CN1415591A - Technical method of dehydrogenating alcohols - Google Patents
Technical method of dehydrogenating alcohols Download PDFInfo
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- CN1415591A CN1415591A CN 01133361 CN01133361A CN1415591A CN 1415591 A CN1415591 A CN 1415591A CN 01133361 CN01133361 CN 01133361 CN 01133361 A CN01133361 A CN 01133361A CN 1415591 A CN1415591 A CN 1415591A
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Abstract
A process for dehydrogenating alcohols features that after the dehydrogenating catalyst whose active component is nano-class metal component is loaded in reactor, the dehydrogenating reaction on raw alcohol takes place to generate aldehyde and ketone whose number of C atoms isequal to that of alcohol. Its advantages are high selectivity, low reaction temp and long service life of catalyst.
Description
1, technical field
The present invention relates to the processing method of alcohols catalytic dehydrogenation, especially the processing method of low-carbon alcohol dehydrogenation such as C1-C10.
2, background technology
Alcohol dehydrogenase is a kind of main method of preparation aldehyde, ketone, prepares acetaldehyde, dehydrogenation of isopropanol as alcohol dehydrogenase and prepares acetone, sec-butyl alcohol dehydrogenizing and prepare that methylethylketone, cyclohexanol dehydrogenation prepare pimelinketone, the n-Octanol dehydrogenation prepares octanal etc.
Metal or its alloys such as copper, zinc, nickel, platinum, palladium, rhodium have fine catalytic activity and very high product selectivity for the dehydrogenation of alcohol, because precious metals such as platinum cost an arm and a leg, mainly use copper or brass alloys as catalyzer.Use the copper or the brass of shapes such as grain, net, fiber to carry out catalytic dehydrogenation in the past as catalyzer, but because the active surface area of such catalyzer unit mass is very little, catalytic activity is very low, the alcohol conversion that reaches is very low, the temperature of reaction that requires is very high, the easy carbon distribution of catalyst surface need repeat regeneration.
Developed the Zinc oxide catalyzer afterwards again, and, but still needed higher temperature of reaction, and selectivity and life of catalyst are not high though this catalyzer has improved activity.The main in the recent period reduction copper catalyst that adopts, this catalyzer is main catalyst component with the copper of going back ortho states, is added with metal oxides such as zinc, magnesium, chromium, calcium to improve the dispersity and the stability of copper crystallite.Perhaps appendix is on carriers such as aluminum oxide, diatomite, zeolite.Though improved the dispersity of copper like this, improved the transformation efficiency of catalytic activity and alcohol, because the adding of carrier or the 3rd component causes the optionally reduction of product; And catalyzer still can in use produce carbon distribution, need repeat regeneration.
As English Patent BP1,444,484 and 1,500,884, it is main that CuO is adopted in United States Patent (USP) 4453015 introductions such as grade, with MgO, Cr
2O
3, ZnO etc. is for helping catalyst component, with SiO
2, Al
2O
3Make catalyzer Deng for carrier or binding agent, be used for the dehydrogenation of Virahol, sec-butyl alcohol and hexalin etc. after the CuO reduction.The dehydrogenation reaction temperature is between 200-300 ℃, though the transformation efficiency of alcohol can reach more than 80%, the selectivity of purpose product ketone is lower, between 90%-95%, still has the space of raising.And the type catalyzer is carbon distribution inactivation gradually in use, needs to repeat charcoal regeneration.
Also have the patent introduction to adopt precious metals such as more highly active palladium, rhodium to be stated from α-Al
2O
3Go up as mellow wine dehydrogenating, introduce as United States Patent (USP) 3981923, adopting platiniferous is Pt/ α-Al of 0.25w%
2O
3Be catalyzer, be used for alcohol dehydrogenase, have the shortcoming of above catalyzer equally, and the price of catalyzer is also high.
3, summary of the invention
At the deficiencies in the prior art, the objective of the invention is to by using a kind of new catalyzer, be used for the dehydrogenation of alcohol, improve the selectivity that reaction generates aldehyde, ketone, and the carbon distribution problem that has catalyzer does not hardly need catalyzer is regenerated, and has improved the work-ing life of catalyzer.
