqi Hengyi Construction Co ltd
Dalian Institute of Chemical Physics of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The present invention relates to one kind of catalyst and its preparation in the synthesis reaction of benzene and hydrogen peroxide to produce phenol. The catalyst has carrier of natural red clay and active component comprising one or several oxides of V, Mn, Cu, W, Mo, Cr, Co, Fe, etc. The preparation process includes dissolving the oxalate, nitrate or acid ammonium salt of the metal(s) in solvent, adding carrier, soaking, stoving, grinding, high temperature decomposing and calcination. The catalyst is used in the synthesis reaction of benzene and hydrogen peroxide to produce phenol.

Description

A kind of catalyst and the application in benzene and the reaction of hydrogen peroxide synthesizing phenol
Technical field
The present invention relates to the application in benzene and the reaction of hydrogen peroxide synthesizing phenol of a kind of catalyst and this catalyst, process conditions and process that this catalyst has related to carrier, the Preparation of catalysts of catalyst and used this catalyst synthesizing phenol.
Background technology
Phenol is a kind of important, basic Organic Chemicals, can be used for producing chemical products and intermediates such as phenolic resins, bisphenol-A, caprolactam.Phenol has important purposes in industrial production such as industrial chemicals, synthetic fibers, plastics, synthetic rubber, medicine, agricultural chemicals, coating, dyestuff and oil refining.In addition, can also be used as solvent, experiment reagent and disinfectant.2000 in the world the output of phenol reach 6,600,000 tons.
The commercial run of the existing production of phenol mainly is a cumene method, and 90% phenol is produced by the method in the world.This method is the technical process of a multistep reaction.In the decomposable process of intermediate product dicumyl peroxide, used the concentrated sulfuric acid, existed the danger and the serious environmental problem of blast, and the economic benefit of production phenol depends on the utilization ratio of accessory substance-acetone as catalyst.As starting point, must to develop the process route of a direct synthesizing phenol of benzene with the angle of economy, the energy and environment.
Domestic and international research mainly is divided three classes: N 2O hydroxylating method, H 2O 2Hydroxylating method and O 2(air) hydroxylating method.
Nineteen eighty-three, (J.Phys.Chem.1983 87:903-905) at first proposes with N people such as Japanese scholar Iwamoto 2O under catalyst action, generates phenol with benzene direct oxidation in gas phase as oxidant.People (WO9527691,1994 such as Kharitonov A S; US5756861,1998; J, Catal, 1993,139:435-443) the ZSM-5 molecular sieve that adopts the iron modification is as catalyst, fixed bed reactors, temperature is in the time of 400 ℃, and the conversion ratio of benzene is 50.3%, and the selectivity of phenol reaches 87.8%.
Document (J.Catal, 1991,131:294-297; J.Catal, 1994,146:476-482) and patent (US5233097,1993; US5569791,1996) etc. report is with H 2O 2Be oxidant, under the effect of catalyst, benzene and hydrogen peroxide synthesizing phenol, wherein in the US5233097 patent, the conversion ratio of benzene reaches 92%, and the selectivity of phenol is up to 97%.
Document (J.Catal.1995,155:158-162:J.Mol.Catal, 1997,120:149-154) report is an oxygen source with oxygen, the modification heteropoly acid is a catalyst, in liquid phase or gas phase the benzene oxidation is generated phenol, people such as Niwa (Science, 2002,295:105-107) with the palladium film as catalyst, logical benzene, oxygen and helium on one side of film, logical hydrogen of another side and helium, the conversion ratio of benzene is 2%-16%, and selectivity is 80%-97%.
With the hydrogen peroxide is oxidant, the reaction condition gentleness, and selectivity height, accessory substance mainly are water, are eco-friendly synthetic routes.The used catalyst of the method mainly is HTS (TS), it costs an arm and a leg, proportion is little, the industrial separation difficulty, only at the catalyst recovery yield height, the situation that recycling rate of waterused is good just has the value of application, therefore, need one of exploitation cheap, easily reclaim the catalyst that can reuse.
Summary of the invention
The object of the present invention is to provide a kind of catalyst carrier, is to utilize natural mineral, through after the character that processing to change natural clay as the carrier of catalyst.
