CN208883742U - A kind of production system of 1,3 butylene glycol - Google Patents
A kind of production system of 1,3 butylene glycol Download PDFInfo
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- CN208883742U CN208883742U CN201821197092.7U CN201821197092U CN208883742U CN 208883742 U CN208883742 U CN 208883742U CN 201821197092 U CN201821197092 U CN 201821197092U CN 208883742 U CN208883742 U CN 208883742U
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Abstract
The utility model provides a kind of production system of 1,3-BDO, including micro passage reaction；With in the pipeline that is connected of micro passage reaction outlet and device；With in the pipeline and device exports the hydrogenation reaction kettle that is connected.The production system of 1,3-BDO provided by the utility model greatly improves the conversion per pass of the selectivity of 3- hydroxybutyraldehyde and acetaldehyde in acetaldehyde condensation reaction process, improves the selectivity and yield index of final products 1,3-BDO；The production cost for also reducing 1,3-BDO simultaneously, providing one can be with the process system of the production 1,3-BDO of industrial applications.
Description
Technical field
The utility model belongs to the production system of 1,2-PD synthesis technical field more particularly to a kind of 1,3-BDO
System.
Background technique
1,3-BDO, referred to as 1,3-BDO, molecular formula C4H10O2, it is a kind of colourless, tasteless liquid, nothing under room temperature
Corrosivity, to skin irritation very little, toxicity is very low, is widely used.1.3- butanediol have dihydric alcohol it is reactive, odorless,
The features such as low toxicity, good water solubility, it is mainly used for organic synthesis, is the raw material of polyester resin, alkyd resin, the raw material of plasticizer,
The raw material of polyurethane coating can be made into unsaturated polyester resin, wetting agent and softness with monomers such as phthalic anhydride, maleic anhydrides
Agent, the intermediate of medicine, dyestuff, surfactant, plasticiser, coupling agent, solvent, food addition and flavouring agent, it is also possible to make
Textile, tobacco and paper humidizer and softening agent, cheese or the antibacterial agent of meat etc..In addition, it is also used as moisturizer wide
It is general to be used in cosmetics, such as in toner, cream, lotion, toothpaste product.1,3 butylene glycol can be divided into technical grade and LO+ grades.
The former price is relatively low, is widely used as production, nitre to the less high industrial solvent of DPG quality requirements and unsaturated-resin
The raw materials for production of base fiber varnish etc.；The latter's price is higher, is mainly used in fragrance, cosmetics, detergent, food additives etc.
The field of high-quality feedstocks demand.As 1,3-BDO is mainly used as moisturizer in cosmetics, and there is good antibacterial work
With can be used for the production of various toners, ointment and toothpaste.And due to 1,3-BDO have antibacterial action, it also by with
Make the antibacterial agent of dairy products, meat products.1,3-BDO is as a kind of important organic synthesis intermediate, in answering for every field
With being continuously developed, extend.Due to the hypotoxicity and excellent performance of 1,3- fourth, developing prospect is good.
In prior art, the production method of 1,3-BDO mainly has: (1) acetaldehyde condensation hydrogenation technique；(2) propylene and first
Aldehyde condensation hydrolysis；(3) methacrylaldehyde is reacted with 2,2-dimethyl-1,3-propanediol；(4) bioanalysis etc..With regard to the work of 1,3-BDO
For industry production, above-mentioned common industrialized preparing process is all there is selectivity is low, and by-product is more, and post-processing difficulty etc. is asked
Topic.In contrast, acetaldehyde condensation hydrogenation technique is the prevailing technology for producing 1,3-BDO.The thus life of current 1,3 butylene glycol
Production method mainly uses acetaldehyde condensation hydrogenation method, but the country is in laboratory development phase, even if using flask or instead
The laboratory installations such as kettle are answered, the problems such as it is low to still remain conversion ratio, poor selectivity, do not there is the report of industrial production device.And
And the 1,3-BDO industrial process of foreign literature introduction, it is that 1,3-BDO is prepared using acetaldehyde condensation hydrogenation technique,
Intermediate product is that (2,6- dimethyl, 1,3- dioxane, 4- hexanol) repeated hydrogenation generates 1,3-BDO.There is also choosings for the technique
The problems such as selecting property and not high 1,3 butylene glycol yield.
Therefore, how to find one kind and be capable of the exploitation high conversion rate of industrial applications, good, high-purity 1, the 3- fourth of selectivity
Glycol production system solves technical problem present in above-mentioned practical application, to realization 1,3-BDO large-scale industry metaplasia
It produces, the solution close quarters situation that domestic high-end market relies primarily on import at present is most important, also becomes many manufacturing enterprises in the industry
One of with line research staff's urgent problem to be solved.
Utility model content
In view of this, the technical problem to be solved by the present invention is to provide a kind of production system of 1,3-BDO,
Production system provided by the utility model substantially increases conversion ratio, selectivity and the purity of 1,3-BDO product, Er Qiegong
Skill route is simple, is suitble to industrialized production.
The utility model provides a kind of production system of 1,3-BDO, including micro passage reaction；
With in the pipeline that is connected of micro passage reaction outlet and device；
With in the pipeline and device exports the hydrogenation reaction kettle that is connected.
Preferably, the channel diameter of the micro passage reaction is 5~25mm；
The shell sizes of the micro passage reaction are 100~800mm；
The pipe range of the micro passage reaction is 50~30000mm.
Preferably, the micro passage reaction includes single hose micro passage reaction or shell and tube micro passage reaction；
The acetaldehyde solution and catalyst are sent into the tube side of micro passage reaction.
Preferably, the system also includes pipe-line mixers；
The pipe-line mixer is provided with acetaldehyde solution import and catalyst inlet；
The outlet of the pipe-line mixer is connected with the import of the micro passage reaction.
Preferably, the system also includes stuffing rectification columns；
In the pipeline and outlet of device is connected with the feed inlet of the stuffing rectification column, the stuffing rectification column
The import that tower top outlet is connected with the import of the micro passage reaction is connected, the outlet of the tower reactor of the stuffing rectification column with
Hydrogenation reaction kettle is connected.
Preferably, the number of segment of the stuffing rectification column is 2~5 sections；
Every section of bed stuffing height of the stuffing rectification column is 2~5 meters.
Preferably, which is characterized in that the system also includes lightness-removing column, thin film evaporator and Second distillation columns.
Preferably, the outlet of the hydrogenation reaction kettle is connected with the side line import of the lightness-removing column, the lightness-removing column
Tower reactor outlet is connected with the import of the thin film evaporator；
The Second distillation column is stuffing rectification column.
Preferably, the number of segment of the Second distillation column is 3~6 sections；
Every section of bed stuffing height of the Second distillation column is 3~6 meters；
The Second distillation column is exported with sideline product.