The processing method of dehydrogenating alcohol of the present invention comprises: the alcohols reaction raw materials contacts with dehydrogenation catalyst in being seated in reactor, dehydrogenation reaction taking place generate the ketone identical with the raw alcohol carbonatoms, is characterized in that employed dehydrogenation catalyst is is the dehydrogenation catalyst of active ingredient with the nano metal component.
Above-mentioned dehydrogenation catalyst is meant metal that nano level has dehydrogenation functionality directly as catalyzer, or nanometer dehydrogenation metal component is supported on catalyzer prepared on the carrier.But inorganic oxides such as carrier aluminum oxide.Described dehydrogenation metal component can be selected from one or more among VIB in the periodic table of elements, VIII, IB, the IIB, mainly is the metal such as copper, copper zinc alloy, nickel, platinum, palladium of nanometer.
Catalyzer of the present invention is nanometer copper metal or Nanometre Cu-Zn alloy catalyst preferably.
The preparation of above-mentioned nano metal can by in high vacuum chamber through the gas starting arc to melting of metal, evaporation, collect preparation through cold-trap cooling then.Concrete preparation process can be with reference to Chinese patent CN1037073, CN2218600.The nano metal component is supported on supported catalyst, can adopt arc plasma process to prepare nano metal particles, by the high pressure collision it is loaded on the carrier then, and thin shell type nano metal/carried catalyst is made in activated processing.
Above-mentioned nano metal particles size can be 1-100nm, better is 1-20nm, preferably 1-10nm.
The reaction conditions that alcohol dehydrogenase of the present invention prepares aldehydes or ketones is generally:
Temperature of reaction: 100～350 ℃;
Reaction pressure: 0.01～0.5MPa;
Charging alcohol air speed (weight): 0.5～10.0h
-1
Described alcohols reaction raw materials generally is primary alconol and the secondary alcohol of carbonatoms at the alkyl of 1-12, also can be that carbonatoms is the cycloalkyl alcohol between the 5-10.What the primary alconol that is used for dehydrogenation system aldehyde was relatively more commonly used is ethanol, octanol etc., and what be used for that the alcohol of dehydrogenation system ketone relatively uses always mainly contains Virahol, sec-butyl alcohol, hexalin, secondary octanol etc.
The method that dehydrogenating alcohol of the present invention prepares aldehydes or ketones both can be a tandem reaction sequence, also can be the rhythmic reaction process.For example can realize by following process: metallic catalyst is loaded in the encloses container, and this container can be the flask, still of glass or metal etc.High boiling solvent is housed in the container, and nano-metal particle is suspended in this solvent, and solvent and catalyzer account for the 1/2-2/3 of container volume.Encloses container is equipped with heating jacket, whipping appts, lower curtate is equipped with the gas feed mouth and pneumatic outlet is left at feed distributor, top.The dehydrogenation reaction of alcohol is carried out in this container.
At first metallic catalyst is added in the reactor in the desired amount, add high boiling solvent to the long-pending 1/2-2/3 place of kettle, start whipping appts, stirring velocity is decided to be that the particulate that makes metallic catalyst all scatters and the uniform mixing stirring.For copper or brass alloys catalyzer, after raw catalyst is packed reactor into, catalyzer be reduced, feed nitrogen and hydrogen mixture or hydrogen during reduction, warming while stirring is to 150-200 ℃, and constant temperature 4-8 hour, reduction finished.For metallic reducings such as platinum, palladium at normal temperatures constant temperature finish.For nano nickel catalyst, in the solvent of reactor of the nanometer nickel of preparation being packed into, under the condition that guarantees oxide compounds such as ingress of air not, be directly used in the dehydrogenation of catalytic alcohol under the secluding air state.
After above operation is finished, keep stirring and hydrogen atmosphere, the solvent that is suspended in catalyzer in the reactor is risen to temperature of reaction, raw alcohol gasification post-heating is to temperature of reaction, enter reactor by the reactor bottom through sparger, stop to enter hydrogen, the alcohol of gas in still under whipped state with the catalyzer contact reacts, remove hydrogen, aldehydes or ketones, hydrogen and the unreacted alcohol of reaction generation are still with gas phase effusion reactor with this understanding, cool and isolate hydrogen, product liquid is isolated product aldehydes or ketones and unreacted alcohol.
