CN1232351C - Preparation and uses of methylacrolein catalyst produced by oxidation of isobutene or tert-butyl alcohol - Google Patents
Preparation and uses of methylacrolein catalyst produced by oxidation of isobutene or tert-butyl alcohol Download PDFInfo
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- CN1232351C CN1232351C CN 02124256 CN02124256A CN1232351C CN 1232351 C CN1232351 C CN 1232351C CN 02124256 CN02124256 CN 02124256 CN 02124256 A CN02124256 A CN 02124256A CN 1232351 C CN1232351 C CN 1232351C
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Abstract
The present invention relates to a method for preparing a composite catalyst. The main constituents of the composite catalyst contain molybdenum, bismuth and ferrum; the composite catalyst is mainly applied to the reaction of preparing methylacrolein by selectively oxidizing isobutylene or tertiary butyl alcohol. In the catalyst preparation process, the two steps of preparation technologies in the prior art respectively used for preparing molybdenum oxide and calcifying catalysts are merged into one step; compared with the prior art, the novel preparation method has the advantages of simple technology and energy saving; the added molybdenum components can be uniformly mixed with the active components in the composite catalyst so as to effectively replenish the loss of the molybdenum components in the composite catalyst.
Description
Technical field the present invention relates to the preparation method that a kind of principal constituent contains the composite catalyst of molybdenum, bismuth and iron, and this catalyzer is mainly used in iso-butylene or trimethyl carbinol selective oxidation generates in the reaction of Methylacrylaldehyde.
The background technology Methylacrylaldehyde, 69 ℃ of boiling points are the important intermediate of synthesize methyl acrylic acid and methyl methacrylate, also are the synthetic intermediates of important organic productss such as synthetic drugs, dyestuff.Methylacrylaldehyde generally is being raw material by the iso-butylene or the trimethyl carbinol, under the effect of catalyzer, by airborne oxygen selectivity oxidized obtaining.
Many improved catalyzer are used to iso-butylene or Oxidation of t-Butanol prepares in the reaction of Methylacrylaldehyde.Nearly all catalyzer all contains molybdenum, bismuth and iron as its main component.
Yet, in the industrial production of Methylacrylaldehyde, a lot of catalyzer only just can demonstrate higher catalytic efficiency under the reaction conditions more than 400 ℃, under high like this temperature and continual successive reaction condition, still exist the short subject matter of catalyst life always.
In molybdenum, bismuth and iron combination catalyst, molybdenum is to make catalyzer have the topmost composition of oxidation activity, but it is easy to distillation.Generating Methylacrylaldehyde by iso-butylene or Oxidation of t-Butanol is a strong exothermic reaction, easily forms a plurality of or large stretch of local superheating district at the catalyst reaction floor.In these local superheating districts, molybdenum distils consumingly, causes that the content of molybdenum seriously runs off in the catalyzer, causes the irreversible decline of catalyst activity.The method of the short problems of many solution catalyst lifes was once proposed, as with inert substance with catalyst dilution (Japan's special permission discloses 10614/1972); Use piped catalyzer (Japan's special permission communique 36739/1987); In reaction tubes, form two reaction zones (day patent application 127013/1976 of the present disclosure); From the unstripped gas outlet that enters the mouth, with catalyzer by active by little to big order filling (Japanese patent laid-open publication gazette 38331/1988; Japan's special permission discloses 217932/1992) etc.These methods have been alleviated the serious problem that runs off of molybdenum component in the local superheating district to a certain extent, but can not guarantee the deterioration problem of long term inhibition catalyzer.Therefore, these methods can not satisfy industrial requirement.Nineteen ninety-five, SUMITOMO CHEMICAL chemical industry Co., Ltd. patent (CN 1099024) propose in ready-made catalyzer, to add molybdenum oxide as catalyzer in the replenishing of loss molybdenum.1999, Lanzhou chemical industrial company patent (CN 1042200) proposed directly activity of such catalysts component ammonium molybdate partly to be made into the form adding of molybdenum oxide.But the molybdenum oxide of SUMITOMO CHEMICAL chemical industry Co., Ltd. patent (CN 1099024) and Lanzhou chemical industrial company patent (CN 1042200) all is by ammonium molybdate is added thermosetting at high temperature (300～600 ℃) with for a long time, so not only cause energy dissipation, and in industrial production, more than prepare this reaction process of molybdenum oxide by ammonium molybdate, this can make the facility investment of industrial production Methylacrylaldehyde and production cost improve greatly.
Summary of the invention the objective of the invention is to find a kind of preparation to be produced the novel method of the catalyzer of Methylacrylaldehyde by iso-butylene or Oxidation of t-Butanol, it compared with prior art, simple except having technology, save outside the advantage of the energy, the molybdenum component that also has an interpolation can uniform distribution in catalyzer, makes the molybdenum component that runs off in the catalyzer can access more effective additional characteristics.
