阅读说明：本技术 一种反应精馏制备β-羟基醛的方法 (A kind of method that reactive distillation prepares beta-hydroxy aldehyde ) 是由 崔龙 张玉善 于 2019-08-27 设计创作，主要内容包括：本发明提供一种反应精馏制备β-羟基醛的方法,通过羟醛缩合反应生成β-羟基醛,包括：在反应精馏过程中引入水。通过反应精馏制备β-羟基醛,并在反应精馏过程中引入水,能够减少不饱和醛副产物的生成,并阻止其进入后续的生产过程,同时能够有效避免副反应产生的原料额外损耗,提高目标产物的收率,且有利于最终产物的纯化精制,降低了对后续提纯工艺的要求,提高生产的经济效益。(The present invention provides a kind of method that reactive distillation prepares beta-hydroxy aldehyde, generates beta-hydroxy aldehyde by aldol reaction, comprising: water is introduced in reactive distillation processes.Beta-hydroxy aldehyde is prepared by reactive distillation, and water is introduced in reactive distillation processes, the generation of unsaturated aldehyde by-product can be reduced, and it is prevented to enter subsequent production process, the raw material excess loss that can effectively avoid side reaction to generate simultaneously, improves the yield of target product, and is conducive to the purifying purification of final product, the requirement to subsequent purification technique is reduced, the economic benefit of production is improved.)

1. a kind of method that reactive distillation prepares beta-hydroxy aldehyde generates beta-hydroxy aldehyde by aldol reaction, which is characterized in that It include: that water is introduced in reactive distillation processes.

2. the method that reactive distillation according to claim 1 prepares beta-hydroxy aldehyde, which is characterized in that the reactive distillation mistake Journey carries out in reactive distillation column, and the water is added by the condensation reaction area of the reactive distillation column and tower top.

3. the method that reactive distillation according to claim 2 prepares beta-hydroxy aldehyde, which is characterized in that the reactive distillation column Condensation reaction area and tower top be added water mass ratio be (0.1~10.0): 1.

4. the method that reactive distillation according to claim 2 or 3 prepares beta-hydroxy aldehyde, which is characterized in that the reaction essence The operating pressure for evaporating tower is -0.08~0.20MPa.

5. the method for preparing beta-hydroxy aldehyde according to any reactive distillation of claim 2~4, which is characterized in that institute occurs Stating residence time of the material of aldol reaction in the reactive distillation column is 0.5~8.0 hour.

6. the method for preparing beta-hydroxy aldehyde according to any reactive distillation of claim 2~5, which is characterized in that described anti- Answer the tower top temperature of rectifying column for the dew-point temperature of the raw material of generation aldol reaction under the conditions of operating pressure.

7. the method for preparing beta-hydroxy aldehyde according to any reactive distillation of claim 2~6, which is characterized in that described anti- The bottom temperature of rectifying column is answered to be not higher than the bubble point temperature that operating pressure condition is lauched.

8. the method for preparing beta-hydroxy aldehyde according to any reactive distillation of claim 2~7, which is characterized in that described The material for being located at the tower reactor of the reactive distillation column is sent back to the reactive distillation using forced circulation pump in reactive distillation processes The tower top of tower.

9. the method that any reactive distillation prepares beta-hydroxy aldehyde according to claim 1~8, which is characterized in that the hydroxyl The raw material of aldehyde condensation reaction includes at least a kind of with α-hydrogen aldehyde.

10. the method that reactive distillation according to claim 9 prepares beta-hydroxy aldehyde, which is characterized in that the water with it is described The mass ratio of aldehyde is (0.2~5) in the raw material of aldol reaction: 1.

11. the method that reactive distillation according to claim 9 or 10 prepares beta-hydroxy aldehyde, which is characterized in that described to have α-hydrogen aldehyde is at least one of ethyl aldehyde, propyl aldehyde or normal-butyl aldehyde.

12. the method for preparing beta-hydroxy aldehyde according to any reactive distillation of claim 9~11, which is characterized in that described It is reacted with α-hydrogen aldehyde with formaldehyde and generates the beta-hydroxy aldehyde.

13. the method that any reactive distillation prepares beta-hydroxy aldehyde according to claim 1~12, which is characterized in that described The raw material of aldol reaction reacts under the catalytic action of basic catalyst, and the basic catalyst is organic base, inorganic base Or at least one of strong base-weak acid salt.

14. the method that any reactive distillation prepares beta-hydroxy aldehyde according to claim 1~13, which is characterized in that adjust The pH to 7.0~8.5 of the raw material of the aldol reaction.

