CN101612594A - A kind of method of preparing supported iron-based composite catalyst by dipping method - Google Patents

A kind of method of preparing supported iron-based composite catalyst by dipping method Download PDF

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Publication number
CN101612594A
CN101612594A CN200810115728A CN200810115728A CN101612594A CN 101612594 A CN101612594 A CN 101612594A CN 200810115728 A CN200810115728 A CN 200810115728A CN 200810115728 A CN200810115728 A CN 200810115728A CN 101612594 A CN101612594 A CN 101612594A
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carrier
phenol
based composite
catalyst
active component
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张敬畅
张小亮
曹维良
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Beijing University of Chemical Technology
Hainan Institute of Science and Technology
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Beijing University of Chemical Technology
Hainan Institute of Science and Technology
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Abstract

A kind of method of preparing supported iron-based composite catalyst by dipping method belongs to the organic chemistry synthesis technical field.The manufacturing cycle of existing supported iron-based composite catalyst is long, and catalysis of phenol synthesizing benzene diphenol productive rate is not high.The present invention is by after flooding 5-20min with catalyst carrier in the solution that contains active component presoma and surfactant, dry and in 400-900 ℃ of calcining 1-10h, obtains supported iron-based composite catalyst; Described catalyst carrier is γ-Al 2O 3, diatomite, sepiolite or zeolite molecular sieve; Described active component presoma is nitrate; Described surfactant is tartaric acid, AEO3, AEO9 or EDTA.The inventive method manufacturing cycle is short, catalysis of phenol synthesizing benzene diphenol productive rate height, and easy and product separation.

Description

A kind of method of preparing supported iron-based composite catalyst by dipping method
Technical field
The invention belongs to the organic chemistry synthesis technical field, be specifically related to a kind of method of preparing supported iron-based composite catalyst by dipping method.
Background technology
Adjacent, hydroquinones is crucial organic intermediate, and hydrogen peroxide oxidation phenol prepares benzenediol, because of its inexpensive to the close friend of environment and raw material, becomes the most rising benzenediol production technology of 21 century.Hydrogen peroxide oxidation phenol prepares the benzenediol reaction, be in fact hydrogen peroxide Pyrogentisinic Acid's in the presence of catalyst hydroxylating, so the choice and application of catalyst is the key of this technology.
Being applied to hydrogen peroxide oxidation phenol at present prepares the benzenediol catalyst for reaction and mainly contains: molecular sieve, composite metal oxide and loaded catalyst and metal-organic complex etc. that hetero atom replaces.Wherein, supported iron-based composite catalyst is higher because of catalytic activity, cheap and have very big commercial development advantage, but make because of this catalyst adopts coprecipitation, exist manufacturing cycle long, the process complexity, can't guarantee the co-precipitation of all active components, active component easily runs off, and catalysis of phenol synthesizing benzene diphenol productive rate is not high, the shortcoming of separating with the product difficulty.
Summary of the invention
The objective of the invention is to solve prior art problems, and provide a kind of preparation technology simple, and the catalysis of phenol hydroxylating is synthesized the preparation method of the high supported iron-based composite catalyst of benzenediol productive rate.
The method of preparing supported iron-based composite catalyst by dipping method provided by the present invention may further comprise the steps:
1) catalyst carrier is vacuumized 1-3h, standby;
2) the active component presoma is added and step 1) in the isopyknic water of catalyst carrier in dissolve, and add surfactant and stir, obtain mixed solution, the consumption of surfactant is the 1-5% of mixed liquor volume;
3) with step 1) in catalyst carrier in step 2) in the mixed solution that obtains behind the dipping 5-20min, dry and in 400-900 ℃ of calcining 1-10h, obtain supported iron-based composite catalyst.
Wherein, the catalyst carrier step 1) is γ-Al 2O 3, diatomite, sepiolite or zeolite molecular sieve.
Step 2) the active component presoma described in is a nitrate; In preferred ferric nitrate, copper nitrate, nitric acid tin, plumbi nitras, zinc nitrate, magnesium nitrate or the lanthanum nitrate one or more.
Step 2) surfactant described in is tartaric acid, AEO3, AEO9 or ethylenediamine tetra-acetic acid (EDTA).