The contained component of composite oxide catalyst by iso-butylene or Oxidation of t-Butanol production Methylacrylaldehyde that the present invention obtains is represented with following formula:
MoaWbBicFedSbeCofZngKhCsiOx
Wherein Mo is that molybdenum, W are that tungsten, Bi are that bismuth, Fe are that iron, Sb are that antimony, Co are that cobalt, Zn are that zinc, K are that potassium, Cs are that caesium, O are oxygen.A, b, c, d, e, f, g, x represent every kind of atoms of elements than a=12+ (1.2～4.8), b=0～3.8, c=0.1～1.0, d=0.8～3 respectively, e=0～1.5, f=5～8, g=0～0.5, h=0～0.8, i=0～0.05, x is the numerical value that satisfies other element oxidation state.
It is characterized in that containing in the process of composite catalyst of molybdenum, bismuth and iron in the preparation principal constituent, usefulness in the existing technology two step process are prepared the reaction of the molybdenum oxide in catalyzer molybdenum source as a supplement respectively and a step is merged in the roasting reaction of catalyzer, wherein 1) as a supplement the molybdenum oxide in catalyzer molybdenum source directly heat together and produce by ammonium molybdate and activity of such catalysts component; 2) amount of the raw material ammonium molybdate of preparation molybdenum oxide is 1.2～4.8: 12 (W/W) with the ratio of the amount of the ammonium molybdate of preparation catalyst activity component needs; 3) technological temperature of preparation molybdenum oxide and the roasting of catalyzer single stage method is 450～550 ℃, and the time is 8～10 hours.
The present invention adds the molybdenum source that the replenishes form with ammonium molybdate in the after baking stage of catalyzer, 450～550 ℃ of maturing temperatures, and the roasting time of catalyzer extends to 8～10 hours by 3 hours of general catalyzer.Add with such method and to prevent the molybdenum source that catalyst degradation need replenish, saved not only that (CN 1099024 in the previous patent; CN 1042200) preparation molybdenum oxide technology, make production technique simple, and can also make catalyzer with in the process of heat (450～550 ℃ altogether of ammonium molybdates, 8 hours) roasting fully, the composite oxide catalyst that obtains has Methylacrylaldehyde transformation efficiency height, the advantage that catalyst life is long.
Specify the present invention with embodiment below.The selectivity definition of term transformation efficiency and Methylacrylaldehyde is as follows:
Embodiment 1
100 parts of ammonium molybdates, 2.46 parts of ammonium paratungstates and 4.6 parts of cesium nitrates join in 200 parts the water, stirring heating (solution A).Simultaneously with 46.16 parts iron nitrate, the magnesium nitrate of 83.78 parts Xiao Suangu and 12.02 parts joins in 140 parts the water successively, makes solution B.Solution B is joined in the solution A, stir and form mud.
8.4 parts 60% aqueous nitric acid are joined in 80 parts the water, behind the solution homogeneous phase, add 13.74 parts Bismuth trinitrate.After the Bismuth trinitrate dissolving, add 20.58 parts nickelous nitrate and 4.82 parts ANTIMONY TRIOXIDE SB 203 99.8 PCT, mix, add 33 part 28% ammoniacal liquor then, obtain containing the blue solution of white precipitate.The solution heated and stirred is evaporated contained water, obtains solid.30 parts ammonium molybdates and this solid are mixed the back under 500 ℃, calcification 8 hours, the catalyzer that obtains (I) has following component:
Mo
15.6W
0.1Bi
0.9Fe
1.3Sb
1.2Co
6.2Zn
0.3K
0.06O
x
Embodiment 2
The ammonium molybdate of 159 grams is dissolved in the water of 1200ml in heating with under stirring, adds the Xiao Suangu of 139.6 grams, the iron nitrate of 72.20 grams successively.After fully stirring, the slow Bismuth trinitrates that add by 8.57 grams, the solution that the nitric acid of 15ml60% and 150ml water are formed, and then add the cesium nitrate that restrains by 35.2, the solution that the nitric acid of 10ml 60% and 100ml water are formed.Fully stir above-mentioned solution, with ammoniacal liquor with solution pH=3～4 that neutralize.Solution boiled off moisture in Rotary Evaporators after, obtain solid.The solid and 40 ammonium molybdates that restrain that obtain are mixed, under 550 ℃, roasting 10 hours.The catalyzer that obtains (II) has following component:
Mo
15.1Bi
0.3Fe
3.0Co
8.0Cs
3.0O
x
Embodiment 3
Being evaluated in the microreactor that has online gas-chromatography of catalyzer carried out.The catalyzer (I) of 1 gram is packed in φ 3 reaction tubess, will consist of iso-butylene 5% then, nitrogen 75%, the mixed gas of oxygen 20% (V/V), reacts under 340 ℃ temperature of reaction by reaction tubes with the air speed of 1800/h.Online gas chromatographic analysis result shows that conversion for isobutene is 99.2%, and the selectivity of Methylacrylaldehyde is 86%.Reaction continued after 4000 hours, and conversion for isobutene is 99.5%, and the selectivity of Methylacrylaldehyde is 85.7%.