Another object of the present invention is to provide a kind of catalyst, is carrier with the natural clay after the modification, as active component, makes it have cheap, simple, the eco-friendly characteristics of preparation with metal oxide.
Another purpose of the present invention is to provide a kind of above-mentioned Preparation of catalysts method.
Another purpose of the present invention is the process that above-mentioned catalyst is used for benzene direct oxidation synthesizing phenol.
Carrier provided by the present invention is to be formed by the special red clay modification of a kind of performance, and this clay originates in Hangjin Banner western part, the Inner Mongol, and its source is abundant, 1,000,000,000 tons of prospective reserves.Contain quartz in this clay, feldspar, calcite, illite, ores such as attapulgite, its chemical composition mainly is a sial, contains a certain amount of rare earth element.Utilize after the domestic natural ore deposit land reform carrier, have great importance for exploitation and the natural resources that make full use of China as catalyst.Its preparation method is following several mode: (1) after sulfuric acid solution soaked a period of time, suction filtration was dried, and grinds with natural clay.
(2), and then handle drying with sulfuric acid solution with the natural clay high-temperature calcination.
(3) natural clay is handled with sulfuric acid solution, and then high-temperature calcination.
The concentration of above-mentioned sulfuric acid solution is 0.1-5mol/l, calcining heat between 500 ℃-1000 ℃, the concentration 0.2-0.5mol/l of preferably sulfuric acid, 600 ℃-900 ℃ of calcining heats.
The invention provides a kind of catalyst, is carrier with the natural red clay of modification, and metal oxide is formed as activity, its active component is by vanadium, manganese, copper, tungsten, molybdenum, chromium, cobalt, one or more compositions in the oxide of iron etc., its loading is 0.1%-15%, preferred 1.0%-7.5% (in metal w%).Its preparation method is: according to the corresponding oxalates of each metal of the accurate weighing of percentage by weight, the acid ammonium salt of nitrate or this metal, be dissolved in the solvent, add carrier, make it to become pasty state, at room temperature dry, certain temperature is dried in baking oven again, grind, certain temperature more than the decomposition temperature of the corresponding salt of metal institute is calcined a period of time, makes it to become oxide.The bake out temperature in the above-mentioned Preparation of Catalyst and the temperature of calcining all adopt current techique.
The method of a kind of benzene and hydrogen peroxide catalyzed synthesizing phenol, adopt above-mentioned catalyst synthetic, its catalytic process is a liquid and solid phase reaction, with the glacial acetic acid is solvent, hydrogen peroxide with 10%-50% is a hydroxylating agent, preferred 25%-35%, and hydrogen peroxide slowly adds in the reaction system by dropping funel, at 20 ℃-80 ℃, synthesis under normal pressure 2-12 hour.Its preferable reaction temperature is 30 ℃-60 ℃, and the reaction time is 4-8 hour.
The rate of addition of hydrogen peroxide has very big influence for product selectivity, and rate of addition is too fast, and the concentration of the hydrogen peroxide of reaction system is big, generates benzoquinones easily, and the selectivity of phenol will reduce.
The present invention can increase the intersolubility of benzene and hydrogen peroxide owing to use acetate as solvent, and can be in certain scope their ratio of modulation.Accessory substance mainly is a benzoquinones, only occurs diphenol in a few experiments.
Product analysis of the present invention is to finish at the capillary gas chromatograph of temperature programming, separates with the OV-1 capillary column of 35m～0.32mm, and sample size is 0.5 μ L, adopts internal standard method, utilizes working curve accurately to obtain the content of phenol in the reactant liquor.
The specific embodiment
Below by embodiment in detail the present invention is described in detail:
Example 1: preparation carrier
Take by weighing the natural red clay of 50.0g, soak a period of time with the sulfuric acid solution of the 0.25mol/l of 150ml after, suction filtration, oven dry is ground the back as carrier.
Example 2: preparation carrier
Natural red clay 800 ℃ of calcinings, is handled the back as carrier under the condition identical with example 1.
