CN104128195A - Catalyst for preparing cyanopyridine and preparation method thereof - Google Patents
Catalyst for preparing cyanopyridine and preparation method thereof Download PDFInfo
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- CN104128195A CN104128195A CN201410316037.5A CN201410316037A CN104128195A CN 104128195 A CN104128195 A CN 104128195A CN 201410316037 A CN201410316037 A CN 201410316037A CN 104128195 A CN104128195 A CN 104128195A
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- catalyst
- oxide
- cyanopyridine
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Abstract
The invention relates to a catalyst for preparing cyanopyridine and a preparation method thereof. The catalyst for preparing the cyanopyridine is composed of a main catalyst of a vanadium oxide, a cocatalyst composed of other transition metal oxide, alkali metal oxide, oxide of fifth group metal element and oxide of phosphor, and a carrier. Through the relative experiment, the catalyst has the characteristics of high catalysis efficiency, low production cost, wide application scope, good economic benefit, obvious energy saving effect, and convenient usage.
Description
Technical field
The present invention relates to a kind of catalyst for the preparation of cyanopyridine and preparation method.
Background technology
The main method of suitability for industrialized production nicotinonitrile is as raw material, at NH taking 3-picoline at present
3, O
2and under catalyst action, make i.e. 3-picoline ammonia oxidation by ammoxidation reaction.Ammoxidation reaction refers to alkene, aromatic hydrocarbons, alkane hydrocarbons and their derivates and air (O
2), NH
3be blended on catalyst the class reaction that reaction obtains cyanides, reaction expression:
R-CH
3+NH
3+?O
2——?R-CN+H
2O
This reacts the possible reaction mechanism mechanism of reaction: first R-CH
3under catalyst action, dehydrogenation generates R-CH
2free radical, this free radical oxygen uptake forms R-CHO, subsequently R-CHO and NH
3condensation forms nitrile, or first oxidized formation R-COOH of R-CHO, then with NH
3effect generates acid amides and is hydrolyzed formation nitrile again.
Ammoxidation reaction process is a complicated process, and except main reaction, side reaction is more, and its difficult point is in the preparation of catalyst.The catalyst of ammoxidation reaction not only requires conversion ratio high, and it selectively also wants high.The possible reaction mechanism of 3-picoline prepared by ammoxidation nicotinonitrile: multistep dehydrogenation and the oxidation after catalyst absorption of 3-picoline, generate formaldehyde pyridine or pyridinecarboxylic acid, then carry out cyanogenation and generate product.The oxygen that participates in reaction in oxidation reaction is not gas phase oxygen but Lattice Oxygen on catalyst surface; The ammonia that participates in reaction in cyanogenation is not vapor phase ammonia but is adsorbed on the NH on catalyst surface
2or-NH
2.And it is more faster than oxidation rate according to experimental fact cyaniding speed, therefore controlling the step of reaction speed is dehydrogenation and oxidation, again because the intermediate product that synthesizes cyanopyridine is easily by deep oxidation, therefore require catalyst to have calculation and the middle calculation of confession [O] and suitable confession [O] activity in rational dehydrogenation.This is just for the preparation of catalyst provides theoretical foundation.
Patent application (publication number CN102336706A) has been announced taking V-Cr or V-P master's or V-Sb system fused salt as catalyst, the technique of catalysis 3-picoline prepared by ammoxidation nicotinonitrile.According to the disclosed content of this application file, thermal conductivity factor that this preparation method has is high, and conversion ratio is high, selectively high, the advantage of growing service life.But from this application file, lack necessary technical characterictic, therefore insider cannot understand its concrete technology contents summary of the invention
The invention provides a kind of catalyst of can efficient catalytic preparing cyanopyridine.
A kind of catalyst of preparing cyanopyridine of the present invention be the co-catalyst forming by the barium oxide of major catalyst with other the oxide of oxide, phosphorus of transition metal oxide, alkali metal oxide, the 5th family's metallic element, and carrier forms.
The preparation of the invention of cocatalyst cyanopyridine catalyst of transition metal oxides of iron, molybdenum, chromium oxide or a mixture of several kinds of oxides, either five elements of metal oxide bismuth oxide, is the carrier used for porous 3 oxidation 2 aluminium and titanium dioxide.
The mass percent that the present invention prepares tenor in the catalytic component of cyanopyridine and aluminium oxide, titanium oxide is: V: Fe: Mo: Cr: Bi: K: P: Al
2o
3: TiO
2=1-10%: 0.1-1%: 0.1-1%: 0.2-2%: 0.1-1%: 0.1-1%: 0.5-5%: 50-75%: 10-20%.
The catalyst components content that the present invention preferably prepares cyanopyridine is: vanadic anhydride: 28g, di-iron trioxide: 1.45g, molybdenum trioxide: 2.5g, chromium oxide 1.72g, bismuth oxide 2.4g, potassium chloride, 1.5g, phosphorus pentoxide 9g, carrier A l
2o
3: 180g, TiO
2: 40g.