Technical field

The present invention relates to chemical production fields, and in particular to a kind of method that reactive distillation prepares beta-hydroxy aldehyde.

Background technique

Beta-hydroxy aldehyde is the important intermediary for producing multiple product, in the industrial production, is usually passed through with containing α-hydrogen aldehyde Aldol reaction is crossed to prepare beta-hydroxy aldehyde.The principle of aldol reaction are as follows: there is α-hydrogen aldehyde, generated under base catalysis Carbanion, then carbanion carries out nucleophilic addition to aldehydes or ketones as nucleopilic reagent, generates beta-hydroxy aldehyde.But beta-hydroxy Aldehyde is very easy to thermal dehydration and generates alpha-beta unsaturation aldehydes or ketones, is to prepare most important by-product in beta-hydroxy aldehyde, directly affects The yield of beta-hydroxy aldehyde.Such as in the presence of basic catalyst, normal-butyl aldehyde is reacted with formaldehyde generates intermediate product monomethylol fourth Base aldehyde (MMB), monomethylol butyl aldehyde (MMB) continuation is reacted with formaldehyde is made dihydroxymethyl butyl aldehyde (DMB), then hydrogenates To 2- ethyl -2- (hydroxymethyl) -1,3- propane diol (TMP).In reaction process, monomethylol butyl aldehyde (MMB) is extremely unstable It is fixed, it is prone to dehydration and generate unsaturated aldehyde by-product 2- ethyl-acrylic aldehyde (EA), this reaction is reversible. 2- ethyl-acrylic aldehyde (EA) is the most important by-product for preparing 2- ethyl -2- (hydroxymethyl) -1,3- propane diol (TMP) Object, for content about in 15-25% or so, reaction process is as follows:

2- ethyl-acrylic aldehyde (EA) output finally will affect 2- ethyl -2- (hydroxymethyl) -1,3- propane diol (TMP) yield.Therefore, control by-product 2- ethyl-acrylic aldehyde (EA) generation has very important significance.For upper Reaction is stated, Chinese patent literature CN1238753A is disclosed by being directly distilled to recover by-product EA to reduce by-products content The step of, although the utilization rate of raw material can be improved in this method, but be distilled to recover by-product and exacerbate monomethylol butyl aldehyde (MMB) it is decomposed into the reaction of 2- ethyl-acrylic aldehyde (EA), more 2- ethyls-acrylic aldehyde (EA) is caused to return reaction Device keeps burdensome reactor for treatment, bulky and process complicated.

Summary of the invention

Therefore, the technical problem to be solved in the present invention is that how to effectively control unsaturated aldehydes during aldol reaction Output, improve beta-hydroxy aldehyde yield, to provide a kind of method that reactive distillation prepares beta-hydroxy aldehyde.

A kind of method that reactive distillation prepares beta-hydroxy aldehyde generates beta-hydroxy aldehyde by aldol reaction, comprising: reaction Water is introduced in distillation process.

Further, the reactive distillation processes carry out in reactive distillation column, and the water is by the reactive distillation column Condensation reaction area and tower top are added.

Further, the mass ratio that water is added in the condensation reaction area of the reactive distillation column and tower top is (0.1~10.0): 1。

Further, the operating pressure of the reactive distillation column is -0.08~0.20MPa.

Further, it is 0.5 that residence time of the material of the aldol reaction in the reactive distillation column, which occurs, ~8.0 hours.

Further, the tower top temperature of the reactive distillation column is the original of generation aldol reaction under the conditions of operating pressure The dew-point temperature of material.

Further, the bottom temperature of the reactive distillation column is not less than the bubble point temperature that operating pressure condition is lauched.

Further, the tower reactor of the reactive distillation column will be located at using forced circulation pump in the reactive distillation processes Material send the tower top of the reactive distillation column back to.

Further, the raw material of the aldol reaction includes at least a kind of with α-hydrogen aldehyde.

Further, the mass ratio of aldehyde is (0.2~5) in the raw material of the water and the aldol reaction: 1.

Further, described to have α-hydrogen aldehyde at least one of ethyl aldehyde, propyl aldehyde or normal-butyl aldehyde.

Further, described that there is α-hydrogen aldehyde the generation beta-hydroxy aldehyde is reacted with formaldehyde.

Further, the raw material of the aldol reaction reacts under the catalytic action of basic catalyst, the alkalinity Catalyst is at least one of organic base, inorganic base or strong base-weak acid salt.

Further, the pH to 7.0~8.5 of the raw material of the aldol reaction is adjusted.