Compare with existing supported iron-based composite catalyst, the present invention has following beneficial effect:
1) the inventive method reaction condition gentleness, manufacturing cycle is short, energy consumption is low, cheap, environmental friendliness.
2) the decentralization height of surfactant in the prepared catalyst of the present invention, be applied to hydrogen peroxide oxidation phenol and prepare phenol conversion height (83%) in the benzenediol reaction, the clarification of gained benzenediol water white transparency, productive rate can reach 70%～80%, and catalyst easily separates with product, and post processing is simple.
The invention will be further described below in conjunction with the specific embodiment.
The specific embodiment
Embodiment 1
1) takes by weighing 1g γ-Al 2O 3Carrier vacuumizes 1h;
2) with active component presoma Fe (NO 3) 39H 2O, Cu (NO 3) 22H 2O, Sn (NO 3) 22H 2O and Pb (NO 3) 22H 2O is dissolved in γ-Al with 1g 2O 3Stir in isopyknic water, add the surfactant A EO-3 of liquor capacity 1%;
3) with γ-Al 2O 3Carrier is in step 2) in solution in flood 5min, drying, and in 400 ℃ the calcining 1h, obtain supported iron-based composite catalyst, wherein, the content of active component is respectively 2.011mmol Fe 2O 3/ g carrier, 0.336mmol CuO/g carrier, 0.278mmol SnO/g, 0.015mmol PbO/g carrier.
Prepare application in the benzenediol reaction at hydrogen peroxide oxidation phenol:
In 2.65g phenol and 0.0378g catalyst, the hydrogenperoxide steam generator that drips 3.19g 30% (is phenol/H 2O 2(mol ratio) is 1: 1) after, in 70 ℃ of reaction 1h.Reaction finishes afterreaction liquid through extracted with diethyl ether, and the conversion ratio that gas chromatographic analysis obtains phenol is 70%, and the selectivity of benzenediol is 100%, and the selectivity of catechol is 60%.
Embodiment 2
1) takes by weighing 1g γ-Al 2O 3Carrier vacuumizes 2h;
2) with active component presoma Fe (NO 3) 39H 2O, Cu (NO 3) 22H 2O, Sn (NO 3) 22H 2O, Zn (NO 3) 22H 2O is dissolved in γ-Al with 1g 2O 3In isopyknic water, stir, add the surfactant A EO-3 of liquor capacity 5%;
3) with γ-Al 2O 3Carrier is in step 2) in solution in flood 10min, drying, and in 600 ℃ the calcining 10h, obtain supported iron-based composite catalyst, wherein, the content of active component is respectively 1.675mmolFe 2O 3/ g carrier, 0.336mmol CuO/g carrier, 0.278mmol SnO/g carrier, 0.015mmol ZnO/g carrier.
Prepare application in the benzenediol reaction at hydrogen peroxide oxidation phenol:
In 2.65g phenol and 0.0378g catalyst, the hydrogenperoxide steam generator that drips 3.19g 30% (is phenol/H 2O 2(mol ratio) is 1: 1) after, in 70 ℃ of reaction 1h.Reaction finishes afterreaction liquid through extracted with diethyl ether, and the conversion ratio that gas chromatographic analysis obtains phenol is 71%, and the selectivity of benzenediol is 100%, and the selectivity of catechol is 50%.
Embodiment 3
1) takes by weighing 1g γ-Al 2O 3Carrier vacuumizes 2h;
2) with active component presoma Fe (NO 3) 39H 2O, Cu (NO 3) 22H 2O, Sn (NO 3) 22H 2O, La (NO 3) 22H 2O is dissolved in γ-Al with 1g 2O 3In isopyknic water, stir, add the surfactant tartaric acid of liquor capacity 3%;
3) with γ-Al 2O 3Carrier is in step 2) in solution in flood 10min, drying, and in 550 ℃ the calcining 10h, obtain supported iron-based composite catalyst, wherein, the content of active component is respectively 1.34mmol Fe 2O 3/ g carrier, 0.336mmol CuO/g carrier, 0.278mmol SnO/g carrier, 0.015mmol LaO/g carrier.
