CN102600827A - Catalyst for aldol condensation reaction and preparation method thereof - Google Patents
Catalyst for aldol condensation reaction and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for aldol condensation reaction and a preparation method of the catalyst. The catalyst is prepared by an immersion method, the active ingredient main catalyst is alkali metals or alkaline earth metals, and the cocatalyst is rare earth metals; and the catalyst is obtained by loading one or more of alkali metals or alkaline earth metals on a carrier, simultaneously loading one or more of rare earth metals and calcining at a certain temperature. The catalyst has the characteristics of simple preparation method, low price, high catalytic activity and long life.
Description
Technical field
The Catalysts and its preparation method that the present invention relates to, being mainly used in the low-carbon (LC) linear chain aldehyde is that raw material contacts with catalyst under gas phase state and carries out aldol reaction to produce senior unsaturated aldehyde.
Background technology
Aldol reaction is a kind of very important reaction in the organic chemical reactions; Be used to form the C-C key to increase strand; Its product can be the product hydroxy aldehyde that does not dewater, and also can be the dehydration product unsaturated aldehyde, if reaction under gas phase condition; Because reaction temperature is higher, what obtain usually all is the dehydration product unsaturated aldehyde.
The used catalyst of aldol reaction can be the hydroxide solution of alkali metal or alkaline-earth metal; Be lower than the aldehyde of 15 carbon and/or the aldol reaction of ketone as doing catalyst with the aqueous solution of NaOH among the Chinese patent CN00128456.8; Because catalyst system therefor is an alkali lye, it is cumbersome that reaction finishes the back separating treatment.
If carry out aldol condensation with vapor phase method; The separation of product is just than being easier to; The catalyst that is generally used for the vapor phase method aldol condensation can be with the hydroxide of alkali metal or alkaline-earth metal, oxide, soluble-salt even load on inert carrier, as producing beta-unsaturated ketone with inert particle such as aluminium oxide, silica as the aldol condensation that carrier loaded alkaline metal cpds is used for acetone etc. among the Chinese patent CN01809710.3.
Prepared a kind of solid base catalyst among the Chinese patent CN101367041A; Consist of
wherein 0.6≤x＜2; This catalyst is used for multiple aldol reaction; Such as the condensation reaction of furfural and acetone, 145 ℃ are reacted 10h down, and the conversion ratio of furfural reaches 98%; The furfural acetone selectivity is 85%, and yield is 83.3%.This catalyst is a kind of cobalt aluminium complex type catalyst with spinel structure, and the preparation process is complicated, and selectivity is not high.
Unsaturated aldehyde such as methacrylaldehyde, crotonaldehyde etc. have purposes widely in industry, methacrylaldehyde is the simplest aliphatic unsaturated aldehyde; Because existing vinyl double bond in the molecular structure; The carbonyl conjugated double bond is arranged again, and therefore, its chemical property is very active; Be a kind of important organic synthesis intermediate, in industry, be mainly used in and produce acrylic acid, methionine, pyridine, 3-hydroxy propanal etc.
Wherein, methacrylaldehyde prepares the 3-hydroxy propanal through hydration, repeated hydrogenation preparation 1, and ammediol has good application prospects, and raw materials used methacrylaldehyde can be equipped with methacrylaldehyde like U.S. Pat 2451485 usefulness propylene legal systems through the preparation of propylene selective oxidation.Also can pass through formaldehyde, the preparation of acetaldehyde aldol condensation, get methacrylaldehyde with this legal system like U.S. Pat 2277887, US2288306 etc.These two kinds of methods are suitability for industrialized production all.The propylene method can be come in petroleum refining owing to raw material in a large number; Therefore become the method for main production methacrylaldehyde; But well-known, the world oil reserves are many not as natural gas and coal, along with the exhaustion of petroleum resources; Formaldehyde acetaldehyde condensation method is because therefore raw material can will inevitably obtain development further in a large number from gas chemical industry and Coal Chemical Industry.So be necessary this method is further studied.The prepared catalyst of the present invention just can be used for vapor phase method catalysis formaldehyde, the acetaldehyde aldol condensation is produced methacrylaldehyde.