Preferably, the steam (vapor) outlet of the thin film evaporator is connected with the side line import of the Second distillation column.
The utility model additionally provides a kind of production technology of 1,3-BDO, comprising the following steps:
1) acetaldehyde solution and catalyst are sent into micro passage reaction after carrying out condensation reaction, add acidic materials tune
After system is neutral, intermediate product is obtained；
2) after the intermediate product for obtaining above-mentioned steps carries out hydrogenation reaction, 1,3-BDO is obtained.
Preferably, the inlet amount of the acetaldehyde solution is 5~35kg/h；
The inlet amount of the catalyst is 0.2~2kg/h；
The time of the condensation reaction is 2~30min；
The temperature of the condensation reaction is 0~50 DEG C.
Preferably, the micro passage reaction includes single hose micro passage reaction or shell and tube micro passage reaction；
The channel diameter of the micro passage reaction is 5~25mm；
The shell sizes of the micro passage reaction are 100~800mm；
The pipe range of the micro passage reaction is 50~30000mm；
The acetaldehyde solution and catalyst are sent into the tube side of micro passage reaction.
It preferably, further include the mixing step in pipe-line mixer before the feeding；
The mass concentration of the acetaldehyde solution is 20%~80%；
The catalyst includes aqueous slkali；
The mass concentration of the aqueous slkali is 0.01%~5%；
The acetaldehyde solution and the flow-rate ratio of aqueous slkali are 10:(0.02~2).
Preferably, the aqueous slkali includes one of sodium hydroxide solution, potassium hydroxide solution and sodium bicarbonate solution
Or it is a variety of；
The pH value of the neutrality is 5~8；
The acidic materials include one of acetic acid, dilute hydrochloric acid, dilute sulfuric acid, formic acid, benzoic acid, carbonic acid and hydrofluoric acid or
It is a variety of.
It preferably, further include rectifying separating step before the hydrogenation reaction；
The pressure of the rectifying separation is 10~50KPa；
The tower top temperature of the rectifying separation is -20~2 DEG C；
The bottom temperature of the rectifying separation is 40~85 DEG C；
The mode of the rectifying separation is material filling type rectifying separation；
The temperature of the hydrogenation reaction is 30~100 DEG C；
The pressure of the hydrogenation reaction is 1.5~5.5MPa；
The time of the hydrogenation reaction is 0.5~4 hour；
Preferably, further include filtering after the hydrogenation reaction, de- light separation, evaporate separation and again one in rectification step
It is a or multiple；
The de- pressure gently separated is 5~50KPa；
The de- tower top temperature gently separated is 20~70 DEG C；
The de- bottom temperature gently separated is 100~150 DEG C.
The utility model additionally provides a kind of production system of 1,3-BDO, including micro passage reaction；
With in the pipeline that is connected of micro passage reaction outlet and device；
With in the pipeline and device exports the hydrogenation reaction kettle that is connected.
Preferably, the system also includes pipe-line mixers；
The pipe-line mixer is provided with acetaldehyde solution import and catalyst inlet；
The outlet of the pipe-line mixer is connected with the import of the micro passage reaction；
The system also includes stuffing rectification columns；
In the pipeline and outlet of device is connected with the feed inlet of the stuffing rectification column, the stuffing rectification column
Tower top outlet is connected with the import of the micro passage reaction, tower reactor outlet and the hydrogenation reaction kettle phase of the stuffing rectification column
Connection；
The number of segment of the stuffing rectification column is 2~5 sections；
Every section of bed stuffing height of the stuffing rectification column is 2~5 meters.
Preferably, the system also includes lightness-removing column, thin film evaporator and Second distillation columns；
The outlet of the hydrogenation reaction kettle is connected with the side line import of the lightness-removing column, the tower reactor outlet of the lightness-removing column
It is connected with the import of the thin film evaporator；
The steam (vapor) outlet of the thin film evaporator is connected with the side line import of the Second distillation column；
The Second distillation column is preferably stuffing rectification column；
The number of segment of the Second distillation column is 3~6 sections；
Every section of bed stuffing height of the Second distillation column is 3~6 meters；
The Second distillation column is exported with sideline product.
The utility model provides a kind of production system of 1,3-BDO, including micro passage reaction；With the microchannel
In the pipeline that reactor outlet is connected and device；With in the pipeline and device exports the hydrogenation reaction kettle that is connected.With it is existing
There is technology to compare, all there is selectivity for the common industrialized preparing process of existing 1,3-BDO for the utility model
The problems such as low, by-product is more, and post-processing is difficult.And acetaldehyde condensation hydrogenation technique, either it is in laboratory development phase also
It is that also to still remain conversion ratio low in industrialized method, the problems such as poor selectivity.
The utility model provide it is a kind of use acetaldehyde for raw material, condensation reaction back end hydrogenation prepares the industry of 1,3-BDO
Change production system.The production system first using acetaldehyde as raw material, then and catalyst, in micro passage reaction condensation reaction generate 3-
Hydroxybutyraldehyde is directly added into acidic materials for reacting rear material in microchannel and is neutralized to neutrality after condensation reaction.Containing not anti-
Repeated hydrogenation obtains product 1,3 butylene glycol and by-product n-butanol after answering the crude product material rectifying of acetaldehyde to isolate acetaldehyde.This is practical
The production system of the 1,3-BDO of novel offer, greatly improve in acetaldehyde condensation reaction process the selectivity of 3- hydroxybutyraldehyde and
The conversion per pass of acetaldehyde improves the selectivity and yield index of final products 1,3-BDO；1,3- fourth is also reduced simultaneously
The production cost of glycol, providing one can be with the process route of the production 1,3-BDO of industrial applications.
The experimental results showed that can be by the selectivity of 1,3-BDO by 60% using production system provided by the utility model
~70% is promoted to 85% or more, and yield is promoted to 98% by 85%, and 99.5% or more purity effectively improves target product
Selectivity and yield, timeliness cost and energy consumption.
Detailed description of the invention
Fig. 1 is the Major Systems general flow chart of 1,3 butylene glycol production system provided by the utility model；
Fig. 2 is the system flow schematic diagram for the 1,3 butylene glycol production system that the utility model embodiment 1 provides.
Specific embodiment
In order to further appreciate that the utility model, carried out below with reference to preferred embodiment of the embodiment to the utility model
Description, but it is to be understood that these descriptions are only to further illustrate the feature and advantage of the utility model rather than to this reality
The limitation required with new patent.
All raw materials of the utility model, are not particularly limited its source, buying on the market or according to this field skill
The preparation of conventional method known to art personnel.
All raw materials of the utility model, are not particularly limited its purity, and the utility model preferably uses technical pure or two
The purity of propylene glycol preparation field routine.