Reaction has very high selectivity because metal catalyst of the present invention is to alcohol dehydrogenase, and the side reaction of generation is few.
The employed high boiling solvent of said process can be selected for use reactant and product and catalyzer inert high boiling solvent, is that polyisobutene between the 500-10000 or polybutene, refining Vaseline or white oil, refined white wax and molecular weight are the polyoxyethylene glycol between the 500-10000 etc. as molecular weight.
Temperature of reaction of the present invention determine that preferably can keep the pure and mild product of reactant is gas phase, between 100-350 ℃, often be between 130-250 ℃ generally.
The inlet amount of alcohol of the present invention is 0.5-10h by the weight space velocity with the ratio of catalyzer
-1Between, the best is 1-6h
-1Between.
By process of the present invention, alcohol dehydrogenation on metallic catalyst can reach the selectivity of very high ketone or aldehyde, and the temperature of reaction is low, and produces carbon distribution hardly on the catalyzer, and the use mission of catalyzer is long.Following embodiment illustrates that the present invention can reach such effect.
4, embodiment
Embodiment 1
Make a copper nanoparticle end (median size is 6nm) catalyzer 10.0g by the above method of mentioning patent disclosure and pack in the 500ml there-necked flask, add the 350ml molecular weight and be 2000 polyisobutene.Flask outfit electric mixing device and electrically heated cover are as the dehydrogenation reaction still, a bite of reactor is equipped with a glass inlet pipe, be inserted into drag always, connect a gas distributor, have micropore on the sparger, determine the size of micropore and distribution so that feed gas enters with superfine bubble and is evenly distributed; Feed distributor is at the bottommost of flask, and makes it not bump with agitating fins; Inlet mouth connects electric heating tube as feed heater, and electric heating tube is connected with a glass threeway again, and an end of threeway connects two mouthfuls of flasks that a 250ml is equipped with the electrically heated cover as the charging vaporizer, the pure charging volume pump of another mouthful of this flask connection; The other end of threeway is connected with sources of hydrogen through a cock.Another of reactor mouthful connection one Glass tubing is as the reaction product outlet, the glass pipe end is tried one's best on solvent liquid level away from liquid level, Glass tubing connects condenser, gas-liquid separator and product liquid receptor, gas separated emptying after the condensation, prolong preferably adopts chilled brine or more cryogenic refrigerant condensation, and this example uses-5 ℃ chilled brine as refrigerant.
Behind connection of above system and good seal, reactor is heated to 100 ℃, start stirring, regulating stirring velocity evenly rolls catalyst fines, open the water of condensation inlet valve and advance water of condensation to prolong, simultaneously reactor, heating tube are heated to 180 ℃, material carburetor is heated to 150 ℃, hydrogen air inlet cock is opened, enter normal pressure hydrogen to reactor, amounts of hydrogen is 500ml/min, feeds hydrogen 4 hours, stop into hydrogen, catalyst reduction finishes.Start fresh feed pump, enter sec-butyl alcohol by 20g/h, the sec-butyl alcohol vaporization is after heating tube is heated to 180 ℃, enter reactor, with the catalyzer contact reacts, reaction product is overflowed with gas phase and is gone out hydrogen through condensation, gas-liquid separation, and product liquid is through gas chromatographic analysis, contain methylethylketone 45.3w%, sec-butyl alcohol 54.6w%.The transformation efficiency of sec-butyl alcohol is 53.9%, and the selectivity of methylethylketone is 99.7%.
Embodiment 2
Use the same equipment of embodiment 1, take same operating process, 10.0g Nanometre Cu-Zn alloy (contain zinc 50w%, copper zinc median size is 15nm) powder is packed in the reactor, add No. 50 refining Chinese wax of 350ml, after pressing the operating process catalyst reduction of embodiment 1, temperature of reaction kettle is heated to 150 ℃, advances Virahol by 30g/h, carries out the test that dehydrogenation of isopropanol prepares acetone, product liquid contains acetone 37.6w% through gas chromatographic analysis, Virahol 62.2w%.
