CN1843620A - Catalyst for synthesizing allyl alcohol by reduction of acrolein and preparation method thereof - Google Patents
Catalyst for synthesizing allyl alcohol by reduction of acrolein and preparation method thereof Download PDFInfo
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- CN1843620A CN1843620A CN 200610025205 CN200610025205A CN1843620A CN 1843620 A CN1843620 A CN 1843620A CN 200610025205 CN200610025205 CN 200610025205 CN 200610025205 A CN200610025205 A CN 200610025205A CN 1843620 A CN1843620 A CN 1843620A
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Abstract
The invention relates to a method for preparing solid oxide catalyst which is used to hydrogen transfer of acrolein gas to compose allyl alcohol. Said catalyst is selected from one or the mixture of alumina, titanium oxide, silicon oxide, zirconium oxide and zeolite molecule screen as carrier; using the oxide of metal tin as active component; using at least one of boron, aluminum, gallium, or indium and at least one of magnesium, zinc, or cadmium oxide as auxiliary gent. The invention has better activity and selectivity.
Description
Technical field
The present invention relates to a kind of soild oxide Catalysts and its preparation method that is used for methacrylaldehyde gas phase hydrogen transfer reduction synthesizing allyl alcohol.
Background technology
Allyl alcohol is a class important chemical intermediate and a fine chemical product.Owing to contain two keys and hydroxyl in the molecule, can participate in oxidation, reduction, esterification, etherificate and addition reaction, having a wide range of applications aspect medicine, spices, the organic synthesis.
The preparation method of relevant allyl alcohol, patent and document all have a lot of reports.With the methacrylaldehyde is raw material, and preparing allyl alcohol by selective reduction is an important process route.GB734247, GE858247, US3109865, US3686333, US4072727, US4096193 etc. have reported the multi-metallic catalyst system based on metal Cd, and methacrylaldehyde under high pressure prepares allyl alcohol with hydrogen reaction, allyl alcohol selectivity 71～78%, but, because severe reaction conditions, selectivity is not high, and catalyst life is short.
Except utilizing the hydrogen reducing methacrylaldehyde to prepare the allyl alcohol, primary alconol, secondary alcohol also can come synthesizing allyl alcohol by hydrogen migration selective reduction methacrylaldehyde.Course of reaction is shown below:
US 2779801 has reported with the aluminium isopropoxide to be catalyst, methacrylaldehyde and isopropyl alcohol obtain allyl alcohol through the liquid phase hydrogen migration, this technology path is simple, reaction temperature is low, yield is high, but catalyst costs an arm and a leg, the active facile hydrolysis of character, catalyst and product separation difficulty.US2767221 has reported with MgO-ZnO to be catalyst, and methacrylaldehyde and ethanol synthesis prepare allyl alcohol, allyl alcohol selectivity 71.7%, but the conversion ratio of methacrylaldehyde is not high, and only 48%.US 4731488 has reported to be the three-way catalyst system Mg of key component with magnesia again
aX
bY
cO
d, acrolein conversion rate and allyl alcohol selectivity have reached 90% and 92% respectively, but the magnesia series catalysts has a fatal shortcoming, easy and airborne CO
2Reaction generates carbonate, makes catalysqt deactivation.
Tin ash is the important semi-conducting material of a class, and a lot of application are arranged in the middle of catalysis.Have bibliographical information (Bull.Chem.Soc.Jpn., 1994,67,1107-1112) aqua oxidation tin can catalysis isopropyl alcohol reduction aromatic acid, aromatic ketone, halogenated hydrocarbons and aromatic alcohol derivative generate the reaction of corresponding hydrocarbon compound.But relevant for the reaction that the hydrogen migration of tin oxide catalyzing propone aldehyde gas phase prepares allyl alcohol, patent and document yet there are no report.
Summary of the invention
The objective of the invention is to develop a kind of soild oxide Catalysts and its preparation method that is used for methacrylaldehyde gas phase hydrogen transfer reduction synthesizing allyl alcohol.