All noun expression of the utility model and abbreviation belong to the expression of this field routine noun and abbreviation, each noun list
Up to be in its related application field with abbreviation it is explicit, those skilled in the art according to noun express and referred to as, energy
It is enough clear accurately uniquely to be understood.
The utility model provides a kind of production technology of 1,3-BDO, which comprises the following steps:
1) acetaldehyde solution and catalyst are sent into micro passage reaction after carrying out condensation reaction, add acidic materials tune
After system is neutral, intermediate product is obtained；
2) after the intermediate product for obtaining above-mentioned steps carries out hydrogenation reaction, 1,3-BDO is obtained.
Acetaldehyde solution and catalyst are sent into micro passage reaction after progress condensation reaction by the utility model first, then plus
After entering acidic materials modulation neutrality, intermediate product is obtained.
The design parameter of the acetaldehyde solution is not particularly limited in the utility model, with well known to those skilled in the art
For the acetaldehyde solution of such reaction, those skilled in the art can be according to practical condition, raw material condition and production
Product require to be selected and adjusted, and the mass concentration of acetaldehyde solution described in the utility model is preferably 20%~80%, more preferably
It is 30%~70%, more preferably 40%~60%.
The inlet amount of the acetaldehyde solution is not particularly limited in the utility model, with use well known to those skilled in the art
In the inlet amount of such reaction, those skilled in the art can want according to practical condition, raw material condition and product
It asks and is selected and adjusted, the inlet amount of acetaldehyde solution described in the utility model is 5~35kg/h, more preferably 10~
30kg/h, more preferably 15~25kg/h.
The specific choice of the acetaldehyde solution is not particularly limited in the utility model, with well known to those skilled in the art
For the custom catalysts of such reaction, those skilled in the art can according to practical condition, raw material condition and
Product requirement is selected and is adjusted, and catalyst described in the utility model preferably includes aqueous slkali, specifically more preferably hydroxide
One of sodium solution, potassium hydroxide solution and sodium bicarbonate solution are a variety of, more preferably sodium hydroxide solution, potassium hydroxide
Solution or sodium bicarbonate solution.The mass concentration of aqueous slkali described in the utility model is preferably 0.01%~5%, more preferably
0.05%~4.5%, more preferably 0.1%~4%, more preferably 0.5%~3.5%, more preferably 1%~3%, more preferably
It is 1.5%~2.5%.
The inlet amount of the catalyst is not particularly limited in the utility model, is used for well known to those skilled in the art
The inlet amount of the catalyst of such reaction, those skilled in the art can according to practical condition, raw material condition and
Product requirement is selected and is adjusted, and the inlet amount of catalyst described in the utility model is preferably 0.2~2kg/h, more preferably
0.5~1.8kg/h, more preferably 0.8~1.5kg/h, more preferably 1.0~1.3kg/h.
The parameter of the micro passage reaction is not particularly limited in the utility model, with well known to those skilled in the art
For the conventional parameter of micro passage reaction, those skilled in the art can according to practical condition, raw material condition with
And product requirement is selected and is adjusted, the utility model is to be further ensured that reaction effect, improves the performance parameter of product, institute
It states micro passage reaction and preferably includes single hose micro passage reaction or shell and tube micro passage reaction, more preferably tubulation declines
Channel reactor.The channel diameter (caliber) of micro passage reaction described in the utility model is preferably 5~25mm, and more preferably 8
~22mm, more preferably 10~20mm, more preferably 12~18mm.The shell sizes of micro passage reaction described in the utility model
Preferably 100~800mm, more preferably 200~700mm, more preferably 300~600mm, more preferably 400~500mm.This
The pipe range of micro passage reaction described in utility model is preferably 50~30000mm, more preferably 500~25000mm, more preferably
1000~20000mm, more preferably 5000~15000mm, more preferably 8000~12000mm.Acetaldehyde described in the utility model
Solution and catalyst are preferably sent in the tube side of micro passage reaction, i.e., reaction medium walks tube side, and heat transferring medium walks shell side.
The utility model is to further increase reaction effect, and pipe is preferably also included in front of the feeding micro passage reaction
Mixing step in road mixer, i.e. the utility model preferably mix acetaldehyde solution and catalyst in pipe-line mixer
Afterwards, it is re-fed into micro passage reaction and carries out condensation reaction.The utility model does not have the design parameter of the pipe-line mixer
Especially limitation, with the Common Parameters well known to those skilled in the art for such mixer, those skilled in the art can
To be selected and be adjusted according to practical condition, raw material condition and product requirement, more preferably micro-channel mixer.
The parameter of the condensation reaction is not particularly limited in the utility model, with well known to those skilled in the art such
The conventional parameter of condensation reaction, those skilled in the art can want according to practical condition, raw material condition and product
It asks and is selected and adjusted, the utility model is to be further ensured that reaction effect, improves the performance parameter of product, and the condensation is anti-
The time answered is preferably 2~30min, more preferably 7~25min, more preferably 12~20min.Condensation described in the utility model
The temperature of reaction is preferably 0~50 DEG C, more preferably 0~40 DEG C, more preferably 0~30 DEG C, more preferably 0~20 DEG C, can also
Think 5~20 DEG C, or is 10~15 DEG C.The pressure of condensation reaction described in the utility model is preferably normal pressure.
The utility model preferably uses micro-channel mixer and is used as mixing place, logical in micro-channel mixer used
Road characteristic dimension reaches micron order, before reactions, is spread by convection action and molecule, and raw material has been carried out the mixed of molecular level
It closes, improves the mass transfer effect in reaction process, provide guarantee for subsequent reactions.The utility model especially answers microchannel plate
Device is as reacting environment, the characteristics of channel diameter low using micro passage reaction, efficient mass transfer effect and storeroom it is abundant
Mixing carries out condensation reaction reaction for acetaldehyde solution and provides guarantee, and the temperature parameter control for keeping it crucial is more acurrate, so as to
It is enough to guarantee that reaction carries out at low temperature, the control range of reaction temperature is effectively widened, with being conducive to actual production control；And
And raw material is laminar state in channel, and air-teturning mixed phenomenon is not present, effectively prevents extra between material in reaction process connect
The chance of touching, reduces the generation of side reaction, to effectively improve the selectivity of 1,3-BDO, solves synthesis 1,3- fourth
The defects of diol product is selectively low, and by-product is high.
The specific choice of the acidic materials is not particularly limited in the utility model, with well known to those skilled in the art
For adjusting the acidic materials of pH value, those skilled in the art can be according to practical condition, raw material condition and production
Product require to be selected and adjusted, and acidic materials described in the utility model preferably include acetic acid, dilute hydrochloric acid, dilute sulfuric acid, formic acid, benzene
One of formic acid, carbonic acid and hydrofluoric acid are a variety of, more preferably acetic acid, dilute hydrochloric acid, dilute sulfuric acid, formic acid, benzoic acid, carbonic acid or
Hydrofluoric acid.