In U.S. Pat 2277887, Hermann Schulz etc. also carries out aldol condensation with formaldehyde and acetaldehyde and prepares methacrylaldehyde, makees catalyst with Cu, Ag, Ni, Cr etc., but requires can not contain Fe and Al in the catalyst.
In U.S. Pat 2288306, Hans Wagner etc. has developed and has used formaldehyde, the acetaldehyde aldol condensation technology as raw material, and this technology also is one of technology of suitability for industrialized production methacrylaldehyde in early days; Catalyst system therefor is the phosphate of alkali metal and alkaline-earth metal; Used carrier is clay, aluminium oxide etc., and the methacrylaldehyde yield can reach 90%, and this patent is not added rare earth metal in active component; If this catalyst is improved, can obtain higher yield and selectivity.
Crotonaldehyde popular name crotonaldehyde is the important source material of multiple fine chemicals, can be used to produce sorbic acid anticorrisive agent etc., and the preparation method makes aldol with acetaldehyde condensation under alkali condition, dehydration preparation under the diluted acid condition then.Like Chinese patent CN02109587.6 is exactly this method of usefulness, if but under gas phase condition, carry out self aldol condensation of acetaldehyde with the prepared catalyst of the present invention, then can directly obtain crotonaldehyde.
Summary of the invention
The object of the present invention is to provide a kind of gas phase aldol reaction that can be used for by solid catalyst of the senior unsaturated aldehydes of preparation such as low-carbon (LC) linear chain aldehyde such as formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde and preparation method thereof.It is characterized in that used carrier has higher specific surface area and bigger aperture, active component and co-catalyst loaded on the carrier that infusion process can be an incipient impregnation, also can be non-incipient impregnation through infusion process.This preparation method is simple, and Heat stability is good is active high, with low cost, and can regenerate, and can be widely used in the vapor phase method aldol condensation and prepare senior unsaturated aldehyde by the low-carbon (LC) linear chain aldehyde.
Total technical conceive is such:
Carrier can be selected metal oxide such as the activated alumina with both sexes for use, or acid silica gel, also can select for use hydrotalcite to do carrier; Carrier is dried at a certain temperature; If the aperture is too little, can reach desired aperture, dry for standby then through the reaming processing.
Active component alkali metal or alkaline-earth metal can be used its labile salt such as carbonate, bicarbonate, nitrate, nitrite, acetate etc.; Dissolve by catalyst proportion requirement weighing and with appropriate amount of deionized water; Be mixed with certain density solution, obtain solution I; The co-catalyst of selecting for use is the oxide or the soluble-salt of rare earth metal, if oxide, be earlier with strong acid such as nitric acid etc. with its dissolving, the thulium consumption must be prepared by a certain percentage, obtains solution II; With stirring after solution I and the II mixing; Carrier impregnation in mixed solution, is placed a period of time, treat to take out after the abundant load; Oven dry is handled at a certain temperature earlier, in the temperature programming stove, promptly obtains used catalyst with calcination process under the air-flow protection of oxygen-containing atmosphere again.
The concrete operations scheme is following: carrier is example with the activated alumina, and average pore size is 5.0～10.5nm, and specific area is at 200～600m
2/ g.Carrier dries by the fire 1.0～12.0h down at 80～120 ℃, places drier subsequent use.Then according to carrier in the nitrate solution of aluminium element certain molar ratio preparation active component; Dissolving back fully is subsequent use, and its raw material of the rare earth element of interpolation possibly be a nitrate, also possibly be oxide; If nitrate; Directly weighing dissolving makes its solution, exists if rare earth element is a form with oxide, re-uses after then must with a certain amount of dilute nitric acid solution it being dissolved earlier.Above-mentioned salt solution mix is even, then wherein, leave standstill 1.0～24.0h with carrier impregnation.Take out dipping catalyst well,,, remove the inside redundant moisture, simultaneously also more firm having loaded on the carrier of active component so need in baking oven, to dry by the fire under 80～120 ℃ earlier 1.0～12.0h owing to the catalyst behind the dipping is moistening.The tube furnace that then catalyst is placed air stream protection is in 400～800 ℃ of following roasting 1.0～10.0h.Cool to room temperature gets final product.