Embodiment 4
Being evaluated in the microreactor that has online gas-chromatography of catalyzer carried out.The catalyzer (II) of 1 gram is packed in φ 3 reaction tubess, will consist of iso-butylene 5% then, nitrogen 75%, the mixed gas of oxygen 20% (V/V), reacts under 340 ℃ temperature of reaction by reaction tubes with the air speed of 1800/h.Online gas chromatographic analysis result shows that conversion for isobutene is 99.7%, and the selectivity of Methylacrylaldehyde is 89%.Reaction continued after 4000 hours, and conversion for isobutene is 99.6%, and the selectivity of Methylacrylaldehyde is 90.2%.
Embodiment 5
Being evaluated in the microreactor that has online gas-chromatography of catalyzer carried out.The catalyzer (I) of 1 gram is packed in φ 3 reaction tubess, will consist of the trimethyl carbinol 5% then, nitrogen 75%, the mixed gas of oxygen 20% (V/V), reacts under 350 ℃ temperature of reaction by reaction tubes with the air speed of 1800/h.Online gas chromatographic analysis result shows that the transformation efficiency of the trimethyl carbinol is 99.0%, and the selectivity of Methylacrylaldehyde is 85.5%.Reaction continued after 4000 hours, and the transformation efficiency of the trimethyl carbinol is 99.3%, and the selectivity of Methylacrylaldehyde is 85.7%.
Embodiment 6
Being evaluated in the microreactor that has online gas-chromatography of catalyzer carried out.The catalyzer (II) of 1 gram is packed in φ 3 reaction tubess, will consist of the trimethyl carbinol 5% then, nitrogen 75%, the mixed gas of oxygen 20% (V/V), reacts under 350 ℃ temperature of reaction by reaction tubes with the air speed of 1800/h.Online gas chromatographic analysis result shows that the transformation efficiency of the trimethyl carbinol is 99.3%, and the selectivity of Methylacrylaldehyde is 88.5%.Reaction continued after 4000 hours, and the transformation efficiency of the trimethyl carbinol is 99.3%, and the selectivity of Methylacrylaldehyde is 90.0%.
Claims (1)
- A kind of principal constituent contains the preparation method of molybdenum, bismuth and iron composite catalyst, it is characterized in that containing in the process of composite catalyst of molybdenum, bismuth and iron in the preparation principal constituent, usefulness in the existing technology two step process are prepared the reaction of the molybdenum oxide in catalyzer molybdenum source as a supplement respectively and a step is merged in the roasting reaction of catalyzer, wherein 1) as a supplement the molybdenum oxide in catalyzer molybdenum source directly heat together and produce by ammonium molybdate and activity of such catalysts component; 2) amount of the raw material ammonium molybdate of preparation molybdenum oxide is 1.2～4.8: 12 (W/W) with the ratio of the amount of the ammonium molybdate of preparation catalyst activity component needs; 3) technological temperature of preparation molybdenum oxide and the roasting of catalyzer single stage method is 450～550 ℃, and the time is 8～10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02124256 CN1232351C (en) | 2002-07-12 | 2002-07-12 | Preparation and uses of methylacrolein catalyst produced by oxidation of isobutene or tert-butyl alcohol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02124256 CN1232351C (en) | 2002-07-12 | 2002-07-12 | Preparation and uses of methylacrolein catalyst produced by oxidation of isobutene or tert-butyl alcohol |
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|---|---|
| CN1467032A CN1467032A (en) | 2004-01-14 |
| CN1232351C true CN1232351C (en) | 2005-12-21 |
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| CN 02124256 Expired - Lifetime CN1232351C (en) | 2002-07-12 | 2002-07-12 | Preparation and uses of methylacrolein catalyst produced by oxidation of isobutene or tert-butyl alcohol |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314487C (en) * | 2004-11-26 | 2007-05-09 | 上海华谊丙烯酸有限公司 | Catalyst for selectively oxidizing tertiary butanol or isobutene to synthesize methyl acrylic aldehyde and its use |
| FR2940801B1 (en) * | 2009-01-06 | 2012-08-17 | Arkema France | PROCESS FOR THE PRODUCTION OF A METHYL METHACRYLATE DERIVED FROM BIOMASS |
| CN102389806A (en) * | 2011-10-08 | 2012-03-28 | 连云港阳方催化科技有限公司 | Catalyst for synthesizing acrolein through catalytic oxidation of propylene and preparation method for catalyst |
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