The specific range of the neutrality is not particularly limited in the utility model, with well known to those skilled in the art such
The neutral range of the pH value of reaction, those skilled in the art can be according to practical condition, raw material condition and products
It is required that being selected and being adjusted, the pH value of neutrality described in the utility model is preferably 5~8, more preferably 5.5~7.5, more preferably
It is 6~7.
The utility model obtains intermediate product after above-mentioned steps, and the utility model does not have the ingredient of the intermediate product
There is special limitation, in the present invention, the intermediate product preferably includes 3- hydroxybutyraldehyde, crotonaldehyde, acetaldehyde and water, i.e., main
Product is 3- hydroxybutyraldehyde, further includes the water etc. in by-product crotonaldehyde and unreacted acetaldehyde and raw material.
After the intermediate product that the utility model then obtains above-mentioned steps carries out hydrogenation reaction, 1,3-BDO is obtained.
The utility model is to further increase reaction effect, the intermediate product carry out before hydrogenation reaction it is also preferable to include
Intermediate product is preferably first carried out rectifying by rectifying separating step, i.e. the utility model, after separating acetaldehyde, then carries out hydrogenation reaction.
The design parameter that the utility model separates the rectifying is not particularly limited, with well known to those skilled in the art for such
The common rectifying separation parameter of reaction, those skilled in the art can be according to practical condition, raw material condition and production
Product require to be selected and adjusted, and the pressure of rectifying separation described in the utility model is preferably 10~50KPa, more preferably 15~
45KPa, more preferably 20~40KPa, more preferably 25~35KPa.The tower top temperature of rectifying separation described in the utility model is excellent
It is selected as -20~2 DEG C, more preferably -18~0 DEG C, more preferably -15~-3 DEG C, more preferably -12~-5 DEG C, more preferably -10
~-7 DEG C.The bottom temperature of rectifying separation described in the utility model is preferably 40~85 DEG C, and more preferably 50~75 DEG C, more preferably
It is 60~65 DEG C.The mode of rectifying separation described in the utility model is preferably material filling type rectifying separation.
The design parameter of the hydrogenation reaction is not particularly limited in the utility model, with well known to those skilled in the art
The parameter of common hydrogenation reaction for such reaction, those skilled in the art can be according to practical conditions, raw material
Situation and product requirement are selected and are adjusted, and the pressure of hydrogenation reaction described in the utility model is preferably 1.5~5.5MPa,
More preferably 2~5MPa, more preferably 2.5~4.5MPa, more preferably 3~4MPa.Hydrogenation reaction described in the utility model
Temperature is preferably 30~100 DEG C, more preferably 40~90 DEG C, more preferably 50~80 DEG C, more preferably 60~70 DEG C.This is practical
The time of the novel hydrogenation reaction is preferably 0.5~4 hour, more preferably 1~3.5 hour, more preferably 1.5~3 hours,
More preferably 2~2.5 hours.Hydrogenation reaction described in the utility model is preferably catalytic hydrogenation reaction, and the hydrogenation reaction is urged
Agent includes one of Raney's nickel catalyst, palladium-carbon catalyst and rhodium catalyst or a variety of, more preferably Raney's nickel catalyst,
Palladium-carbon catalyst or rhodium catalyst.
The utility model is the effect for being further ensured that final products, the whole production technology of complete and refinement, described plus hydrogen
It is also preferable to include filtering, de- light separation, evaporation separation and rectification step again after reaction, more preferably successively it is filtered point
From, de- light separation, evaporation separation and rectification step again.
The design parameter of above-mentioned steps is not particularly limited in the utility model, is used for well known to those skilled in the art
The post-processing step of such reaction, those skilled in the art can be according to practical condition, raw material condition and products
It is required that being selected and being adjusted, filtering described in the utility model is preferably separated by filtration, and is specially separated by filtration catalyst.This reality
It is preferably the de- light separation of rectifying with the novel de- light separation.The de- pressure gently separated described in the utility model is preferably 5~
50KPa, more preferably 15~40KPa, more preferably 25~30KPa.The de- tower top temperature gently separated described in the utility model is excellent
It is selected as 20~70 DEG C, more preferably 30~60 DEG C, more preferably 40~50 DEG C.The de- tower reactor temperature gently separated described in the utility model
Preferably 100~150 DEG C of degree, more preferably 110~140 DEG C, more preferably 120~130 DEG C.Evaporation point described in the utility model
From mode be preferably thin film evaporation separation.The pressure of rectifying again described in the utility model is preferably 1-50KPa, more preferably
5~45KPa, more preferably 10~40KPa, more preferably 20~30KPa.The tower top temperature of rectifying again described in the utility model
Preferably 100-140 DEG C, more preferably 105~135 DEG C, more preferably 120~132 DEG C, more preferably 122~130 DEG C, it is more excellent
It is selected as 123~126 DEG C.The bottom temperature of rectifying again described in the utility model is preferably 100-170 DEG C, more preferably 110~
155 DEG C, more preferably 125~135 DEG C.The mode of rectifying again described in the utility model is preferably material filling type rectifying separation.
The utility model is the effect for being further ensured that final products, the whole production technology of complete and refinement, above-mentioned steps
It is specifically as follows:
(1) be condensed unit: before going into operation first to process system suppress examination it is close, confirm system without leak source, acetaldehyde solution and alkali
Liquid is passed into micro passage reaction after being mixed together, and keeps micro passage reaction temperature at 0~50 DEG C, acetaldehyde solution concentration
In 20%~100% range, the concentration range of lye is 0.01%~1%, and the ratio that is passed through of acetaldehyde solution and lye is 10:
(0.02~2).Acetum is passed through after condensation reaction in reaction mass, reaction mass is neutralized to neutrality.
(2) acetaldehyde separative unit: contain the objects such as acetaldehyde, 3- hydroxybutyraldehyde, crotonaldehyde, water in the material after acetaldehyde condensation
Material carries out hydrogenation reaction production 1,3-BDO after first passing through de- acetaldehyde tower separation removal acetaldehyde again.The utility model is used and is filled out
Expect rectifying column separation removal acetaldehyde, the tower operating pressure be 0~50KPa, tower top temperature be -20~2 DEG C, bottom temperature be 40~
85 DEG C, which uses three sections of stainless steel cloth fillers.
(3) hydrogenation unit: the material after de- acetaldehyde is added in hydrogenation reaction kettle, the sky being passed through in nitrogen replacement reaction kettle
Gas is passed through hydrogen displacement nitrogen after the completion of displacement again, then begins to warm up heating, start when maintaining the temperature at 50~80 DEG C or so
It is passed through hydrogen, keeps the pressure of reaction kettle under conditions of 2.0~5.5MPa after hydrogenation reaction 0.5-4 hours, sampling analysis is anti-
It answers in material without stopping hydrogenation reaction after the materials containing carbonyl such as crotonaldehyde, trihydroxy-butyraldehyde, acetaldehyde.