The specific embodiment
Embodiment 1:
Present embodiment relates generally to the catalyst carrier of estimating formaldehyde, acetaldehyde gas phase cross aldol condensation prepared in reaction methacrylaldehyde with fixed bed reactors.Fixed bed reactors divide two sections, and first section is preheating section, and second section is conversion zone.Filled the glass pellet of inertia in the preheating section reactor, its objective is fully vaporizes the material liquid that adds becomes gas phase state.In order to let the raw material of vaporization be easy to flow, can feed inert gas such as N
2Carry the raw material of having vaporized.Contain not reacted raw material and target product methacrylaldehyde in the gas after reaction finishes, also have inert nitrogen gas, air communication is crossed the cold-trap cooling collect, obtain mix products.With its result of gas chromatographic analysis.
At first estimating the activity of carrier with these fixed bed reactors, is that 10～20 purpose carrier activated aluminas dry by the fire the 12.0h processing down at 110 ℃ with particle diameter, measures 10ml in reactor, and recharging the 10ml particle diameter in the beds upper end is 10～20 purpose glass pellets.The reaction raw materials amount of substance is than being formaldehyde/acetaldehyde=2: 1, and reaction velocity is 1.0h
-1, the temperature of preheating is 250 ℃, and the conversion zone temperature is 320 ℃, and its product methacrylaldehyde is collected through the cold-trap cooling.Analyze with gas-chromatography, methacrylaldehyde is 99.0% in the acetaldehyde selectivity, and the molar yield of raw material acetaldehyde is 38.9%, and the methacrylaldehyde yield is 38.5%.
Adopting said method to estimate particle diameter equally is 10～20 purpose silica gel, and the gas chromatographic analysis result is, methacrylaldehyde is 60.4% in the acetaldehyde selectivity, and the molar yield of raw material acetaldehyde is 28.5%, and the methacrylaldehyde yield is 17.2%.
Embodiment 2:
The catalyst of present embodiment preparation, carrier is an activated alumina, does not add any alkali metal or alkali earth metal, has only added a small amount of rare-earth metals La, and the amount of component materials is than being Al: La=1: 0.01, its preparation method is following:
Carrier activated alumina processing method is said with embodiment 1.Take by weighing the 2.17g lanthanum nitrate hexahydrate in beaker A, add the 60ml deionized water and stirring, obtain solution I up to dissolving fully; The activated alumina particle 61.00g that takes by weighing the front oven dry again places beaker B; Solution I is added among the beaker B, and the limit edged stirs, and adds the back and places dipping; 24.0h back evaporate to dryness redundant moisture is taken out catalyst; 110 ℃ of baking 12.0h place 600 ℃ of calcination process 10.0h of dry oxygen-containing atmosphere with above-mentioned catalyst, the required catalyst that is cooled to room temperature and is again in baking oven.
Adopt the method among the embodiment 1 to estimate this routine catalyst consequently, methacrylaldehyde is 95.4% in the acetaldehyde selectivity, and the molar yield of raw material acetaldehyde is 30.7%, and the methacrylaldehyde yield is 29.3%.