The soild oxide catalyst that is used for methacrylaldehyde gas phase hydrogen transfer reduction synthesizing allyl alcohol among the present invention, be to be carrier with a kind of or its mixture in aluminium oxide, titanium oxide, silica, zirconia and the zeolite molecular sieve, preferred aluminium oxide, silica and H-beta-zeolite molecular sieve; Tin oxide with 5～40% (quality) is active component, and preferred content is 15～30% (quality); With at least a in boron, aluminium, gallium or the indium oxide of 0.1～20% (quality) is first auxiliary agent, and preferred boron oxide or aluminium oxide are first auxiliary agent, and content is 2～10% (quality); With at least a in magnesium, zinc or the cadmium oxide of 0.01～10% (quality) is second auxiliary agent, and preferred content is 0.1～5% (quality), prepares by coprecipitation.
The Preparation of Catalyst raw material is: Xi Yuan is SnCl
45H
2O or SnCl
22H
2O; The first auxiliary agent raw material is boric acid, aluminum nitrate, gallium nitrate or indium nitrate; The second auxiliary agent raw material is magnesium nitrate, zinc nitrate or cadmium nitrate.
Catalyst of the present invention is to adopt the coprecipitation preparation, detailed process is: a certain amount of Xi Yuan, the first auxiliary agent raw material, the second auxiliary agent raw material are joined in 5% the dilute nitric acid solution, obtain homogeneous transparent solution, take with precipitant solution then and the mode that adds of drip is carried out co-precipitation.Precipitation temperature is 60～80 ℃, and pH is controlled at 8.8～10.0.Precipitating reagent is alkali metal hydroxide, sodium carbonate, sodium acid carbonate, ammonium carbonate, carbonic hydroammonium or ammoniacal liquor.Precipitation after filtration, washing, at 120 ℃ of dry catalyst precursors.Catalyst precursor and carrier mixed grinding is even, the polyvinyl alcohol water solution binding agent of adding 2%, mold becomes certain shape, in 100～200 ℃ of drying 1～24h, then at 300～600 ℃ of roasting 1～10h.
Catalyst of the present invention is mainly used in preparation allyl alcohol product, and reaction raw materials is methacrylaldehyde and alcohols reducing agent.The alcohols reducing agent is a kind of in ethanol, isopropyl alcohol, the sec-butyl alcohol.Methacrylaldehyde and reducing agent are mixed by a certain percentage, squeeze into preheater by constant-flux pump by certain flow rate, the raw material after the preheating enters fixed bed reactors, and product is collected through cooling.Reaction process condition is: methacrylaldehyde/alcohol (mol ratio) is 1～10; Reaction temperature is 200～400 ℃, and reaction pressure is a normal pressure, and air speed is 0.10～2.0h
-1
Catalyst of the present invention has activity, characteristics that selectivity is high, and the present invention is further illustrated below by some embodiment.
The specific embodiment
In following examples unless otherwise specified outside, all degrees are quality %.
[embodiment 1] is with 23.27gSnCl
45H
2O, 8.88g boric acid, 12.73g magnesium nitrate are dissolved in rare nitric acid of 50ml5%, obtain solution 1; The ammonia spirit 2 of preparation 10% is as precipitating reagent.Under 60 ℃, with solution 1 and 2 and drip add and carry out co-precipitation, the drop rate of adjusting two solution makes pH be stabilized in 9.0.The precipitation after filtration, the washing, 120 ℃ of dry 5h.Should precipitate and SiO
2The carrier mixed grinding is even, adds 2% polyvinyl alcohol water solution, kneads into bulk, be squeezed into 40～60 purpose particles, and in 150 ℃ of dry 6h, 300 ℃ of roasting 5h obtains consisting of 10%SnO
2-5%B
2O
3-2%MgO/SiO
2Catalyst.
The 10ml catalyst is packed in 6 millimeters of internal diameters, long 300 millimeters the stainless steel fixed bed reactors, load inert filler up and down, carry out the evaluation of catalyst.The hydrogen transfer reduction agent is an isopropyl alcohol, is that 5.0 raw material is squeezed into reactor with constant-flux pump, 350 ℃ of reaction temperatures, liquid air speed 0.60h with feed molar ratio methacrylaldehyde/isopropyl alcohol
-1Analyze with Tianjin, island GC-2014 type gas-chromatography, calculate acrolein conversion rate and allyl alcohol selectivity.Reaction result is listed in table 1.