Example 3: the preparation of vanadium containing catalysts
Taking by weighing 1.50g oxalic acid/citric acid is dissolved in the 15ml water, low-grade fever, take by weighing the 1.50g ammonium metavanadate again, be dissolved in above-mentioned solution, the dissolving back adds the 20.00g carrier fully, make it thorough impregnation and become pasty state, at room temperature dry in the air to half-dried,, grind then in drying in oven, at 800 ℃ of calcining finished products, loading is 10% (in the w% of vanadium).
Example 4: the preparation of Cu-contained catalyst
Take by weighing the 3.82g copper nitrate and be dissolved in the water of metering, add the 10.00g carrier, thorough impregnation becomes pasty state, at room temperature dries in the air to half-dried, then in drying in oven, grinds, and at 500 ℃ of calcining finished products, loading is 10% (in the w% of copper).
Example 5: benzene and hydrogen peroxide synthesizing phenol
Take by weighing 1.00g catalyst T-Cu-A, add benzene and acetate, mechanical agitation, heat temperature raising is to certain temperature, begin to drip the hydrogen peroxide (mol ratio of benzene and hydrogen peroxide is 1/1.8) of metering, dripped off afterreaction 4 hours, the product analysis result: the conversion ratio of benzene is 5.9%, phenol selectivity 95.0%.
Example 6: benzene and hydrogen peroxide synthesizing phenol
With example 5 identical conditions under, use catalyst T-Mn-A instead, the product analysis result is: the conversion ratio of benzene is 5.9%, phenol selectivity 80.7%.
Example 7: benzene and hydrogen peroxide synthesizing phenol
With example 5 identical conditions under, use catalyst T-V-B instead, the product analysis result: the conversion ratio of benzene is 7.6%, phenol selectivity 90.4%.
Example 8: metal oxide loading difference is to the evaluation of catalyst
According to the preparation method in the example 3, preparation catalyst series (the loading difference of vanadium), with example 5 identical conditions under, investigate the influence of loading, and compared two kinds of carrier: A-and directly used carrier loaded; B-handles back loading with sulfuric acid solution.Analysis result such as following table 1:
By table 1 as seen, the loading of two kinds of carriers was at 2.5% o'clock, and conversion ratio is the highest, and is higher with the carrier activity of sulfuric acid treatment, is labeled as T-V-B-2.5%.
The influence of the loading of table 1 vanadium
Carrier Loading Conversion ratio Selectivity
????A ??15.0％ ????3.0％ ????87.5％
????A ??10.0％ ????5.9％ ????88.8％
????A ??7.5％ ????9.7％ ????89.1％
????A ??5.0％ ????8.6％ ????94.5％
????A ??3.0％ ????9.5％ ????94.8％
????A ??2.5％ ????10.9％ ????96.3％
????A ??2.0％ ????8.9％ ????96.2％
????A ??1.0％ ????9.3％ ????98.8％
????A ??0.1％ ????2.0％ ????99.1％
????B ??15.0％ ????4.5％ ????88.5％
????B ??10.0％ ????7.6％ ????90.4％
????B ??7.5％ ????10.7％ ????91.0％
????B ??5.0％ ????10.7％ ????90.6％
????B ??3.0％ ????10.5％ ????93.0％
????B ??2.5％ ????12.1％ ????92.8％
????B ??2.0％ ????10.4％ ????94.8％
????B ??1.0％ ????10.2％ ????98.9％
????B ??0.1％ ????3.5％ ????99.4％
Example 9: temperature is to the influence of benzene and the reaction of hydrogen peroxide synthesizing phenol
Take by weighing 1.00g catalyst T-V-B-2.5%, add benzene and acetate, mechanical agitation, after heating rose to different temperatures, the hydrogen peroxide (mol ratio of benzene and hydrogen peroxide is 1/1.8) that begins to drip metering dripped off afterreaction 4 hours, analysis result such as table 2:
By table 2 as seen: when temperature during greater than 40 ℃, conversion ratio increases not obvious, and selectivity also has a declining tendency, and mainly is the temperature height, and the peroxidating degree increases; When being lower than 40 ℃, conversion ratio and selectivity all descend, so the optimum temperature of reaction should be 40 ℃.