Prepare application in the benzenediol reaction at hydrogen peroxide oxidation phenol:
In 2.65g phenol and 0.0378g catalyst, the hydrogenperoxide steam generator that drips 3.19g 30% (is phenol/H 2O 2(mol ratio) is 1: 1) after, in 70 ℃ of reaction 1h.Reaction finishes afterreaction liquid through extracted with diethyl ether, and the conversion ratio that gas chromatographic analysis obtains phenol is 80%, and the selectivity of benzenediol is 100%, and the selectivity of catechol is 75%.
Embodiment 4
1) takes by weighing 1g sepiolite carrier, vacuumize 2h;
2) with active component presoma Fe (NO 3) 39H 2O, Cu (NO 3) 22H 2O, Sn (NO 3) 22H 2O, Mg (NO 3) 22H 2O be dissolved in the isopyknic water of 1g sepiolite in, stir, add the surfactant A EO-9 of liquor capacity 3%;
3) with the sepiolite carrier in step 2) in solution in flood 10min, drying, and in 750 ℃ the calcining 10h, obtain supported iron-based composite catalyst, wherein, the content of active component is respectively 1.005mmol Fe 2O 3/ g carrier, 0.336mmol CuO/g carrier, 0.278mmol SnO/g, 0.015mmol MgO/g carrier.
Prepare application in the benzenediol reaction at hydrogen peroxide oxidation phenol:
In 2.65g phenol and 0.0378g catalyst, the hydrogenperoxide steam generator that drips 3.19g 30% (is phenol/H 2O 2(mol ratio) is 1: 1) after, in 70 ℃ of reaction 1h.Reaction finishes afterreaction liquid through extracted with diethyl ether, and the conversion ratio that gas chromatographic analysis obtains phenol is 75%, and the selectivity of benzenediol is 100%, and the selectivity of catechol is 40%.
Embodiment 5
1) takes by weighing the 1g diatomite support, vacuumize 3h;
2) with active component presoma Fe (NO 3) 39H 2O, Cu (NO 3) 22H 2O, Sn (NO 3) 22H 2O is dissolved in the diatomite with 1g, stirs, and adds 3% surfactant EDTA of liquor capacity;
3) with diatomite support in step 2) in solution in flood 10min, drying, and in 800 ℃ the calcining 10h, obtain supported iron-based composite catalyst, wherein, the content of active component is respectively 0.67mmol Fe 2O 3/ g carrier, 0.336mmol CuO/g carrier, 0.278mmol SnO/g carrier.
Prepare application in the benzenediol reaction at hydrogen peroxide oxidation phenol:
In 2.65g phenol and 0.0378g catalyst, the hydrogenperoxide steam generator that drips 3.19g 30% (is phenol/H 2O 2(mol ratio) is 1: 1) after, in 70 ℃ of reaction 1h.Reaction finishes afterreaction liquid through extracted with diethyl ether, and the conversion ratio that gas chromatographic analysis obtains phenol is 65%, and the selectivity of benzenediol is 100%, and the selectivity of catechol is 30%.
Embodiment 6
1) takes by weighing 1g γ-Al 2O 3Carrier vacuumizes 2h;
2) with active component presoma Fe (NO 3) 39H 2O, Cu (NO 3) 22H 2O, Sn (NO 3) 22H 2O be dissolved in the isopyknic water of 1g γ-Al2O3 in, stir, add the surfactant TEO-3 of liquor capacity 3%;
3) with γ-Al 2O 3Carrier is in step 2) in solution in flood 10min, drying, and in 550 ℃ the calcining 10h, obtain supported iron-based composite catalyst, wherein, the content of active component is respectively 1.34mmol Fe 2O 3/ g carrier, 0.183mmol CuO/g carrier, 0.278mmol SnO/g carrier.
Prepare application in the benzenediol reaction at hydrogen peroxide oxidation phenol:
In 2.65g phenol and 0.0378g catalyst, the hydrogenperoxide steam generator that drips 3.19g 30% (is phenol/H 2O 2(mol ratio) is 1: 1) after, in 70 ℃ of reaction 1h.Reaction finishes afterreaction liquid through extracted with diethyl ether, and the conversion ratio that gas chromatographic analysis obtains phenol is 75%, and the selectivity of benzenediol is 100%, and the selectivity of catechol is 60%.
