CN101462044B - Catalyst for producing crotonaldehyde - Google Patents
Catalyst for producing crotonaldehyde Download PDFInfo
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- CN101462044B CN101462044B CN2009100281926A CN200910028192A CN101462044B CN 101462044 B CN101462044 B CN 101462044B CN 2009100281926 A CN2009100281926 A CN 2009100281926A CN 200910028192 A CN200910028192 A CN 200910028192A CN 101462044 B CN101462044 B CN 101462044B
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- catalyst
- molecular sieve
- crotonaldehyde
- alkaline earth
- metal oxide
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Abstract
The invention provides a catalyst for producing crotonaldehyde, which takes a complex consisting of alkaline earth metal oxide and a molecular sieve or alumina as a carrier, and is prepared by supporting alkaline metal oxide by adopting an impregnation method. Alkaline earth metal is magnesium, calcium or barium, the molecular sieve is an HZSM-5, Hbeta, HY, USY or rare earth Y(ReY) molecular sieve, the alumina is gamma-Al2O3, and alkaline metal is lithium, sodium, potassium or cesium. The mass ratio of the alkaline earth metal oxide and the molecular sieve or the alumina which are taken as the carrier of the catalyst is 1: 20-20: 1, and the mass of the alkaline metal oxide is 1 to 30 percent of the total mass of the complex consisting of the alkaline earth metal oxide and the molecular sieve or the alumina. Compared with a solid catalyst reported by literature, the catalyst has better low-temperature activity, namely the reaction temperature is lower than that of the catalyst reportedby literature when the conversion rate of acetaldehyde is equivalent to the selectivity of the crotonaldehyde. The method also additionally produces tolyl aldehyde with higher added value when synthesizing a main product, namely the crotonaldehyde, and further promotes the economic benefit of the catalyst.
Description
Technical field
The present invention relates to a kind of catalyst of producing crotonaldehyde.
Background technology
Crotonaldehyde claims 2-crotonaldehyde, Beta-methyl methacrylaldehyde again.Crotonaldehyde is a kind of important organic chemical industry's intermediate, has extensive use in fields such as food, resin, binding agent and dyestuffs.Crotonaldehyde and ketenes reaction synthesizing efficient, low toxicity food preservative sorbic acid (potassium) can make epoxy resin raw material and epoxy plasticizer with the butadiene reaction, can obtain the heat stable resin raw material with the pentaerythrite reaction.The crotonaldehyde oxidation can make crotonic acid, and its copolymer is used as binding agent in papermaking, medicine and textile industry.Crotonaldehyde can also with ethylenediamine synthetic asphalts additive, with nitrogenous organic matter synthetic lubricant fluid viscosity index improver etc.
It is liquid phase condensation, the dehydration two-step reaction technique of raw material that the suitability for industrialized production of present crotonaldehyde generally adopts with acetaldehyde, i.e. acetaldehyde condensation in dilute NaOH solution generates the 3-hydroxybutyraldehyde, and dehydration generates crotonaldehyde in dilute acetic acid solution then.Condensation and dehydration can be carried out in tank reactor or tower reactor.But this technology is owing to adopt dilute sodium hydroxide and spirit of vinegar respectively as condensation and dehydration catalyst, the technology water yield of being brought into by catalyst is very big, produce the water yield that 1 ton of crotonaldehyde brings into and reach 50 tons more than, cause having a large amount of waste water to need discharging, and crotonaldehyde and water easily form azeotropic mixture, it is bigger to separate a large amount of water consumptions, and acid, base catalyst easily produce corrosion to equipment simultaneously.Chinese patent CN1807381 has reported that the employing organic amine substitutes NaOH as aldol condensation catalyst, makes reaction become gentle, is easy to control, and has reduced the corrosion of highly basic to equipment.