[embodiment 2] catalyst preparation process and catalytic reaction condition are with embodiment 1, and difference is to improve active component SnO
2Consumption, catalyst consists of 20%SnO
2-5%B
2O
3-2%MgO/SiO
2Reaction result sees Table 1.
[embodiment 3] catalyst preparation process and catalytic reaction condition are with embodiment 1, and difference is to improve active component SnO
2Consumption, catalyst consists of 30%SnO
2-5%B
2O
3-2%MgO/SiO
2Reaction result sees Table 1.
[embodiment 4] catalyst preparation process and catalytic reaction condition are with embodiment 3, and difference is carrier S iO
2Be changed to α-Al
2O
3, catalyst consists of 30%SnO
2-5%B
2O
3-2%MgO/ α-Al
2O
3Reaction raw materials molar ratio methacrylaldehyde/isopropyl alcohol is 3.0, and reaction result sees Table 1.
[embodiment 5] catalyst preparation process and catalytic reaction condition are with embodiment 3, and difference is carrier S iO
2Be changed to H-β zeolite, catalyst consists of 30%SnO
2-5%B
2O
3-2%MgO/H-β; Hydrogen transfer reduction agent isopropyl alcohol is changed to ethanol, and the mol ratio of methacrylaldehyde/ethanol is 3.0, and reaction result sees Table 1.
[embodiment 6] catalyst preparation process and catalytic reaction condition are with embodiment 1, and difference is the second auxiliary agent raw material magnesium nitrate is changed to cadmium nitrate, and catalyst consists of 10%SnO
2-5%B
2O
3-2%CdO/SiO
2Hydrogen transfer reduction agent isopropyl alcohol is changed to ethanol, and the mol ratio alcohol of methacrylaldehyde/ethanol is 5.0, and reaction result sees Table 1.
[embodiment 7] catalyst preparation process and catalytic reaction condition are with embodiment 6, and difference is the first auxiliary agent raw material boric acid is changed to gallium nitrate, and catalyst consists of 10%SnO
2-5%Ga
2O
3-2%CdO/SiO
2Reaction result sees Table 1.
[embodiment 8] catalyst preparation process and catalytic reaction condition are with embodiment 2, difference is the first auxiliary agent raw material boric acid is changed to aluminum nitrate, the content of the second auxiliary agent MgO doubles, and the ammonia spirit of precipitating reagent 10% is changed to 10% NaOH solution, carrier S iO
2Be changed to TiO
2, catalyst consists of 20%SnO
2-5%B
2O
3-4%MgO/TiO
2Hydrogen transfer reduction agent isopropyl alcohol is changed to ethanol, and the mol ratio of third rare aldehyde/ethanol is 5.0, and reaction result sees Table 1.
[embodiment 9] catalyst preparation process and catalytic reaction condition are with embodiment 8, and difference is the second auxiliary agent raw material magnesium nitrate is changed to zinc nitrate, and the NaOH solution of precipitating reagent 10% is changed to 20% Na
2CO
3Solution, carrier TiO
2Be changed to ZrO
2, catalyst consists of 20%SnO
2-5%Al
2O
3-4%ZnO/ZrO
2Hydrogen transfer reduction agent ethanol is changed to sec-butyl alcohol, and the mol ratio of methacrylaldehyde/sec-butyl alcohol is 5.0, and reaction result sees Table 1.
[embodiment 10] catalyst preparation process and catalytic reaction condition are with embodiment 8, and difference is the first auxiliary agent raw material aluminum nitrate is changed to indium nitrate, and the NaOH solution of precipitating reagent 10% is changed to 20% NaHCO
3Solution, carrier ZrO
2Be changed to SiO
2, catalyst consists of 20%SnO
2-5%In
2O
3-4%MgO/SiO
2Hydrogen transfer reduction agent ethanol is changed to sec-butyl alcohol, and the mol ratio of methacrylaldehyde/sec-butyl alcohol is 5.0, and reaction result sees Table 1.
[embodiment 11] catalyst preparation process and catalytic reaction condition are with embodiment 10, and difference is carrier S iO
2Change Al
2O
3-SiO
2, catalyst consists of 20%SnO
2-5%In
2O
3-4%MgO/Al
2O
3-SiO
2The mol ratio of methacrylaldehyde/sec-butyl alcohol is 2.0, and reaction result sees Table 1.