Embodiment 3
The 10g nanometer nickel (median size is 10nm) of preparation is gone back the powder of ortho states, be sealed in the 100ml polyoxyethylene glycol-5000, use the same equipment of embodiment 1, guaranteeing under the complete secluding air state of nanometer nickel, pack in the reactor, the polyoxyethylene glycol-5000 that adds 250ml, system feeds hydrogen exchange air wherein, reactor keeps stirring and being heated to 200 ℃, and feed heater also is heated to charging 200 ℃, and vaporizer is heated to 150 ℃, advance hexalin by 10g/h, carry out the test that cyclohexanol dehydrogenation prepares pimelinketone, product liquid contains pimelinketone 34.2w% through gas chromatographic analysis, hexalin 65.7w%.
Embodiment 4
Use the same equipment of embodiment 1, take same operating process, the powder (median size 6nm) of 2g nanometer platinum is packed in the reactor of 250ml, the polyisobutene-2500 that adds 150ml, after by the operating process of embodiment 1 catalyzer being reduced, temperature of reaction kettle is heated to 150 ℃, advance ethanol by 10g/h, carry out the test that alcohol dehydrogenase prepares acetaldehyde, the cold ethanol that adopts-20 ℃ is as the refrigerant of prolong, cooling product liquid down contains acetaldehyde 28.2w% through gas chromatographic analysis, ethanol 61.5w%.
Embodiment 5
Use the same equipment of embodiment 1, take same operating process, the powder of 10g Nanometre Cu-Zn alloy (containing zinc 50%, the median size 20nm of copper zinc alloy) is packed in the reactor, add the polyisobutene-5000 of 350ml, after by the operating process of embodiment 1 catalyzer being reduced, temperature of reaction kettle is heated to 230 ℃, advances n-Octanol by 10g/h, carries out the test that the n-Octanol dehydrogenation prepares n-octaldehyde, product liquid contains octanal 45.2w% through gas chromatographic analysis, n-Octanol 54.5w%.
Claims (10)
1, a kind of processing method of dehydrogenating alcohol, comprise: the alcohols reaction raw materials contacts with dehydrogenation catalyst in being seated in reactor, dehydrogenation reaction taking place generate the aldehydes or ketones identical with the raw alcohol carbonatoms, it is characterized in that described dehydrogenation catalyst is is the dehydrogenation catalyst of active ingredient with the nano metal component.
2,, it is characterized in that the reaction conditions that described alcohol dehydrogenase prepares aldehydes or ketones is according to the described dehydrogenating alcohol processing method of claim 1:
Temperature of reaction: 100～350 ℃;
Reaction pressure: 0.01～0.5MPa;
Alcohol feed weight air speed: 0.5～10.0h
-1
3,, it is characterized in that described nano metal component is to be selected from one or more among VIB, VIII, IB, the IIB in the periodic table of elements according to the described dehydrogenating alcohol processing method of claim 1.
4,, it is characterized in that described nano metal component is to be selected from copper, copper zinc alloy, nickel, platinum and the metallic palladium one or more according to the described dehydrogenating alcohol processing method of claim 1.
5,, it is characterized in that described dehydrogenation catalyst is nanometer copper metal or Nanometre Cu-Zn alloy catalyst according to the described dehydrogenating alcohol processing method of claim 1.
6,, it is characterized in that it is 1-100nm that described nano metal particles is on average expected directly according to the described dehydrogenating alcohol processing method of claim 1.
7, according to the described dehydrogenating alcohol processing method of claim 1, the median size that it is characterized in that described nano metal particles is 1-20nm.
8,, it is characterized in that described alcohols reaction raw materials is that to be selected from carbonatoms be in the cycloalkyl alcohol between the 5-10 one or more at the primary alconol of the alkyl of 1-12 and secondary alcohol and carbonatoms according to the described dehydrogenating alcohol processing method of claim 1.