Embodiment 3:
The catalyst of present embodiment preparation, its carrier is an activated alumina, active component is the Li element, does not add any thulium, and the amount of component materials is than being Al: Li=1: 0.04, its preparation method is following:
Carrier activated alumina processing method is said with embodiment 1.Take by weighing the 1.38g lithium nitrate in 100ml beaker A, add the 60ml deionized water dissolving, obtain solution I; The activated alumina particle 61.00g that takes by weighing the front oven dry again places beaker B, and solution I is added among the beaker B, and the limit edged stirs; Add the back and place dipping, the evaporate to dryness redundant moisture is taken out catalyst behind the 24.0h, 110 ℃ of baking 12.0h in baking oven; Again above-mentioned catalyst is placed 600 ℃ of calcination process 10.0h of dry oxygen-containing atmosphere, the required catalyst that is cooled to room temperature and is.
Adopt the method among the embodiment 1 to estimate this routine catalyst consequently, methacrylaldehyde is 88.0% in the acetaldehyde selectivity, and the molar yield of raw material acetaldehyde is 95.1%, and the methacrylaldehyde yield is 83.7%.
Embodiment 4:
The catalyst of present embodiment preparation, its carrier is an activated alumina, and active component is the Li element, and co-catalyst is La, and the amount of component materials ratio is: Al: Li: La=1: 0.04: 0.01, its preparation method was following:
Carrier activated alumina processing method is said with embodiment 1.At first take by weighing the 1.38g lithium nitrate in 100ml beaker A; Add the 30ml deionized water dissolving, obtain solution I, take by weighing the 2.17g lanthanum nitrate hexahydrate again in beaker B; Add the 30ml deionized water and stirring up to dissolving fully; Obtain solution II, solution I and solution II are mixed, obtain mixed solution I II.The activated alumina particle 61.00g that takes by weighing the front oven dry again places beaker C; Mixed solution I II is added among the beaker C, and the limit edged stirs, and adds the back and places dipping; 24.0h back evaporate to dryness redundant moisture is taken out catalyst; 110 ℃ of baking 12.0h place 600 ℃ of calcination process 10.0h of dry oxygen-containing atmosphere with above-mentioned catalyst, the required catalyst that is cooled to room temperature and is again in baking oven.
Adopt the method among the embodiment 1 to estimate this routine catalyst consequently, methacrylaldehyde is 99.0% in the acetaldehyde selectivity, and the molar yield of raw material acetaldehyde is 94.7%, and the methacrylaldehyde yield is 93.8%.
Embodiment 5:
The catalyst of present embodiment preparation, carrier is a silica gel, does not add any alkali metal or alkali earth metal, has only added a small amount of thulium Y, and the amount of component materials is than being Si: Y=1: 0.01, its preparation method is with embodiment 2:
Carrier silica gel is 110 ℃ of baking 6.0h processing down.Take by weighing the 1.13g yittrium oxide in beaker A, add an amount of dilute nitric acid dissolution, treat to add the 30ml deionized water again after its dissolving fully, obtain solution I; The silica gel particle 30.00g that takes by weighing the front oven dry again places beaker B; Solution I is added among the beaker B, and the limit edged stirs, and adds the back and places dipping; 24.0h back evaporate to dryness redundant moisture is taken out catalyst; 110 ℃ of baking 12.0h place 600 ℃ of calcination process 10.0h of dry oxygen-containing atmosphere with above-mentioned catalyst, the required catalyst that is cooled to room temperature and is again in baking oven.
Adopt the method among the embodiment 1 to estimate this routine catalyst consequently, methacrylaldehyde is 95.5% in the acetaldehyde selectivity, and the molar yield of raw material acetaldehyde is 42.6%, and the methacrylaldehyde yield is 40.7%.
Embodiment 6:
The catalyst of present embodiment preparation, its carrier is a silica gel,, active component is the Na element, does not add any thulium, and the amount of component materials is than being Si: Na=1: 0.04, and its preparation method is following:
Carrier activated silica gel processing method is said with embodiment 1.Take by weighing 1.70g sodium nitrate in 100ml beaker A, add the 30ml deionized water dissolving, obtain solution I; The silica gel particle 30.00g that takes by weighing the front oven dry again places beaker B, and solution I is added among the beaker B, and the limit edged stirs; Add the back and place dipping, the evaporate to dryness redundant moisture is taken out catalyst behind the 24.0h, 110 ℃ of baking 12.0h in baking oven; Again above-mentioned catalyst is placed 600 ℃ of calcination process 10.0h of dry oxygen-containing atmosphere, the required catalyst that is cooled to room temperature and is.