The catalyst of each embodiment of table 1 is formed and reaction result
| Embodiment | Catalyst is formed (accounting for the percentage by weight of carrier) | Reducing agent | Methacrylaldehyde/reducing agent (mole) | Acrolein conversion rate (%) | Allyl alcohol selectivity (%) |
| 1 | 10％SnO 2-5％B 2O 3- 2％MgO/SiO 2 | Isopropyl alcohol | 5.0 | 80 | 86 |
| 2 | 20％SnO 2-5％B 2O 3- 2％MgO/SiO 2 | Isopropyl alcohol | 5.0 | 85 | 87 |
| 3 | 30％SnO 2-5％B 2O 3- 2％MgO/SiO 2 | Isopropyl alcohol | 5.0 | 90 | 85 |
| 4 | 30％SnO 2-5％B 2O 3- 2％MgO/α-Al 2O 3 | Isopropyl alcohol | 3.0 | 80 | 83 |
| 5 | 30％SnO 2-5％B 2O 3- 2％MgO/H-β | Ethanol | 3.0 | 82 | 77 |
| 6 | 10％SnO 2-5％B 2O 3- 2％CdO/SiO 2 | Ethanol | 5.0 | 75 | 82 |
| 7 | 10％SnO 2-5％Ga 2O 3- 2％CdO/SiO 2 | Ethanol | 5.0 | 70 | 83 |
| 8 | 20％SnO 2-5％Al 2O 3- 4％MgO/TiO 2 | Ethanol | 5.0 | 74 | 84 |
| 9 | 20％SnO 2-5％Al 2O 3- 4％ZnO/ZrO 2 | Sec-butyl alcohol | 5.0 | 88 | 83 |
| 10 | 20％SnO 2-5％In 2O 3- 4％MgO/SiO 2 | Sec-butyl alcohol | 5.0 | 82 | 88 |
| 11 | 20％SnO 2-5％In 2O 3- 4％MgO/Al 2O 3-SiO 2 | Sec-butyl alcohol | 2.0 | 75 | 84 |
Claims (7)
1, a kind of soild oxide catalyst that is used for methacrylaldehyde gas phase hydrogen transfer reduction synthesizing allyl alcohol, it is characterized in that this catalyst is is carrier with at least a in aluminium oxide, titanium oxide, silica, zirconia or the zeolite molecular sieve, tin oxide with 5～40 quality % is active component, with at least a in boron, aluminium, gallium or the indium oxide of 0.1～20 quality % is first auxiliary agent, is second auxiliary agent with at least a in magnesium, zinc or the cadmium oxide of 0.01～10 quality %.
2, catalyst according to claim 1, the content that it is characterized in that this activity of such catalysts component tin oxide are 15～30 quality %, and the content of first auxiliary agent is 2～10 quality %, and the content of second auxiliary agent is 0.1～5 quality %.
3, catalyst according to claim 1, the raw material that it is characterized in that active component tin oxide is hydration butter of tin or stannous chloride, the first auxiliary agent raw material is boric acid, aluminum nitrate, gallium nitrate or indium nitrate, and the second auxiliary agent raw material is zinc nitrate, magnesium nitrate or cadmium nitrate.
4, a kind of according to the described Preparation of catalysts method of claim 1, it is characterized in that this catalyst precursor is is that 60～80 ℃ and pH are under 8.8～10.0 the condition in temperature, carry out co-precipitation in the material solution with the precipitating reagent aqueous solution and drip adding active component and auxiliary agent, prepare by washing and drying then.
5,, it is characterized in that precipitating reagent is a kind of in alkali metal hydroxide, sodium carbonate, sodium acid carbonate, ammonium carbonate, carbonic hydroammonium or the ammoniacal liquor according to the described Preparation of catalysts method of claim 4.
6, want 4 described Preparation of catalysts methods according to right, it is characterized in that with presoma and carrier mixed grinding evenly after, add 2% polyvinyl alcohol water solution binding agent, the mold moulding, at 100～200 ℃ of drying 1～24h, 300～600 ℃ of roasting 1～10h.