Embodiment 7
1) takes by weighing 1g γ-Al 2O 3Carrier vacuumizes 2h;
2) with active component presoma Fe (NO 3) 39H 2O, Cu (NO 3) 22H 2O, Sn (NO 3) 22H 2O is dissolved in γ-Al with 1g 2O 3In isopyknic water, stir, add the surfactant TEO-3 of liquor capacity 3%;
3) with γ-Al 2O 3Carrier is in step 2) in solution in flood 10min, drying, and in 550 ℃ the calcining 10h, obtain supported iron-based composite catalyst, wherein, the content of active component is respectively 1.34mmol Fe 2O 3/ g carrier, 0.549mmol CuO/g carrier, 0.278mmol SnO/g carrier.
Prepare application in the benzenediol reaction at hydrogen peroxide oxidation phenol:
In 2.65g phenol and 0.0378g catalyst, the hydrogenperoxide steam generator that drips 3.19g 30% (is phenol/H 2O 2(mol ratio) is 1: 1) after, in 70 ℃ of reaction 1h.Reaction finishes afterreaction liquid through extracted with diethyl ether, and the conversion ratio that gas chromatographic analysis obtains phenol is 76%, and the selectivity of benzenediol is 100%, and the selectivity of catechol is 50%.
Embodiment 8
1) takes by weighing 1g γ-Al 2O 3Carrier vacuumizes 2h;
2) with active component presoma Fe (NO 3) 39H 2O, Cu (NO 3) 22H 2O, Sn (NO 3) 22H 2O is dissolved in γ-Al with 1g 2O 3In isopyknic water, stir, add the surfactant TEO-3 of liquor capacity 3%;
3) with γ-Al 2O 3Carrier is in step 2) in solution in flood 10min, drying, and in 550 ℃ the calcining 10h, obtain supported iron-based composite catalyst, wherein, the content of active component is respectively 1.34mmol Fe 2O 3/ g carrier, 0.732mmol CuO/g carrier, 0.278mmol SnO/g carrier.
Prepare application in the benzenediol reaction at hydrogen peroxide oxidation phenol:
In 2.65g phenol and 0.0378g catalyst, the hydrogenperoxide steam generator that drips 3.19g 30% (is phenol/H 2O 2(mol ratio) is 1: 1) after, in 70 ℃ of reaction 1h.Reaction finishes afterreaction liquid through extracted with diethyl ether, and the conversion ratio that gas chromatographic analysis obtains phenol is 79%, and the selectivity of benzenediol is 100%, and the selectivity of catechol is 45%.
Embodiment 9
1) takes by weighing 1g γ-Al 2O 3Carrier vacuumizes 2h;
2) with active component presoma Fe (NO 3) 39H 2O, Cu (NO 3) 22H 2O, Sn (NO 3) 22H 2O is dissolved in γ-Al with 1g 2O 3In isopyknic water, stir, add surfactant TEO-3;
3) with γ-Al 2O 3Carrier is in step 2) in solution in flood 10min, drying, and in 550 ℃ the calcining 10h, obtain supported iron-based composite catalyst, wherein, the content of active component is respectively 1.34mmol Fe 2O 3/ g carrier, 1.098mmol CuO/g carrier, 0.278mmol SnO/g carrier.
Prepare application in the benzenediol reaction at hydrogen peroxide oxidation phenol:
In 2.65g phenol and 0.0378g catalyst, the hydrogenperoxide steam generator that drips 3.19g 30% (is phenol/H 2O 2(mol ratio) is 1: 1) after, in 70 ℃ of reaction 1h.Reaction finishes afterreaction liquid through extracted with diethyl ether, and the conversion ratio that gas chromatographic analysis obtains phenol is 82%, and the selectivity of benzenediol is 100%, and the selectivity of catechol is 40%.
Embodiment 10
1) takes by weighing 1g γ-Al 2O 3Carrier vacuumizes 2h;
2) with active component presoma Fe (NO 3) 39H 2O, Cu (NO 3) 22H 2O, Sn (NO 3) 22H 2O is dissolved in γ-Al with 1g 2O 3In isopyknic water, stir, add the surfactant TEO-3 of liquor capacity 3%;
3) with γ-Al 2O 3Carrier is in step 2) in solution in flood 10min, drying, and in 550 ℃ the calcining 10h, obtain supported iron-based composite catalyst, wherein, the content of active component is respectively 1.34mmol Fe 2O 3/ g carrier, 1.098mmol CuO/g carrier, 0.834mmol SnO/g carrier.