9,, it is characterized in that described temperature of reaction is 130-250 ℃ according to the described dehydrogenating alcohol processing method of claim 2.
10, according to the described dehydrogenating alcohol processing method of claim 2, the inlet amount that it is characterized in that described alcohol is 1-6h with the weight space velocity of the ratio of catalyzer
-1Between.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205175B (en) * | 2007-12-06 | 2011-03-16 | 大连理工大学 | Method for preparing aldehydes or ketones compounds by selective catalytic oxidation of alcohols compounds |
| CN102992984A (en) * | 2011-09-13 | 2013-03-27 | 湖南长岭石化科技开发有限公司 | Methyl ethyl ketone preparation method |
| CN103130625A (en) * | 2011-11-30 | 2013-06-05 | 中国科学院大连化学物理研究所 | Method for preparing acetaldehyde and co-producing acetal by using ethanol |
| CN103497212A (en) * | 2013-09-25 | 2014-01-08 | 浙江科技学院 | Preparation method of rosuvastatin calcium intermediate |
| CN105148911A (en) * | 2015-05-28 | 2015-12-16 | 大连理工大学 | Catalyst for preparing acetaldehyde by ethanol dehydrogenation and its preparation method and use |
| CN105363456A (en) * | 2015-11-05 | 2016-03-02 | 华东理工大学 | Copper-based catalyst and preparation method and application thereof |
| CN105873888A (en) * | 2013-12-26 | 2016-08-17 | 花王株式会社 | Method for producing aldehyde |
| CN107537516A (en) * | 2016-06-28 | 2018-01-05 | 中国石油化工股份有限公司 | Catalyst for preparing sec-butyl alcohol and preparation method thereof |
Families Citing this family (1)
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| CN102850200B (en) * | 2012-09-11 | 2015-09-30 | 西安彩晶光电科技股份有限公司 | A kind of method of suitability for industrialized production 4-hydroxy-cyclohexanone |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205175B (en) * | 2007-12-06 | 2011-03-16 | 大连理工大学 | Method for preparing aldehydes or ketones compounds by selective catalytic oxidation of alcohols compounds |
| CN102992984A (en) * | 2011-09-13 | 2013-03-27 | 湖南长岭石化科技开发有限公司 | Methyl ethyl ketone preparation method |
| CN103130625A (en) * | 2011-11-30 | 2013-06-05 | 中国科学院大连化学物理研究所 | Method for preparing acetaldehyde and co-producing acetal by using ethanol |
| CN103130625B (en) * | 2011-11-30 | 2015-03-11 | 中国科学院大连化学物理研究所 | Method for preparing acetaldehyde and co-producing acetal by using ethanol |
| CN103497212A (en) * | 2013-09-25 | 2014-01-08 | 浙江科技学院 | Preparation method of rosuvastatin calcium intermediate |
| CN103497212B (en) * | 2013-09-25 | 2015-11-18 | 浙江科技学院 | A kind of preparation method of rosuvastain calcium intermediate |
| US9688597B2 (en) | 2013-12-26 | 2017-06-27 | Kao Corporation | Method for producing aldehyde |
| CN105873888A (en) * | 2013-12-26 | 2016-08-17 | 花王株式会社 | Method for producing aldehyde |
| CN105873888B (en) * | 2013-12-26 | 2017-11-21 | 花王株式会社 | Method for preparing aldehyde |
| CN105148911A (en) * | 2015-05-28 | 2015-12-16 | 大连理工大学 | Catalyst for preparing acetaldehyde by ethanol dehydrogenation and its preparation method and use |
| CN105148911B (en) * | 2015-05-28 | 2017-10-24 | 大连理工大学 | The catalyst, its preparation method and application of acetaldehyde are prepared for alcohol dehydrogenase |
| CN105363456A (en) * | 2015-11-05 | 2016-03-02 | 华东理工大学 | Copper-based catalyst and preparation method and application thereof |
| CN107537516A (en) * | 2016-06-28 | 2018-01-05 | 中国石油化工股份有限公司 | Catalyst for preparing sec-butyl alcohol and preparation method thereof |
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