7, a kind of Application of Catalyst according to claim 1, it is characterized in that this catalyst is used for methacrylaldehyde gas phase hydrogen transfer reduction synthesizing allyl alcohol, the hydrogen transfer reduction agent is selected from a kind of in ethanol, isopropyl alcohol or the sec-butyl alcohol, methacrylaldehyde and pure reducing agent mol ratio are 1～10, reaction temperature is 200～400 ℃, pressure is normal pressure, and the liquid air speed is 0.10～2.0h
-1
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451677A (en) * | 2011-05-13 | 2012-05-16 | 中国石油大学(华东) | Catalyst for alkane dehydrogenation and device |
| CN101316809B (en) * | 2005-12-01 | 2012-07-25 | 花王株式会社 | Process for producing alpha,beta-unsaturated aldehyde compounds |
| CN103755523A (en) * | 2013-12-02 | 2014-04-30 | 江苏苏博特新材料股份有限公司 | Preparation method for 2-methylallyl alcohol |
| CN105618026A (en) * | 2016-01-05 | 2016-06-01 | 中国石油大学(华东) | Catalyst for catalytic dehydrogenation of alkane as well as preparation method and application method of catalyst |
| CN106278814A (en) * | 2015-06-10 | 2017-01-04 | 万华化学集团股份有限公司 | A kind of method simultaneously preparing methallyl alcohol and cyclododecanone |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6712077A (en) * | 1967-09-01 | 1969-03-04 | ||
| US4072727A (en) * | 1976-08-13 | 1978-02-07 | Celanese Corporation | Silver-cadmium-zinc alloy catalyst for hydrogenation of acrolein to allyl alcohol |
| EP0183225B1 (en) * | 1984-11-27 | 1988-11-09 | Nippon Shokubai Kagaku Kogyo Co., Ltd | Catalyst for vapor-phase hydrogen transfer reaction |
| EP0435655B1 (en) * | 1989-12-26 | 1998-02-25 | Sumitomo Metal Mining Company Limited | Silver-metal oxide composite material and process for producing the same |
| JPH0656722A (en) * | 1992-08-07 | 1994-03-01 | Mitsubishi Petrochem Co Ltd | Production of unsaturated alcohol |
| US5433901A (en) * | 1993-02-11 | 1995-07-18 | Vesuvius Crucible Company | Method of manufacturing an ITO sintered body |
| CN1087555A (en) * | 1993-06-30 | 1994-06-08 | 浙江大学 | The catalyzer of ethene and the direct synthesizing styrene of benzene |
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2006
- 2006-03-29 CN CNB2006100252050A patent/CN100402142C/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101316809B (en) * | 2005-12-01 | 2012-07-25 | 花王株式会社 | Process for producing alpha,beta-unsaturated aldehyde compounds |
| CN102451677A (en) * | 2011-05-13 | 2012-05-16 | 中国石油大学(华东) | Catalyst for alkane dehydrogenation and device |
| CN102451677B (en) * | 2011-05-13 | 2014-04-23 | 中国石油大学(华东) | Catalyst for alkane dehydrogenation and device |
| CN103755523A (en) * | 2013-12-02 | 2014-04-30 | 江苏苏博特新材料股份有限公司 | Preparation method for 2-methylallyl alcohol |
| CN103755523B (en) * | 2013-12-02 | 2016-02-03 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of 2-methallyl alcohol |
| CN106278814A (en) * | 2015-06-10 | 2017-01-04 | 万华化学集团股份有限公司 | A kind of method simultaneously preparing methallyl alcohol and cyclododecanone |
| CN106278814B (en) * | 2015-06-10 | 2019-04-23 | 万华化学集团股份有限公司 | Method that is a kind of while preparing methallyl alcohol and cyclododecanone |
| CN105618026A (en) * | 2016-01-05 | 2016-06-01 | 中国石油大学(华东) | Catalyst for catalytic dehydrogenation of alkane as well as preparation method and application method of catalyst |
| CN105618026B (en) * | 2016-01-05 | 2019-09-03 | 中国石油大学(华东) | Catalyst for alkane catalytic dehydrogenation and preparation method thereof and application method |
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| CN100402142C (en) | 2008-07-16 |
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