(4) 1,3-BDO cut light tower: add after feed separation goes out hydrogenation catalyst after hydrogen, which is grasped using negative pressure
Make, pressure is 0~50KPa, and tower top temperature is 20~70 DEG C, and bottom temperature is 100~150 DEG C, which uses stainless steel cloth
Filler.
(5) it 1,3-BDO product: after removing light component material enters thin film evaporator evaporation removing acetic acid sodium salt, steams
Vapour is directly entered 1,3-BDO product rectifying column, and tower top further removes light component impurity, and tower reactor removes heavy constituent impurity, side
Line produces 1,3 butylene glycol product.
The utility model above-mentioned steps provide a kind of production technology of 1,3-BDO, and the utility model is contracted based on acetaldehyde
It is unstable to close intermediate product 3- hydroxybutyraldehyde, temperature is more than 85 degree or resolves into crotonaldehyde rapidly in acid condition.Or
3- hydroxybutyraldehyde and acetaldehyde can further be condensed as (2,6- dimethyl, 1,3- dioxane, 4- hexanol), and the utility model will be as
What improves the conversion per pass of acetaldehyde, improves the selectivity of 3- hydroxybutyraldehyde, and protects 3- hydroxybutyraldehyde steady before hydrogenation reaction
It is fixed not decompose, technical scale is realized as it, promotes the emphasis of yield and selectivity.The utility model for disadvantage mentioned above and
Own characteristic passes through the reaction temperature of optimal control acetaldehyde condensation, the amount of catalyst sodium hydroxide solution, acetaldehyde condensation reactor
Pattern, the mode of neutralization reaction, the modes such as condition of hydrogenation reaction improve 3- hydroxybutyraldehyde in acetaldehyde condensation reaction process
The conversion per pass of selectivity and acetaldehyde improves the selectivity and yield index of final products 1,3-BDO.Reduce 1,3- fourth
The production cost of glycol, providing one can be with the process route of the production 1,3-BDO of industrial applications.
The utility model provides the production method and system of a kind of 1,3-BDO, and the utility model is preferably with liquid hydrogen
Sodium hydroxide solution is catalyst, and acetaldehyde part occurs condensation reaction and generates acetaldol, and the material after reaction enters rectifying column separation
After removing unreacted acetaldehyde, hydrogenation reaction generates 1,3-BDO crude product, obtains 1,3-BDO product after refining spearation.More
Important is acetaldehyde solution is preferably used, catalyst is sodium hydroxide solution, acetaldehyde solution and sodium hydroxide solution micro- logical
Hybrid reaction in road reactor stablizes the holding reaction temperature of optimization at 0~20 DEG C, and reaction pressure is normal pressure, in microreactor
Acetum (acidic materials) directly are injected in the back segment of microreactor after middle completion condensation reaction, acetaldehyde condensation product is neutralized
To neutrality.Then unreacted acetaldehyde is isolated in rectifying under condition of negative pressure, and return is configured to that acetaldehyde solution is laggard to react in a subtle way
Device is recycled.The 3- hydroxybutyraldehyde solution for isolating unreacted acetaldehyde, which is delivered to again in hydrogenation reaction kettle, is hydrogenated to 1,3- fourth
Glycol product, condensation by-product crotonaldehyde are hydrogenated to n-butanol.
The fluid-mechanics point of view of the slave reaction process of the utility model further inventive is started with, and has been abandoned and has been stirred in previous reaction kettle
The characteristics of mixing mixed flow state response is changed to orderly laminar flow, is more advantageous to the progress of the reaction and the raising of selectivity, especially uses
Micro passage reaction is as reacting environment, the characteristics of channel diameter low using micro passage reaction, makes the raw material be in channel
Laminar condition reduces air-teturning mixed phenomenon, effectively prevents raw material and product contact generates the chance of by-product, it is anti-to reduce series connection
The generation answered further preferably combines micro-channel mixer to mix, to effectively improve the selectivity of 1,3-BDO in product, mentions
The selectivity of 3- hydroxybutyraldehyde and the conversion per pass of acetaldehyde in high acetaldehyde condensation reaction process, and then final products 1 are improved,
The selectivity and yield index of 3- butanediol, simple process, mild condition is easily controllable, is more suitable industrialized production.
The product purity that the utility model obtains is more than or equal to 99%, and the selectivity of coloration≤5,1,3-BDO is up to
To 89% or more.
The utility model additionally provides a kind of production system of 1,3-BDO, which is characterized in that answers including microchannel plate
Device；
With in the pipeline that is connected of micro passage reaction outlet and device；
With in the pipeline and device exports the hydrogenation reaction kettle that is connected.
Selection and composition of the utility model to required equipment in the production system of above-mentioned 1,3-BDO, and it is corresponding
The selection of corresponding equipment and composition in optimum principle, with aforementioned production technology, and corresponding optimum principle can be into
Row corresponds to, and this is no longer going to repeat them.
The mode being connected is not particularly limited in the utility model, in technique well known to those skilled in the art
Conventional connection type, those skilled in the art can according to practical condition, raw material condition and product requirement into
Row selection and adjustment, it is described in the utility model be connected be connected preferably by pipeline, or be connected by pipeline with pump.
Referring to Fig. 1, Fig. 1 is the Major Systems general flow chart of 1,3-BDO production system provided by the utility model.Its
In, 1, pipeline reactor；2, pipeline neutralization reactor；3, hydrogenation reaction kettle, a are acetaldehyde solution, and b is catalyst, and c is acid
Matter, d are hydrogen.
In the present invention, in the production system, including micro passage reaction.The utility model is to the microchannel
The parameter of reactor is not particularly limited, and is with the conventional parameter well known to those skilled in the art for micro passage reaction
Can, those skilled in the art can select and adjust, this reality according to practical condition, raw material condition and product requirement
With novel to be further ensured that reaction effect, the performance parameter of product is improved, the micro passage reaction preferably includes single hose
Micro passage reaction or shell and tube micro passage reaction, more preferably shell and tube micro passage reaction.It is described in the utility model micro-
The channel diameter (caliber) of channel reactor is preferably 5~25mm, and more preferably 8~22mm, more preferably 10~20mm are more excellent
It is selected as 12~18mm.The shell sizes of micro passage reaction described in the utility model are preferably 100~800mm, and more preferably 200
~700mm, more preferably 300~600mm, more preferably 400~500mm.The pipe of micro passage reaction described in the utility model
Long preferably 50~5000mm, more preferably 100~4500mm, more preferably 500~4000mm, more preferably 1000~
3000mm, more preferably 1500~2500mm.Acetaldehyde solution described in the utility model and catalyst are preferably sent to microchannel plate and answer
In the tube side of device, i.e., reaction medium walks tube side, and heat transferring medium walks shell side.