In the present invention, the equipment of the reactive distillation process unit of use includes but is not limited to reactive distillation column, all utilizations The equipment that can be realized reactive distillation process prepares beta-hydroxy aldehyde, within the scope of the present application.For example, use The equipment of reactive distillation process unit is reactive distillation column, i.e. destilling tower, and filler, column plate and heating tube are used in reactive distillation column Etc. internals, filler can be metal or the nonmetallic materials manufacture of regular or scattered heap, can also be using the plates such as bubble column, sieve-plate tower The tower-shaped formula of formula.

Materials stock is continually fed into and is discharged reactive distillation column.Operation processing, reaction solution are carried out using reactive distillation column Body material is sent into equipment by the conversion zone of reactive distillation column, and the internals such as distributor or spraying nozzle reinforcing liquid can be used and exist Distributing homogeneity in inner-tower filling material.The gas material of tower is left after condenser condenses by tower top, infinite reflux is returned in tower.By tower Kettle returns in tower after leaving a part of heated device ebuillition of heated partial gasification of the liquid material of tower, and another part is sent to instead It answers outside rectifying column.Using heater, condenser and strengthen the method for heat preservation and maintain the temperature of reactive distillation column system, in material According to " vapor liquid equilibrium " principle mass transfer and heat transfer occur in tower for each component, occur in tower according to " chemical reaction equilibrium " principle Chemical reaction.

The top that forced circulation pump makes the liquid material of tower reactor send reactive distillation column back to again can be used, be fed again into anti- It answers in rectifying column, improves materials conversion rate.

Technical solution of the present invention has the advantages that

1. the method that reactive distillation provided by the invention prepares beta-hydroxy aldehyde prepares beta-hydroxy aldehyde by reactive distillation, and Water is introduced in reactive distillation processes, is inhibited the positive of beta-hydroxy aldehyde dehydration to carry out, is controlled condensation reaction area beta-hydroxy aldehyde The chemical balance shape for being conducive to generation beta-hydroxy aldehyde and inhibiting to generate unsaturated aldehyde is between its dehydration product unsaturated aldehyde State, the relatively high beta-hydroxy aldehyde of boiling point leave condensation reaction area due to distillation centrifugation and are enriched in reactive distillation process unit Device bottom, and following process unit can be discharged into, and the relatively low unsaturated aldehyde of boiling point is at the top of equipment Hydration reaction area in be enriched with, do not produced by device bottom, by the above method, the life of unsaturated aldehyde by-product can be reduced At, and the raw material excess loss for preventing it from entering subsequent production process, while side reaction capable of effectively being avoided to generate, improve mesh The yield of product is marked, and is conducive to the purifying purification of final product, the requirement to subsequent purification technique is reduced, improves production Economic benefit.

2. the method that reactive distillation provided by the invention prepares beta-hydroxy aldehyde controls water by the condensation reaction of reactive distillation column Area (i.e. feedboard occur below condensation reaction region) and tower top are added, wherein a part of water is added to by condensation reaction area In reactive distillation column, the condensation product beta-hydroxy aldehyde dehydration for being able to suppress tower internal condensation reaction zone generates unsaturated aldehyde by-product, The relatively high beta-hydroxy aldehyde of boiling point leaves condensation reaction area due to distillation centrifugation and is enriched in reactive distillation process unit Device bottom, and following process unit can be discharged into, and the relatively low unsaturated aldehyde of boiling point is in the hydration close to tower top Reaction zone enrichment, another part water are added by reactive distillation tower top, promote unsaturated aldehyde that hydration reaction occurs in hydration reaction area Beta-hydroxy aldehyde is generated, the coal addition position by accurately controlling water keeps the production efficiency of beta-hydroxy aldehyde and yield higher.

Specific embodiment

There is provided following embodiments is to preferably further understand the present invention, it is not limited to the best embodiment party Formula is not construed as limiting the contents of the present invention and protection scope, anyone under the inspiration of the present invention or by the present invention and its The feature of his prior art is combined and any and identical or similar product of the present invention for obtaining, all falls within of the invention Within protection scope.

Method in following embodiments carries out continuous production in the condensation reaction system that reactive distillation column forms.Raw material Metering is continuously added in reactive distillation column, and tower reactor is heated using heater, and tower top condenses gaseous phase materials, top using condenser The material infinite reflux of condensation returns in tower, the devices such as column plate or filler and distributor is equipped in reactive distillation column, and simultaneously Equipped with devices such as temperature thermocouple, pH value meters.