The present invention for the preparation of the preparation method of the catalyst of cyanopyridine is: the nitrate that takes vanadic anhydride, phosphorus pentoxide, potassium oxide and other metal by group component, aforementioned each raw material is added and in oxalic acid aqueous solution, after stirring and dissolving, adds therein carrier again, after fully flooding, high-temperature roasting is carried out in dry processing again, after screening, obtains catalyst
The present invention for the preparation of the preferred preparation method of the catalyst of cyanopyridine is: take 68 g vanadic anhydrides, 5g ferric nitrate, and 7.5g ammonium molybdate, 9g chromic nitrate, 5g bismuth nitrate, 4.5g potassium chloride, 12g phosphorus pentoxide adds in 800mL oxalic acid aqueous solution, at 60-90
ostirring and dissolving at C temperature, then add Al
2o
3: 180g, TiO
2: the catalyst carrier of 40g is flooded, then by the solid after dipping 100 DEG C-200 DEG C fully dry, then at 500 DEG C-900 DEG C roasting 3-10 hour, sieve as size approximately 30 object particles.
Show through related experiment, catalyst of the present invention has that catalytic efficiency is high, production cost is low, applied range, good in economic efficiency, obvious energy conservation, the feature such as easy to use.
Detailed description of the invention
The present invention explains orally by the following examples in detail.
One, catalyst preparation
Take 68 g vanadic anhydrides, 5g ferric nitrate, 7.5g ammonium molybdate, 9g chromic nitrate, 4.8g bismuth nitrate, 5g bismuth nitrate, 4.5g potassium chloride, 12g phosphorus pentoxide adds in 800mL oxalic acid aqueous solution, at 60-90
ostirring and dissolving at C temperature, and add good catalyst carrier (alundum (Al2O3), the titanium dioxide) dipping of the resistance to elevated temperatures of 200-300g.Catalyst after above-mentioned dipping is fully dried at 100 DEG C-200 DEG C, and then roasting 3-10 hour at 500 DEG C-900 DEG C, sieves as size approximately 30 object particles.Just made the mentioned 3-picoline prepared by ammoxidation of the present invention for nicotinonitrile catalyst.
Two, evaluating catalyst
Utilize tubular fixed-bed microreactor, react as example for nicotinonitrile taking 3-picoline prepared by ammoxidation, evaluate the catalytic activity of catalyst of the present invention.
Experimental program is: with air, as oxygen source, 3-picoline, ammonia and water are that raw material is prepared nicotinonitrile.Mixed material (5-10mL/h) is sent into 220 with air (200 mL/min) with certain proportion after mixing
oc preheater, then the raw material after preheating and overfire air are sent into the fixed bed reactors that are wherein filled with aforementioned catalyst of the present invention and carry out ammoxidation reaction.Raw material proportioning when evaluation response is: in 100 mL solution, and 3-picoline: 15 mL, ammoniacal liquor (wt 28%): 42.5 mL, water: 42.5 mL.Product is through the cooling collection of product-collecting tank, and tail gas is emptying after absorbing by tail gas absorption tank.Sampling, analyzes.Result demonstration, the feed stock conversion of catalyst 3-picoline of the present invention ammoxidation and product selectivity are still more than 90%-98%.
Catalyst of the present invention is prepared corresponding cyanopyridine for its picoline similar result.
Claims (6)
1. prepare a catalyst for cyanopyridine, the co-catalyst forming by the barium oxide of major catalyst with other the oxide of oxide, phosphorus of transition metal oxide, alkali metal oxide, the 5th family's metallic element, and carrier forms.
2.?According to claim 1 of the catalyst for the preparation of cyanopyridine, its characteristic is to help catalyst used of transition metal oxides of iron, molybdenum, chromium oxide or a mixture of several kinds of oxides, either five elements of metal oxide is bismuth oxide, with the carrier for porous 3 oxidation 2 aluminium and titanium dioxide.
3. the catalyst of preparing cyanopyridine according to claim 2, is characterized in that the mass percent of tenor in catalytic component and aluminium oxide, titanium oxide is: V: Fe: Mo: Cr: Bi: K: P: Al
2o
3: TiO
2=1-10%: 0.1-1%: 0.1-1%: 0.2-2%: 0.1-1%: 0.1-1%: 0.5-5%: 50-75%: 10-20%.
4. the catalyst of preparing cyanopyridine according to claim 3, is characterized in that catalyst components content is: vanadic anhydride: 28g, di-iron trioxide: 1.45g, molybdenum trioxide: 2.5g, chromium oxide 1.72g, bismuth oxide 2.4g, potassium chloride, 1.5g, phosphorus pentoxide 9g, carrier A l
2o
3: 180g, TiO
2: 40g.
5. the preparation method of the catalyst of preparing cyanopyridine claimed in claim 3, it is characterized in that taking by group component the nitrate of vanadic anhydride, phosphorus pentoxide, potassium oxide and other metal, aforementioned each raw material is added and in oxalic acid aqueous solution, after stirring and dissolving, adds therein carrier again, after fully flooding, high-temperature roasting is carried out in dry processing again, after screening, obtains catalyst.