In the present invention, in the production system, it is also preferable to include pipe-line mixer, more preferably microchannel is mixed
Device.The pipe-line mixer is provided with acetaldehyde solution import and catalyst inlet；The outlet of the pipe-line mixer with it is described micro-
The import of channel reactor is connected.Its role is to the homogeneous before helping condensation reaction mixes, and improves reaction efficiency.This reality
It is not particularly limited with the novel structure and parameter to the pipe-line mixer, with conventional pipeline well known to those skilled in the art
The structure and parameter of mixer, those skilled in the art can want according to practical condition, raw material condition and product
It asks and is selected and adjusted.It in other embodiments, can also be containing other devices of identical function, to help condensation reaction
It carries out, raising reaction effect is preferred embodiment.
In the present invention, in the production system, the pipeline including being connected with micro passage reaction outlet is neutralized
Device.It is connected with the import of device with micro passage reaction outlet in the i.e. described pipeline.Its role is to help to subtract
The generation of few side reaction, meets the condition of subsequent reactions.The utility model does not have in the pipeline with the structure and parameter of device
There is special limitation, with the conventional structure and parameter well known to those skilled in the art in pipeline with device, this field
Technical staff can select and adjust according to practical condition, raw material condition and product requirement.In other embodiment party
In case, the condition of subsequent reactions can also be met containing other devices of identical function to help to reduce the generation of side reaction
For preferred embodiment.
In the present invention, in the production system, including in the pipeline and device outlet be connected plus hydrogen
Reaction kettle.In the i.e. described pipeline and outlet of device is connected with the import of the hydrogenation reaction kettle.Its role is to be added
Hydrogen reaction.The structure and parameter of the hydrogenation reaction kettle is not particularly limited in the utility model, ripe with those skilled in the art
The conventional structure and parameter for hydrogenation reaction device known, those skilled in the art can according to practical condition,
Raw material condition and product requirement are selected and are adjusted, and the utility model hydrogenator described in the utility model is preferably kettle
Formula interval hydrogenator.It in other embodiments, can also be containing other devices of identical function, to help to be added
Hydrogen reaction is preferred embodiment.
In the present invention, in the production system, it is also preferable to include stuffing rectification columns.Pipeline described in the utility model
The outlet for neutralizing device is preferably connected with the feed inlet of the stuffing rectification column, and the tower top outlet of the stuffing rectification column is preferred
The import being connected with the import of the micro passage reaction is connected, the outlet of the tower reactor of the stuffing rectification column preferably with add hydrogen
Reaction kettle is connected.The tower top outlet of stuffing rectification column described in the utility model further preferably with the import phase of the pipe-line mixer
Connection.Feed(raw material)inlet is returned to its role is to isolate unreacted acetaldehyde, while by the acetaldehyde of recycling, is recycled, energy conservation
Environmental protection reduces cost.In other embodiments, it can also be recycled, be saved with helping containing other devices of identical function
Can be environmentally friendly, reducing cost is preferred embodiment.
The structure and parameter of the stuffing rectification column is not particularly limited in the utility model, ripe with those skilled in the art
The structure and parameter for the conventional fillers rectifying column known, those skilled in the art can be according to practical conditions, raw material feelings
Condition and product requirement are selected and are adjusted, and the utility model is the performance for further increasing final products, complete and optimization
Production system, the number of segment of the stuffing rectification column are preferably 2~5 sections, more preferably 3~5 sections, more preferably 3~4 sections.This reality
Bed stuffing height with novel every section of the stuffing rectification column is preferably 2~5 meters, more preferably 2~4 meters, more preferably 3~4
Rice.Form of bio-carrier described in the utility model preferably includes structured packing or random packing, more preferably structured packing.This is practical new
Wire feeding described in type preferably includes stainless steel cloth, porcelain ripple packing, metal corrugated packing, wooden-grid packing, Raschig ring, Bauer
Ring, cascade ring and steel fill out circle one of or it is a variety of, more preferably stainless steel cloth, porcelain ripple packing, metal corrugated packing,
Wooden-grid packing, Raschig ring, Pall ring, cascade ring or steel fill out circle, most preferably BX (stainless steel metal silk screen) filler.This is practical
The feed inlet of the novel stuffing rectification column is preferably in second segment filler in the following, number of segment calculation described in the utility model is preferred
To be calculated from top to bottom by the top of the distillation column to tower reactor.
In the present invention, in the production system, it is also preferable to include lightness-removing column, thin film evaporator and the second rectifying
Tower.The outlet of hydrogenation reaction kettle described in the utility model is preferably connected with the side line import of the lightness-removing column, the lightness-removing column
Tower top outlet (alcohol and water of abjection) be preferably connected with condenser, carry out other utilizations, the tower reactor outlet of the lightness-removing column
It is preferred that be connected with the import of the thin film evaporator, steam (i.e. product) outlet of the thin film evaporator is preferably with described the
The side line import of two rectifying columns is connected.Its role is to separating-purifying final products, while byproduct is recycled, section
Can be environmentally friendly, reduce cost.It in other embodiments, can also be containing other devices of identical function, to help separating-purifying
Final products recycle, energy conservation and environmental protection, and reducing cost is preferred embodiment.
The structure and parameter of above-mentioned apparatus is not particularly limited in the utility model, with well known to those skilled in the art normal
The structure and parameter of lightness-removing column, thin film evaporator and rectifying column is advised, those skilled in the art can be according to actual production feelings
Condition, raw material condition and product requirement are selected and are adjusted, and the utility model is the performance for further increasing final products, complete
Whole and optimization production system, the Second distillation column is preferably stuffing rectification column.The section of Second distillation column described in the utility model
Preferably 3~6 sections of number, more preferably 4~6 sections, more preferably 4~5 sections.Every section of stuffing rectification column described in the utility model is filled out
Bed depth is preferably 3~6 meters, more preferably 4~6 meters, more preferably 4~5 meters.Form of bio-carrier described in the utility model is preferred
Including structured packing or random packing, more preferably structured packing.Wire feeding described in the utility model preferably includes stainless steel
Silk screen, porcelain ripple packing, metal corrugated packing, wooden-grid packing, Raschig ring, Pall ring, cascade ring and steel fill out one of circle
Or a variety of, more preferably stainless steel cloth, porcelain ripple packing, metal corrugated packing, wooden-grid packing, Raschig ring, Pall ring, ladder
Ring or steel fill out circle, most preferably BX (stainless steel metal silk screen) filler.The feed inlet of Second distillation column described in the utility model
It is preferred that going out with sideline product in third section filler in the following, the unloading position of the Second distillation column is preferably side take-off
Mouthful.The discharge port is preferably below first segment filler.Number of segment calculation described in the utility model is preferably by rectifying column
Tower top is calculated from top to bottom to tower reactor.