Adopt solid catalyst to carry out acetaldehyde condensation and prepare crotonaldehyde, can overcome the defective that technology exists when adopting liquid base, acid catalyst, and solid catalyst is easy to separate with product, and is reusable, and its environmental advantage and cost advantage all are fairly obvious.Ji etc. [Applied Catalysis A, 1997,161:93-104.] have reported the method for acetaldehyde condensation processed fructus crotonis aldehyde on silica supported alkali metal oxide catalyst, and the silicate of this catalyst surface may be main active phase, and ZrO
2And ZrO
2-SO
4 2-Show catalytic capability preferably.[Applied catalysis A such as Chang, 2000,190:149-155.] reported acetaldehyde gas-phase reaction processed fructus crotonis aldehyde technology on HX, NaX and three kinds of molecular sieves of KX, under 400 ℃ of reaction temperatures, the acetaldehyde conversion of HX, NaX and three kinds of catalyst of KX is respectively 25.9%, 28.6% and 30.6%, and the selectivity of crotonaldehyde is respectively 46.6%, 60.6% and 55.2%.[Applied Clay Science such as Kaagunya, 1995,10:95-102.] reported the liquid phase aldol reaction of acetaldehyde on the houghite catalyst, the activated centre of acetaldehyde self-condensation reaction is a basic sites, improves base strength and can promote the acetaldehyde self-condensation reaction.Under 90～130 ℃ and 10bar, acetaldehyde conversion is 36.6%, and crotonaldehyde selective is 71.7%.From above document as can be seen, the reaction temperature of acetaldehyde vapour phase condensation reaction is higher on the molecular sieve catalyst of silicon dioxide carried alkali metal and alkali metal exchange, and conversion ratio and crotonaldehyde selective are all lower, especially are difficult to reach simultaneously high conversion and high selectivity.Though the houghite catalyst has also obtained higher selectivity under higher conversion, reaction pressure is higher, has all limited the development of adopting this explained hereafter crotonaldehyde technology.
Summary of the invention
The object of the present invention is to provide a kind of catalyst of producing crotonaldehyde, be used for the acetaldehyde gas solid catalytic reaction.
Described catalyst is the solid acid alkali catalytic agent, and the compound of being made up of alkaline earth oxide and molecular sieve or aluminium oxide is a carrier, adopts infusion process carrying alkali metal oxide to make.Described alkaline-earth metal is magnesium, calcium or barium, and the presoma of alkaline earth oxide can directly use corresponding oxide, also can select corresponding hydroxide or nitrate.Described molecular sieve is HZSM-5, H β, HY, USY or Rare Earth Y (ReY) molecular sieve, and described aluminium oxide is γ-Al
2O
3Described alkali metal thing is lithium, sodium, potassium or caesium, and the presoma of alkali metal oxide can be hydroxide, halide, nitrate or carbonate.As the alkaline earth oxide of catalyst carrier and the mass ratio of molecular sieve or aluminium oxide is 1: 20～20: 1, preferred 1: 10～10: 1.The quality of alkali metal oxide is 1～30%, preferred 3～10% of alkaline earth oxide and molecular sieve or an alumina compound gross mass.
The present invention produces the Preparation of catalysts method of crotonaldehyde, comprises the steps:
1, with the alkali metal presoma, uses dissolved in distilled water, be made into mass concentration and be 5～15% solution;
2, with alkaline earth oxide presoma, aluminium oxide or molecular sieve carrier according to 1: 20～20: 1 quality proportionings, the solution that joins in the step 1 to be joined stirs it is fully mixed;
3, with behind the above-mentioned solution left standstill, put into oven drying to constant weight;
4, the block that drying is obtained is pulverized, and adds the field mountain valley with clumps of trees and bamboo powder of gross mass 5～40%, adds the Ludox of gross mass 5～40% again, extrusion molding;
5, preformed catalyst after the drying, is put into Muffle furnace at 450～600 ℃ of following calcination 4hr in baking oven, and taking-up is put into drier and cooled off.
Another object of the present invention is to utilize the method for the synthetic crotonaldehyde of described production crotonaldehyde catalyst one-step method.
Using catalyst of the present invention, is raw material with high-purity technical acetaldehyde, is carrier gas with nitrogen or hydrogen, and in the fixed bed reactors of the described catalyst of filling, single step reaction generates crotonaldehyde, simultaneously the tolyl aldehyde product of by-product high added value.
Reaction temperature with described Preparation of Catalyst crotonaldehyde is 200～400 ℃, and preferred 250～350 ℃, carrier gas is a nitrogen, and the mass space velocity of acetaldehyde is 0.1～50hr
-1, preferred 0.2～10hr
-1
The reaction mechanism mechanism of reaction of the direct condensation processed fructus crotonis of acetaldehyde gas phase aldehyde experience condensation in the prior art, two reactions steps of dewatering, condensation reaction should be adopted base catalyst, dehydration should adopt acidic catalyst, therefore its catalyst need have alkalescence and acidic catalyst function preferably simultaneously, the carrier that molecular sieve etc. is had the acid catalysis effect in the present invention is compound as carrier with the carrier magnesia with base catalysis, the carrying alkali metal oxide prepares the soda acid bifunctional catalyst, be used for acetaldehyde vapour phase condensation processed fructus crotonis aldehyde, improve the conversion ratio and the selectivity of reaction, and obtain the accessory substance of high added value, improve the economic benefit of this process.