6. the preparation method of the catalyst of preparing cyanopyridine claimed in claim 4, is characterized in that taking 68 g vanadic anhydrides, 5g ferric nitrate, 7.5g ammonium molybdate, 9g chromic nitrate, 5g bismuth nitrate, 4.5g potassium chloride, 12g phosphorus pentoxide adds in 800mL oxalic acid aqueous solution, at 60-90
ostirring and dissolving at C temperature, then add Al
2o
3: 180g, TiO
2: the catalyst carrier of 40g is flooded, then by the solid after dipping 100 DEG C-200 DEG C fully dry, then at 500 DEG C-900 DEG C roasting 3-10 hour, sieve as size approximately 30 object particles.
Priority Applications (1)
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|---|---|---|---|
| CN201410316037.5A CN104128195A (en) | 2014-07-04 | 2014-07-04 | Catalyst for preparing cyanopyridine and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410316037.5A CN104128195A (en) | 2014-07-04 | 2014-07-04 | Catalyst for preparing cyanopyridine and preparation method thereof |
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|---|---|
| CN104128195A true CN104128195A (en) | 2014-11-05 |
Family
ID=51801194
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|---|---|---|---|
| CN201410316037.5A Pending CN104128195A (en) | 2014-07-04 | 2014-07-04 | Catalyst for preparing cyanopyridine and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105233849A (en) * | 2015-09-20 | 2016-01-13 | 潜江市富阳化工有限公司 | Composite catalyst used for synthesis of 3-cyanopyridine, and preparation method and application thereof |
| CN108126723A (en) * | 2017-12-29 | 2018-06-08 | 兄弟科技股份有限公司 | A kind of catalyst for being used to prepare nicotinonitrile and preparation method thereof |
| CN112547042A (en) * | 2020-12-10 | 2021-03-26 | 中触媒新材料股份有限公司 | Preparation method of 2-cyanopyridine catalyst |
| CN115228463A (en) * | 2022-07-29 | 2022-10-25 | 山东明化新材料有限公司 | Composite catalyst and nicotinic acid production method |
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|---|---|---|---|---|
| US3970659A (en) * | 1975-11-18 | 1976-07-20 | Merck & Co., Inc. | Preparation of cyanopyridines |
| CN1424144A (en) * | 2002-12-31 | 2003-06-18 | 武汉大学 | Catalyst for preparing 3-cyanopyridine and preparation and use thereof |
| CN1490313A (en) * | 2002-10-16 | 2004-04-21 | 中国石油化工股份有限公司 | Preparation of 3-cyanopyridine |
| CN101433836A (en) * | 2008-12-05 | 2009-05-20 | 浙江师范大学 | Catalyst for producing 3-cyano pyridine as well as preparation method and use thereof |
| CN101602722A (en) * | 2009-04-29 | 2009-12-16 | 南通醋酸化工股份有限公司 | The synthetic method of 3-cyanopyridine |
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2014
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3970659A (en) * | 1975-11-18 | 1976-07-20 | Merck & Co., Inc. | Preparation of cyanopyridines |
| CN1490313A (en) * | 2002-10-16 | 2004-04-21 | 中国石油化工股份有限公司 | Preparation of 3-cyanopyridine |
| CN1424144A (en) * | 2002-12-31 | 2003-06-18 | 武汉大学 | Catalyst for preparing 3-cyanopyridine and preparation and use thereof |
| CN101433836A (en) * | 2008-12-05 | 2009-05-20 | 浙江师范大学 | Catalyst for producing 3-cyano pyridine as well as preparation method and use thereof |
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Non-Patent Citations (1)
| Title |
|---|
| 姚蒙正，等: "《精细化工产品合成原理》", 30 April 1992, 中国石化出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105233849A (en) * | 2015-09-20 | 2016-01-13 | 潜江市富阳化工有限公司 | Composite catalyst used for synthesis of 3-cyanopyridine, and preparation method and application thereof |
| CN108126723A (en) * | 2017-12-29 | 2018-06-08 | 兄弟科技股份有限公司 | A kind of catalyst for being used to prepare nicotinonitrile and preparation method thereof |
| CN108126723B (en) * | 2017-12-29 | 2021-01-15 | 兄弟科技股份有限公司 | Catalyst for preparing 3-cyanopyridine and preparation method thereof |
| CN112547042A (en) * | 2020-12-10 | 2021-03-26 | 中触媒新材料股份有限公司 | Preparation method of 2-cyanopyridine catalyst |
| CN115228463A (en) * | 2022-07-29 | 2022-10-25 | 山东明化新材料有限公司 | Composite catalyst and nicotinic acid production method |
| CN115228463B (en) * | 2022-07-29 | 2024-01-26 | 山东明化新材料有限公司 | Composite catalyst and nicotinic acid production method |
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Application publication date: 20141105 |