The utility model is the effect for being further ensured that final products, the whole production system of complete and refinement, above-mentioned generation
System is specifically as follows:
Condensation reaction unit: the acetaldehyde solution from acetaldehyde solution preparing tank and the hydrogen from sodium hydroxide solution preparing tank
Sodium hydroxide solution is delivered in micro passage reaction through pump respectively, is reacted in micro passage reaction internal condensation and is generated 3- hydroxyl fourth
Aldehyde, reaction pressure are normal pressure, and successive reaction under the conditions of reaction temperature is maintained at 0~20 degree keeps material in micro passage reaction
The interior residence time is 2~30 minutes.
It neutralizes: according to the pH value of the amount of the sodium hydroxide solution of addition and reacting rear material, in the back segment of microreactor
It is directly injected into acetum and reaction product is neutralized to neutrality.
Acetaldehyde recovery: the material that neutrality is neutralized to after reaction is delivered to rectifying in rectifying column and isolates unreacted acetaldehyde,
It returns to be recycled back in microreactor in acetaldehyde solution preparing tank after condensation and be recycled.
Add hydrogen: rectifying tower reactor material is delivered to hydrogenation reaction in hydrogenator, keeps hydrogenation reaction temperature 20~80
Within the scope of DEG C, pressure hydrogenation reaction within the scope of 1.5~6.0MPa generates 1,3-BDO and by-product n-butanol.
1,3-BDO product purification: the material after adding hydrogen is separated by filtration, the crude product 1 obtained after rectifying, 3- fourth two
Alcohol evaporates desalination after vapour phase condensation using thin film evaporator and re-refines to obtain 1,3-BDO product.
The utility model above-mentioned steps provide a kind of production system of 1,3-BDO, and the utility model is contracted based on acetaldehyde
It is unstable to close intermediate product 3- hydroxybutyraldehyde, temperature is more than 85 degree or resolves into crotonaldehyde rapidly in acid condition.Or
3- hydroxybutyraldehyde and acetaldehyde can further be condensed as (2,6- dimethyl, 1,3- dioxane, 4- hexanol), and the utility model will be as
What improves the conversion per pass of acetaldehyde, improves the selectivity of 3- hydroxybutyraldehyde, and protects 3- hydroxybutyraldehyde steady before hydrogenation reaction
It is fixed not decompose, technical scale is realized as it, promotes the emphasis of yield and selectivity.The utility model for disadvantage mentioned above and
Own characteristic passes through the pattern of optimal control acetaldehyde condensation reactor, the mode of neutralization reaction, the items such as mode of hydrogenation reaction
Part improves the selectivity of 3- hydroxybutyraldehyde and the conversion per pass of acetaldehyde in acetaldehyde condensation reaction process, improves final products 1,
The selectivity and yield index of 3- butanediol.The production cost of 1,3-BDO is reduced, providing one can be with industrial applications
Production 1,3 butylene glycol process route.
The utility model provides the production method and system of a kind of 1,3-BDO, and the utility model is preferably with liquid hydrogen
Sodium hydroxide solution is catalyst, and acetaldehyde part occurs condensation reaction and generates acetaldol, and the material after reaction enters rectifying column separation
After removing unreacted acetaldehyde, hydrogenation reaction generates 1,3-BDO crude product, obtains 1,3-BDO product after refining spearation.More
Important is acetaldehyde solution is preferably used, catalyst is sodium hydroxide solution, acetaldehyde solution and sodium hydroxide solution micro- logical
Hybrid reaction in road reactor stablizes the holding reaction temperature of optimization at 0~20 DEG C, and reaction pressure is normal pressure, in microreactor
Acetum (acidic materials) directly are injected in the back segment of microreactor after middle completion condensation reaction, acetaldehyde condensation product is neutralized
To neutrality.Then unreacted acetaldehyde is isolated in rectifying under condition of negative pressure, and return is configured to that acetaldehyde solution is laggard to react in a subtle way
Device is recycled.The 3- hydroxybutyraldehyde solution for isolating unreacted acetaldehyde, which is delivered to again in hydrogenation reaction kettle, is hydrogenated to 1,3- fourth
Glycol product, condensation by-product crotonaldehyde are hydrogenated to n-butanol.
The fluid-mechanics point of view of the slave reaction process of the utility model further inventive is started with, and has been abandoned and has been stirred in previous reaction kettle
The characteristics of mixing mixed flow state response is changed to orderly laminar flow, is more advantageous to the progress of the reaction and the raising of selectivity, especially uses
Micro passage reaction is as reacting environment, the characteristics of channel diameter low using micro passage reaction, makes the raw material be in channel
Laminar condition reduces air-teturning mixed phenomenon, effectively prevents raw material and product contact generates the chance of by-product, it is anti-to reduce series connection
The generation answered further preferably combines micro-channel mixer to mix, to effectively improve the selectivity of 1,3-BDO in product.This
Utility model carries out condensation reaction using micro passage reaction, and reaction heat removes system in time, and reaction temperature is easily controllable, reduces
The generation of condensation reaction side reaction reduces the generation of acetaldehyde high-shrinkage product therefore reduces toxic by-product, is conducive to mention
The quality of high 1,3 butylene glycol product；Using batch tank hydrogenation reaction process, simple process, easily controllable hydrogenation reaction into
Degree；The desalination mode used is thin film evaporation desalination, and desalination is thorough, it is ensured that salinity noresidue in material；It is mixed using pipeline
Clutch enters back into reactor after mixing to reaction raw materials, catalyst and recycle stock, ensure that material mixes in the reactor
It closes uniformly, space is saved using pipe-line mixer, saves the labor intensity of operation.
The production system of 1,3-BDO provided by the utility model greatly improves 3- hydroxyl in acetaldehyde condensation reaction process
The selectivity of butyraldehyde and the conversion per pass of acetaldehyde improve the selectivity and yield index of final products 1,3-BDO；Together
When also reduce the production cost of 1,3-BDO, simple process, mild condition is easily controllable, and the industrialization that is more suitable is big raw
It produces, providing one can be with the process route of the production 1,3-BDO of industrial applications.
The experimental results showed that can be by the selectivity of 1,3-BDO by 60% using production technology provided by the utility model
~70% is promoted to 85% or more, and yield is promoted to 90% by 85%, and 99.5% or more purity effectively improves target product
Selectivity and yield, timeliness cost and energy consumption.