Table 2 Temperature Influence
Temperature Conversion ratio Selectivity
????20℃ ????4.9％ ????86.1％
????25℃ ????6.9％ ????83.8％
????30℃ ????11.6％ ????87.8％
????40℃ ????12.1％ ????92.8％
????50℃ ????12.7％ ????88.2％
????60℃ ????13.3％ ????88.1％
Example 10: catalyst amount is to the influence of synthetic phenol reactant
Take by weighing the catalyst T-V-B-2.5% of different amounts, add benzene and acetate, mechanical agitation, after heating rose to 40 ℃, the hydrogen peroxide (mol ratio of benzene and hydrogen peroxide is 1/1.8) that begins to drip metering dripped off afterreaction 4 hours, analysis result such as table 3:
Can be reached a conclusion by table 3: under the same conditions, when catalyst consumption was 0.25 gram (benzene that is equivalent to 1 gram catalyst, 17.6 grams), when being lower than 0.20 gram, the conversion ratio of benzene descended.During greater than 0.25 gram, the conversion ratio of benzene changes little.
The influence of table 3 catalyst amount
Catalyst consumption Conversion ratio Selectivity
????1.00g ????12.1％ ????92.8％
????0.50g ????12.6％ ????91.9％
????0.35g ????12.6％ ????92.3％
????0.25g ????12.1％ ????93.8％
????0.20g ????11.8％ ????91.6％
????0.10g ????9.8％ ????94.1％
????0.05g ????3.4％ ????94.3％
????0 Trace
Example 11: the different mol ratio of benzene and hydrogen peroxide is to the influence of reaction
Take by weighing 0.25 gram catalyst T-V-B-2.5%, add benzene and acetate, mechanical agitation, heat to 40 ℃ after, the hydrogen peroxide (benzene is different with the mol ratio of hydrogen peroxide) that begins to drip metering dripped off afterreaction 4 hours, analysis result such as table 4:
As can be seen from Table 4, the preferable mol ratio of benzene and hydrogen peroxide is 1/1.4, and the amount of hydrogen peroxide increases, and the conversion ratio of benzene increases not obvious.
The influence of table 4 rate of charge
Rate of charge benzene/hydrogen peroxide (mol) Conversion ratio Selectivity
????1/2.2 ???12.2％ ??97.3％
????1/1.8 ???12.1％ ??93.8％
????1/1.4 ???12.8％ ??93.4％
????1/0.9 ???10.9％ ??91.6％
????1/0.5 ???5.4％ ??88.5％
Example 12: the catalyst of different disposal method preparation is to the influence of synthetic phenol reactant
According to the preparation method in the example 3, the clay of modifying with three kinds of distinct methods of A, B, C is as carrier, and the loading of vanadium is 2.5% preparation catalyst, with the example 11 identical modification effect of carrier relatively down that reacts completely, analysis result such as table 5:
A-supports after handling with sulfuric acid solution
Support again after the high-temperature calcination of B-elder generation
Support again with the sulfuric acid solution processing after the C-high-temperature calcination
The influence of table 5 carrier
Carrier modification Conversion ratio Selectivity
????A ????12.8％ ????93.4％
????B ????10.2％ ????91.5％
????C ????13.4％ ????93.6％

Claims (8)

1. oxidation catalyst, it is characterized in that the natural red clay with modification is a carrier, metal oxide is as active component, its active component is made up of in the oxide of vanadium, manganese, copper, tungsten, molybdenum, chromium, cobalt and iron one or more, in weight metal, its loading is 0.1%-15%.
2. catalyst as claimed in claim 1 is characterized in that: the loading of catalyst is 1.0%-7.5%.
3. described Preparation of catalysts method of claim 1: the acid ammonium salt of oxalates, nitrate or this metal of metal is dissolved in solvent, adds carrier, by dipping, oven dry, grinding, pyrolytic, the calcining finished product.
4. the special carrier of the described catalyst of claim 1 is characterized in that being prepared from by the following stated method: a kind of natural red clay, handle and/or carrier is made in high-temperature calcination through persulfate solution.
5. catalyst carrier as claimed in claim 4, the concentration that it is characterized in that described sulfuric acid solution is 0.1-5mol/l, calcining heat is between 500 ℃-1000 ℃.
6. catalyst carrier as claimed in claim 5, the concentration that it is characterized in that described sulfuric acid is 0.2-0.5mol/l, calcining heat is 600 ℃-900 ℃.