Prepare application in the benzenediol reaction at hydrogen peroxide oxidation phenol:
In 2.65g phenol and 0.0378g catalyst, the hydrogenperoxide steam generator that drips 3.19g 30% (is phenol/H 2O 2(mol ratio) is 1: 1) after, in 70 ℃ of reaction 1h.Reaction finishes afterreaction liquid through extracted with diethyl ether, and the conversion ratio that gas chromatographic analysis obtains phenol is 83%, and the selectivity of benzenediol is 100%, and the selectivity of catechol is 65%.
Embodiment 11
1) takes by weighing 1g γ-Al 2O 3Carrier vacuumizes 2h;
2) activity is organized presoma Fe (NO 3) 39H 2O, Cu (NO 3) 22H 2O, Sn (NO 3) 22H 2O is dissolved in γ-Al with 1g 2O 3In isopyknic water, stir, add the surfactant TEO-3 of liquor capacity 3%;
3) with γ-Al 2O 3Carrier is in step 2) in solution in flood 10min, drying, and in 550 ℃ the calcining 10h, obtain supported iron-based composite catalyst, wherein, the content of active component is respectively 1.34mmol Fe 2O 3/ g carrier, 1.098mmol CuO/g carrier, 0.556mmol SnO/g carrier.
Prepare application in the benzenediol reaction at hydrogen peroxide oxidation phenol:
In 2.65g phenol and 0.0378g catalyst, the hydrogenperoxide steam generator that drips 3.19g 30% (is phenol/H 2O 2(mol ratio) is 1: 1) after, in 70 ℃ of reaction 1h.Reaction finishes afterreaction liquid through extracted with diethyl ether, and the conversion ratio that gas chromatographic analysis obtains phenol is 74%, and the selectivity of benzenediol is 100%, and the selectivity of catechol is 74%.
Embodiment 12
1) takes by weighing 1g γ-Al 2O 3Carrier vacuumizes 2h;
2) with active component presoma Fe (NO 3) 39H 2O, Cu (NO 3) 22H 2O, Sn (NO 3) 22H 2O is dissolved in γ-Al with 1g 2O 3In isopyknic water, stir, add the surfactant TEO-3 of liquor capacity 3%;
3) with γ-Al 2O 3Carrier is in step 2) in solution in flood 20min, drying, and in 900 ℃ the calcining 10h, obtain supported iron-based composite catalyst, wherein, the content of active component is respectively 1.34mmol Fe 2O 3/ g carrier, 1.098mmol CuO/g carrier, 0.417mmol SnO/g carrier.
Prepare application in the benzenediol reaction at hydrogen peroxide oxidation phenol:
In 2.65g phenol and 0.0378g catalyst, behind the hydrogenperoxide steam generator (being that phenol/H2O2 (mol ratio) is 1: 1) of dropping 3.19g 30%, in 70 ℃ of reaction 1h.Reaction finishes afterreaction liquid through extracted with diethyl ether, and the conversion ratio that gas chromatographic analysis obtains phenol is 77%, and the selectivity of benzenediol is 100%, and the selectivity of catechol is 60%.

Claims (5)

1, a kind of method of preparing supported iron-based composite catalyst by dipping method is characterized in that, may further comprise the steps:
1) catalyst carrier is vacuumized 1-3h, standby;
2) the active component presoma is added and step 1) in the isopyknic water of catalyst carrier in dissolve, and add surfactant and stir, obtain mixed solution, the consumption of surfactant is the 1-5% of mixed liquor volume;
3) with step 1) in catalyst carrier in step 2) in the mixed solution that obtains behind the dipping 5-20min, dry and in 400-900 ℃ of calcining 1-10h, obtain supported iron-based composite catalyst.
2, method according to claim 1 is characterized in that step 1) described in catalyst carrier be γ-Al 2O 3, diatomite, sepiolite or zeolite molecular sieve.
3, method according to claim 1 is characterized in that step 2) described in the active component presoma be nitrate.
4, method according to claim 3 is characterized in that, described active component presoma is one or more in ferric nitrate, copper nitrate, nitric acid tin, plumbi nitras, zinc nitrate, magnesium nitrate or the lanthanum nitrate.