The inventive method is compared with the liquid phase two-step synthetic method has following advantage: (1) adopts solid catalyst, and is environmentally friendly, and equipment is not had corrosion; (2) the synthetic crotonaldehyde of the inventive method acetaldehyde one step condensation reaction, technological process is short; (3) the inventive method does not need to add entry in reaction, and therefore the wastewater flow rate that produces is compared with liquid phase method and significantly reduced, and separating energy consumption also reduces greatly.Compare with the solid catalyst of bibliographical information, the catalyst that the inventive method adopts has better low temperature activity, and just when acetaldehyde conversion was suitable with crotonaldehyde selective, reaction temperature was lower than the catalyst of bibliographical information.And the inventive method is gone back the more tolyl aldehyde of high added value of by-product when synthetic major product crotonaldehyde, further promoted the technology of the present invention economic benefit.
Embodiment
Further describe the present invention below in conjunction with embodiment, but scope of the present invention is not limited to these embodiment.
Embodiment 1～6:
Weighing m 1g alkali metal oxide presoma is used dissolved in distilled water, and mass concentration is 15%.Weighing m 2g alkaline earth oxide presoma and m3gAl
2O
3, add in the alkali metal precursor water solution, stirred 5 hours under the room temperature, left standstill then 12 hours, under 100 ℃, be dried to constant weight.The field cyanogen powder that grinds back adding gross mass 15% mixes, the Ludox that adds gross mass 20% again, after mixing, extrusion molding on the shaping of catalyst machine, in Muffle furnace, calcined 4 hours down then in 550 ℃, cooled catalyst through broken, sieve, get 20～40 order catalyst, it is standby to put into drier.Several Preparation of catalysts conditions see Table 1.
Table 1
| The catalyst sequence number | The alkali metal oxide presoma | m1 /g | The alkaline earth oxide presoma | m2 /g | Al 2O 3m3 /g |
| 1 | KOH | 1.2 | MgO | 95.2 | 4.8 |
| 2 | NaNO 3 | 8.2 | MgO | 25.0 | 75.0 |
| 3 | KF | 6.2 | Mg(OH) 2 | 120.8 | 16.7 |
| 4 | Cs 2CO 3 | 11.6 | Mg(NO 3) 2 | 17.8 | 95.2 |
| 5 | LiOH | 32.0 | Ba(OH) 2 | 11.2 | 90.0 |
| 6 | KNO 3 | 64.5 | Ca(OH) 2 | 105.7 | 20.0 |
Embodiment 7～12:
Get the catalyst 20g among the embodiment 1～6, in the fixed bed reactors of packing into.Under 300 ℃ of normal pressures, reaction temperature, with N
2As carrier gas, acetaldehyde carries out gas chromatographic analysis with the charging of certain quality air speed to the gained product, calculates the selectivity of acetaldehyde conversion, crotonaldehyde selective and main accessory substance tolyl aldehyde.Reaction result sees Table 2.
Table 2
| The catalyst sequence number | Acetaldehyde mass space velocity/h -1 | N 2Flow/mL/min | Acetaldehyde conversion/% | Crotonaldehyde selective/% | Tolyl aldehyde selectivity/% |
| 7 | 0.1 | 0 | 40.0 | 65.4 | 10.6 |
| 8 | 0.3 | 25 | 36.9 | 66.5 | 9.2 |
| 9 | 0.5 | 50 | 49.6 | 58.2 | 16.2 |
| 10 | 1.0 | 100 | 23.3 | 73.3 | 4.7 |
| 11 | 10.0 | 150 | 21.8 | 78.4 | 4.5 |
| 12 | 50.0 | 200 | 20.6 | 80.4 | 4.2 |
Embodiment 13～16:
Weighing m 1 gram alkali metal oxide presoma is used dissolved in distilled water, and mass concentration is 5%.Weighing m 2 gram alkaline earth oxide presomas and m3 gram molecule sieve add in the alkali metal oxide precursor water solution, stir 5 hours under the room temperature, leave standstill then 12 hours, are dried to constant weight under 100 ℃.The field cyanogen powder that grinds back adding gross mass 20% mixes, the Ludox that adds gross mass 20% again, after mixing, extrusion molding on the shaping of catalyst machine, calcined 4 hours down in 550 ℃ in Muffle furnace then, cooled catalyst breakage sieves, get 20～40 order catalyst, it is standby to put into drier.Several Preparation of catalysts conditions see Table 3.