Adopt the method among the embodiment 1 to estimate this routine catalyst consequently, methacrylaldehyde is 84.2% in the acetaldehyde selectivity, and the molar yield of raw material acetaldehyde is 88.5%, and the methacrylaldehyde yield is 74.5%.
Embodiment 7:
The catalyst of present embodiment preparation, its carrier is a silica gel, and active component is the Na element, and co-catalyst is Y, and the amount of component materials is than being Si: Na: Y=1: 0.04: 0.01, its preparation method was following:
Carrier silica gel treatment method is said with embodiment 1.At first take by weighing 1.70g sodium nitrate in 100ml beaker A, add the 15ml deionized water dissolving, obtain solution I; Take by weighing the 1.13g yittrium oxide again in beaker A; Add an amount of dilute nitric acid dissolution, treat to add the 15ml deionized water again after its dissolving fully, obtain solution II; Solution I and solution II are mixed, obtain mixed solution I II.The silica gel particle 30.00g that takes by weighing the front oven dry again places beaker C; Mixed solution I II is added among the beaker C, and the limit edged stirs, and adds the back and places dipping; 24.0h back evaporate to dryness redundant moisture is taken out catalyst; 110 ℃ of baking 12.0h place 600 ℃ of calcination process 10.0h of dry oxygen-containing atmosphere with above-mentioned catalyst, the required catalyst that is cooled to room temperature and is again in baking oven.
Adopt the method among the embodiment 1 to estimate this routine catalyst consequently, methacrylaldehyde is 98.8% in the acetaldehyde selectivity, and the molar yield of raw material acetaldehyde is 92.4%, and the methacrylaldehyde yield is 91.3%.
Embodiment 8:
Present embodiment relates to and prepares crotonaldehyde through acetaldehyde self aldol reaction under gas phase condition and estimate the prepared catalyst of embodiment 4.Reactor is said identical with embodiment 1, and raw material is used acetaldehyde liquid, through N
2Bubbling is brought acetaldehyde steam in the reactor into, control N
2Flow velocity is controlled the raw material air speed at 1.0h
-1, reaction temperature is 320 ℃, and product is collected with cold-trap cooling back, and with gas chromatographic analysis consequently, the crotonaldehyde selectivity is 97.9%, and acetaldehyde conversion is 90.1%, the crotonaldehyde yield is 88.2%.
Embodiment 9～11:
Embodiment 9～11 catalyst system therefors are identical with embodiment 7 with embodiment 1, and reactor and operating condition are with embodiment 8, and the result is shown in table one:
Table one: acetaldehyde self aldol condensation result relatively under the different catalysts proportioning
Claims (7)
- One kind to be used for the low-carbon (LC) linear chain aldehyde be that raw material carries out the catalyst that aldol reaction is produced senior unsaturated aldehyde under gas phase condition; It is characterized in that: the catalyst activity component is one or more among alkali metal or alkaline-earth metal Li, Na, K, Mg, the Ca; Co-catalyst is one or more among rare-earth metal La, Ce, Pr, Nd, Sm, Gd, the Y, and the amount of catalyst component is than being carrier: active component: co-catalyst=1: 0.0001～0.20: 0.0001～0.10.
- 2. claim 1 said Preparation of catalysts method; It is characterized in that: active component and co-catalyst are processed salting liquid; Again carrier is added and dipping; The catalyst that dipping is good dries by the fire 1.0～12.0h earlier under 80～120 ℃ in baking oven, 400～800 ℃ of roasting 1.0～10.0h in oxygen-containing atmosphere promptly obtain required catalyst again.