5, method according to claim 1 is characterized in that step 2) described in surfactant be tartaric acid, AE03, AE09 or EDTA.
CN200810115728A 2008-06-27 2008-06-27 A kind of method of preparing supported iron-based composite catalyst by dipping method Pending CN101612594A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
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CN102463124A (en) * 2010-11-11 2012-05-23 中国石油天然气股份有限公司 Method for preparing phenol from benzene through one-step process
CN103055931A (en) * 2013-01-22 2013-04-24 天津市达利嘉化工科技有限公司 Low-capacity solid acid catalyst for hydroxylation of phenol reaction and preparation method thereof
CN103394353A (en) * 2013-08-13 2013-11-20 唐山师范学院 Catalyst for preparing benzenediol through phenol hydroxylation and preparation method of catalyst
CN103945935A (en) * 2011-11-17 2014-07-23 巴斯夫欧洲公司 Process for producing Sn-containing catalysts
CN104383922A (en) * 2013-07-18 2015-03-04 中国石油大学(北京) Heavy oil hydrogenation iron-based catalyst and application thereof
CN104383923A (en) * 2013-07-18 2015-03-04 中国石油大学(北京) Gasoline and diesel hydrogenation iron-based catalyst and application thereof
CN105597755A (en) * 2015-11-10 2016-05-25 扬州大学 Cubic CuO catalyst, and preparation method thereof
US9409154B2 (en) 2011-11-17 2016-08-09 Basf Se Process for producing Sn-comprising catalysts
CN108380214A (en) * 2018-04-02 2018-08-10 南京万德斯环保科技股份有限公司 A kind of preparation of modified meerschaum and the method applied to wastewater treatment
US10335773B2 (en) 2013-07-18 2019-07-02 China University of Petroleum—Beijing Fe-based hydrogenation catalyst and use thereof

Cited By (15)

* Cited by examiner, † Cited by third party
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CN102463124A (en) * 2010-11-11 2012-05-23 中国石油天然气股份有限公司 Method for preparing phenol from benzene through one-step process
US9409154B2 (en) 2011-11-17 2016-08-09 Basf Se Process for producing Sn-comprising catalysts
CN103945935A (en) * 2011-11-17 2014-07-23 巴斯夫欧洲公司 Process for producing Sn-containing catalysts
CN103055931A (en) * 2013-01-22 2013-04-24 天津市达利嘉化工科技有限公司 Low-capacity solid acid catalyst for hydroxylation of phenol reaction and preparation method thereof
CN103055931B (en) * 2013-01-22 2015-01-07 天津市达利嘉化工科技有限公司 Low-capacity solid acid catalyst for hydroxylation of phenol reaction and preparation method thereof
CN104383923A (en) * 2013-07-18 2015-03-04 中国石油大学(北京) Gasoline and diesel hydrogenation iron-based catalyst and application thereof
CN104383922A (en) * 2013-07-18 2015-03-04 中国石油大学(北京) Heavy oil hydrogenation iron-based catalyst and application thereof
CN104383922B (en) * 2013-07-18 2016-05-11 中国石油大学(北京) A kind of heavy-oil hydrogenation ferrum-based catalyst and application thereof
CN104383923B (en) * 2013-07-18 2016-07-06 中国石油大学(北京) A kind of gasoline, diesel hydrogenation ferrum-based catalyst and application thereof
US10335773B2 (en) 2013-07-18 2019-07-02 China University of Petroleum—Beijing Fe-based hydrogenation catalyst and use thereof
CN103394353A (en) * 2013-08-13 2013-11-20 唐山师范学院 Catalyst for preparing benzenediol through phenol hydroxylation and preparation method of catalyst
CN105597755A (en) * 2015-11-10 2016-05-25 扬州大学 Cubic CuO catalyst, and preparation method thereof
CN105597755B (en) * 2015-11-10 2018-06-29 扬州大学 A kind of cubic phase CuO catalyst and preparation method thereof
CN108380214A (en) * 2018-04-02 2018-08-10 南京万德斯环保科技股份有限公司 A kind of preparation of modified meerschaum and the method applied to wastewater treatment
CN108380214B (en) * 2018-04-02 2019-10-18 南京万德斯环保科技股份有限公司 A kind of preparation of modified meerschaum and method applied to wastewater treatment

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