7. the described catalyst of claim 1 is used for the reaction of benzene and hydrogen peroxide synthesizing phenol, it is characterized in that this reaction makees solvent with acetate, temperature is between 20 ℃-80 ℃, and the reaction time is 2-12 hour, normal pressure is the oxidant synthesizing phenol with the hydrogen peroxide of 10%-50%.
8. catalyst as claimed in claim 7 is used for the reaction of benzene and hydrogen peroxide synthesizing phenol, it is characterized in that its reaction temperature is 30 ℃-60 ℃, and the reaction time is 4-8 hour.
CNB021329087A 2002-09-11 2002-09-11 Accelerating agent and its application in synthesizing carbolic acid using benzene and hydrogen dioxide Expired - Fee Related CN100443172C (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100337745C (en) * 2005-02-01 2007-09-19 中国科学院长春应用化学研究所 Catalytic system for direct oxidizing benzene into phenol with hydrogen peroxide
CN101362098B (en) * 2007-08-09 2010-12-08 黑龙江大学 Vanadium-loading catalyst capable of oxidizing the benzene to phenol using hydrogen peroxide as oxidant, preparation method and use thereof
CN101612586B (en) * 2008-06-25 2011-06-29 中国科学院大连化学物理研究所 Zeolite catalyst, preparation and application thereof
CN101822996B (en) * 2009-03-04 2012-07-18 中国石油天然气股份有限公司 Catalyst composition for reducing sulfur content of gasoline and preparation method thereof
CN101733098B (en) * 2008-11-07 2012-08-08 中国石油天然气股份有限公司 Catalyst for preparing phenol by benzene hydroxylation and preparation method and application thereof
CN110871085A (en) * 2018-08-30 2020-03-10 淄博张店东方化学股份有限公司 Supported catalyst for preparing furfuryl alcohol by catalytic hydrogenation of furfural and preparation method and application thereof
CN111116321A (en) * 2020-01-21 2020-05-08 山东理工大学 Green synthesis method for preparing phenol by benzene hydroxylation
CN112371112A (en) * 2020-11-11 2021-02-19 兰州理工大学 Preparation method of novel catalyst for preparing phenol by benzene hydroxylation

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1060970C (en) * 1996-07-18 2001-01-24 吉林大学 Process for preparing aromatic hydrocarbon oxidation catalyst

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100337745C (en) * 2005-02-01 2007-09-19 中国科学院长春应用化学研究所 Catalytic system for direct oxidizing benzene into phenol with hydrogen peroxide
CN101362098B (en) * 2007-08-09 2010-12-08 黑龙江大学 Vanadium-loading catalyst capable of oxidizing the benzene to phenol using hydrogen peroxide as oxidant, preparation method and use thereof
CN101612586B (en) * 2008-06-25 2011-06-29 中国科学院大连化学物理研究所 Zeolite catalyst, preparation and application thereof
CN101733098B (en) * 2008-11-07 2012-08-08 中国石油天然气股份有限公司 Catalyst for preparing phenol by benzene hydroxylation and preparation method and application thereof
CN101822996B (en) * 2009-03-04 2012-07-18 中国石油天然气股份有限公司 Catalyst composition for reducing sulfur content of gasoline and preparation method thereof
CN110871085A (en) * 2018-08-30 2020-03-10 淄博张店东方化学股份有限公司 Supported catalyst for preparing furfuryl alcohol by catalytic hydrogenation of furfural and preparation method and application thereof
CN110871085B (en) * 2018-08-30 2022-11-29 淄博张店东方化学股份有限公司 Supported catalyst for preparing furfuryl alcohol by catalytic hydrogenation of furfural and preparation method and application thereof
CN111116321A (en) * 2020-01-21 2020-05-08 山东理工大学 Green synthesis method for preparing phenol by benzene hydroxylation
CN111116321B (en) * 2020-01-21 2023-01-03 山东理工大学 Green synthesis method for preparing phenol by benzene hydroxylation
CN112371112A (en) * 2020-11-11 2021-02-19 兰州理工大学 Preparation method of novel catalyst for preparing phenol by benzene hydroxylation

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