Table 3
| The catalyst sequence number | The alkali metal oxide presoma | m1 /g | The alkaline earth oxide presoma | m2 /g | Molecular sieve | m3 /g |
| 13 | KOH | 3.6 | MgO | 25.0 | HZSM-5 | 75.0 |
| 14 | NaOH | 3.9 | MgO | 50.0 | Hβ | 50.0 |
| 15 | KF | 6.2 | Mg(OH) 2 | 108.8 | ReY | 25.0 |
| 16 | KF | 12.3 | Mg(NO 3) 2 | 338.0 | HY | 10.0 |
Embodiment 17～20:
Get the catalyst 20g among the embodiment 13～16, in the fixed bed reactors of packing into.At acetaldehyde fed mass space velocity 0.4h
-1, carrier gas N
2Flow 50mL/min, normal pressure, 300 ℃ of reactions are down carried out gas chromatographic analysis to the gained product, calculate the selectivity of acetaldehyde conversion, crotonaldehyde selective and main accessory substance tolyl aldehyde.Reaction result sees Table 4.
Table 4
| The catalyst sequence number | Reaction temperature/℃ | Acetaldehyde conversion/% | Crotonaldehyde selective/% | Tolyl aldehyde selectivity/% |
| 17 | 200 | 15.1 | 85.1 | 3.4 |
| 18 | 250 | 24.9 | 79.1 | 4.1 |
| 19 | 300 | 34.6 | 72.2 | 6.2 |
| 20 | 400 | 40.3 | 65.3 | 8.7 |
Claims (4)
1. catalyst of producing crotonaldehyde, the compound of being made up of alkaline earth oxide and molecular sieve or aluminium oxide is a carrier, adopt infusion process carrying alkali metal oxide to make, described alkaline-earth metal is magnesium, calcium or barium, described molecular sieve is HZSM-5, H β, HY, USY or Rare Earth Y, and described aluminium oxide is γ-Al
2O
3, described alkali metal is lithium, sodium, potassium or caesium, and the mass ratio of alkaline earth oxide and molecular sieve or aluminium oxide is 1: 20～20: 1, and the quality of alkali metal oxide is 1～30% of alkaline earth oxide and molecular sieve or an alumina compound gross mass.
2. catalyst according to claim 1, it is characterized in that: the mass ratio of alkaline earth oxide and molecular sieve or aluminium oxide is 1: 10～10: 1, and the quality of alkali metal oxide is 3～30% of alkaline earth oxide and molecular sieve or an alumina compound gross mass.
3. a method of producing crotonaldehyde is a raw material with acetaldehyde, is carrier gas with nitrogen, adopts the described catalyst of claim 1, at 200～400 ℃ of next step synthetic crotonaldehydes of temperature, and the by-product tolyl aldehyde.
4. method according to claim 3 is characterized in that: at 250～350 ℃ of next step synthetic crotonaldehydes of temperature, and the by-product tolyl aldehyde.
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016066869A1 (en) | 2014-10-30 | 2016-05-06 | Abengoa Research, S.L. | Microporous catalyst with selective encapsulation of metal oxides, used to produce butadiene precursors |
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|---|---|---|---|---|
| CN102188967B (en) * | 2011-03-24 | 2012-08-15 | 宁波千衍新材料科技有限公司 | Aldol condensation catalyst, and preparation method and application thereof |
| CN103007997A (en) * | 2011-09-28 | 2013-04-03 | 株式会社日本触媒 | Catalyst for preparing crylic acid by lactic acid and method for preparing crylic acid by using same |
| CN102826980B (en) * | 2012-09-04 | 2014-10-15 | 华东理工大学 | Method for preparing methyl ethyl ketone by performing gas phase dehydration on 2,3-butanediol |
| CN105037119B (en) * | 2015-08-21 | 2016-10-05 | 吉林市凇泰化工有限责任公司 | A kind of production process of butenal of improvement |
| CN106631739B (en) * | 2016-12-22 | 2019-10-01 | 福州大学 | Crotonaldehyde reactive distillation production method and device based on solid base |
| CN106883112B (en) * | 2017-02-16 | 2020-09-15 | 福州福大双众化工科技有限公司 | Improved production process of crotonaldehyde |
| CN109422635A (en) * | 2017-09-05 | 2019-03-05 | 东营市海科新源化工有限责任公司 | A kind of preparation method of 1,3 butylene glycol |
| CN114805021B (en) * | 2022-04-27 | 2023-09-19 | 中国科学院青岛生物能源与过程研究所 | Preparation method of 2-propyl-1-heptanol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016066869A1 (en) | 2014-10-30 | 2016-05-06 | Abengoa Research, S.L. | Microporous catalyst with selective encapsulation of metal oxides, used to produce butadiene precursors |
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