- 3. according to claim 2 said Preparation of catalysts methods, it is characterized in that: it is characterized in that said carrier is a kind of in activated alumina, silica gel, diatomite, magnesia, the hydrotalcite.
- 4. according to claim 2 said Preparation of catalysts methods, it is characterized in that: it is characterized in that alkali metal or alkaline-earth metal and rare earth metal all use with its soluble-salt form, soluble-salt is carbonate, bicarbonate, nitrate, nitrite or acetate.
- 5. according to claim 2 said Preparation of catalysts methods, it is characterized in that: preferred activated alumina of carrier or silica gel; Carrier should be processed rule or irregular particle, in 80～120 ℃, dries by the fire 1.0～12.0h earlier.
- 6. according to the said Preparation of catalysts method of claim 1; It is characterized in that: the nitrate of the preferred Li of active component alkali metal or alkaline-earth metal, Na, K, Mg, Ca, and co-catalyst rare-earth metal La, Ce, Pr, Nd, Sm, Gd, preferred its nitrate of Y or oxide.
- 7. method of producing senior unsaturated aldehyde, it is characterized in that the low-carbon (LC) linear chain aldehyde contacts with the described catalyst of claim 1 under gas phase condition carries out self or senior unsaturated aldehyde is produced in the cross aldol condensation reaction.
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| CN105381796A (en) * | 2015-10-15 | 2016-03-09 | 中国科学院山西煤炭化学研究所 | Catalyst for hydrodeoxygenation of organic oxygen containing compound in oil product, preparation method and application |
| CN105392782A (en) * | 2013-06-03 | 2016-03-09 | 加利福尼亚大学董事会 | Methods for producing fuels, gasoline additives, and lubricants |
| CN107824175A (en) * | 2017-11-01 | 2018-03-23 | 唐山中溶科技有限公司 | For synthesizing loaded catalyst and its application of the hydroxy propanal of 2,2 dimethyl 3 |
| US10106480B2 (en) | 2014-10-29 | 2018-10-23 | The Regents Of The University Of California | Methods for producing fuels, gasoline additives, and lubricants using amine catalysts |
| US10138193B2 (en) | 2014-10-29 | 2018-11-27 | The Regents Of The University Of California | Methods for producing fuels, gasoline additives, and lubricants using amine catalysts |
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| CN112390712A (en) * | 2019-08-14 | 2021-02-23 | 中国科学院青岛生物能源与过程研究所 | Method for preparing 1, 3-butanediol by adopting fixed bed continuous reaction |
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| US9738617B2 (en) | 2013-06-03 | 2017-08-22 | The Regents Of The University Of California | Methods for producing fuels, gasoline additives, and lubricants |
| EP3004072B1 (en) * | 2013-06-03 | 2019-11-27 | The Regents of The University of California | Methods for producing fuels, gasoline additives, and lubricants |
| US10106480B2 (en) | 2014-10-29 | 2018-10-23 | The Regents Of The University Of California | Methods for producing fuels, gasoline additives, and lubricants using amine catalysts |
| US10138193B2 (en) | 2014-10-29 | 2018-11-27 | The Regents Of The University Of California | Methods for producing fuels, gasoline additives, and lubricants using amine catalysts |
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| CN107824175A (en) * | 2017-11-01 | 2018-03-23 | 唐山中溶科技有限公司 | For synthesizing loaded catalyst and its application of the hydroxy propanal of 2,2 dimethyl 3 |
| CN109603795A (en) * | 2018-12-13 | 2019-04-12 | 万华化学集团股份有限公司 | Solid base catalyst and the production technology for preparing 4- (2- furyl)-3- butene-2 -one |
| CN112390712A (en) * | 2019-08-14 | 2021-02-23 | 中国科学院青岛生物能源与过程研究所 | Method for preparing 1, 3-butanediol by adopting fixed bed continuous reaction |
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Application publication date: 20120725 |