In order to further illustrate the utility model, with reference to embodiments to 1,3-BDO provided by the utility model
Production system is described in detail, but it is to be understood that these embodiments are under premised on technical solutions of the utility model
Implemented, the detailed implementation method and specific operation process are given, only the spy to further illustrate the utility model
It seeks peace advantage, rather than the limitation to the utility model claims, the protection scope of the utility model are also not necessarily limited to following
Embodiment.
Embodiment 1
Referring to fig. 2, Fig. 2 is the system flow schematic diagram for the 1,3-BDO production system that the utility model embodiment 1 provides.
Wherein, a is acetaldehyde solution, and b is catalyst, and c is acidic materials, and d is hydrogen；1, pipeline reactor；2, pipeline neutralization reactor,
3, hydrogenation reaction kettle, 4, de- acetaldehyde tower, 5, filtering separation device, 6, de- light component rectifying column, 7, thin film evaporator, 8, product fills out
Expect rectifying column.
Reaction member: pipeline reactor specification is fixed tube sheet shell and tube reactor, and diameter of the housing 159mm is internal anti-
It should pipe 19 × 2mm of Φ, length 10000mm.Raw material acetaldehyde and liquid alkaline react in reaction tube after pipe-line mixer mixing,
The low-temperature aqueous solution that shell side is passed through 15 DEG C keeps reaction temperature not higher than 20 DEG C.Acetaldehyde be 80% acetaldehyde solution, liquid alkaline it is dense
The sodium hydroxide solution that degree is 0.4%, the flow velocity of acetaldehyde solution are 15kg/h, and the flow velocity of lye is 0.8kg/h, reactor outlet
Material first detects pH value, then instills 36% acetum, adjusts the pH value of reaction product to 7 or so.
Acetaldehyde separative unit: contain the objects such as acetaldehyde, 3- hydroxybutyraldehyde, crotonaldehyde, water in the material after above-mentioned acetaldehyde condensation
Material after first passing through de- acetaldehyde tower separation removal acetaldehyde, then carries out follow-up hydrogenation reaction production 1,3-BDO.Wherein, using filling out
Expect rectifying column separation removal acetaldehyde, which is 20KPa, and tower top temperature is -3.2 DEG C, and bottom temperature is 75 DEG C, the tower
Using three sections of stainless steel cloth fillers, lightness-removing column side entry feed.
Unreacted acetaldehyde is isolated in rectifying, is recycled back in microreactor and is recycled in return acetaldehyde solution preparing tank after condensation
It uses.
Hydrogenation unit: the material after de- acetaldehyde is added in autoclave interval hydrogenator, and hydrogenation reaction kettle volume is 4L,
Using Raney's nickel catalyst plus hydrogen, catalyst loading 10%, material filling amount is 1.5L, is passed through in nitrogen replacement reaction kettle
Air, be passed through hydrogen displacement nitrogen again after the completion of displacement, then begin to warm up heating, holding hydrogenation reaction temperature is on 40 DEG C of left sides
Start to be passed through hydrogen when right, keep the pressure of reaction kettle under conditions of 3.5MPa, after hydrogenation reaction 2 hours, sampling analysis is anti-
It answers in material without stopping hydrogenation reaction after the materials containing carbonyl such as crotonaldehyde, trihydroxy-butyraldehyde, acetaldehyde.
1,3-BDO cut light tower: the material after adding hydrogen is after filtering to isolate hydrogenation catalyst, using essence
Evaporate de- light crude product 1,3 butylene glycol obtained after separation.Wherein, taking off the pressure gently separated is 30KPa.Tower top temperature is 46 DEG C.Tower
Kettle temperature degree is 137 DEG C.The tower uses stainless steel cloth filler, side entry feed.
Referring to table 1, table 1 is the de- light rear crude product 1 of cut light tower, 3- fourth two in 1 preparation process of the utility model embodiment
The data of alcohol outlet continuous sampling.
Table 1
1,3 butylene glycol product purification:
1,3-BDO product: after removing light component material enters thin film evaporator evaporation removing acetic acid sodium salt, steam
It is directly entered 1,3-BDO product rectifying column (Second distillation column), tower top further removes light component impurity, tower reactor removing weight
Composition impurity, side take-off 1,3-BDO product.
Wherein, product stuffing rectification column be 4 sections of fillers, every section 4 meters of height, pressure 2KPa.Tower top temperature is 118 DEG C.
Bottom temperature is 132 DEG C.The tower uses stainless steel cloth filler, side entry feed, and side line goes out product.
The 1,3-BDO product prepared to the utility model embodiment 1 detects, 1, the 3- fourth after refinement treatment
The purity of glycol is more than or equal to 99.5%, and total recovery is 90%~95%, and coloration is less than 5.
Embodiment 2
Reaction member: according to process shown in Fig. 2, pipeline reactor uses sleeve type structure, inner tube be Φ 19 ×
2, length is the casing of 18000mm, is passed through low temperature water management reaction temperature at 20 degree or less in collet.Raw material acetaldehyde and liquid alkaline exist
After pipe-line mixer mixing, reacted in pipeline reactor, the concentration of reaction raw materials acetaldehyde is 40%, lye sodium hydroxide it is dense
Degree is 0.1%, and the flow velocity of acetaldehyde solution is 1kg/h, and the flow velocity of lye is 0.05kg/h.Reactor outlet material first detects PH
Then value instills 36% acetum, adjust the pH value of reaction product to 7.0 or so.
Acetaldehyde separative unit: contain the objects such as acetaldehyde, 3- hydroxybutyraldehyde, crotonaldehyde, water in the material after above-mentioned acetaldehyde condensation
Material after first passing through de- acetaldehyde tower separation removal acetaldehyde, then carries out follow-up hydrogenation reaction production 1,3-BDO.Wherein, using filling out
Expect rectifying column separation removal acetaldehyde, which is 30KPa, and tower top temperature is 2.2 DEG C, and bottom temperature is 83 DEG C, the tower
Using three sections of stainless steel cloth fillers, lightness-removing column side entry feed.
Hydrogenation unit: the material after de- acetaldehyde is added in autoclave interval hydrogenator, and hydrogenation reaction kettle volume is 4L,
Using Raney's nickel catalyst plus hydrogen, catalyst loading 10%, material filling amount is 1.5L, is passed through in nitrogen replacement reaction kettle
Air, be passed through hydrogen displacement nitrogen again after the completion of displacement, then begin to warm up heating, holding hydrogenation reaction temperature is on 40 DEG C of left sides
Start to be passed through hydrogen when right, keep the pressure of reaction kettle under conditions of 3.8MPa, after hydrogenation reaction 2 hours, sampling analysis is anti-
It answers in material without stopping hydrogenation reaction after the materials containing carbonyl such as crotonaldehyde, trihydroxy-butyraldehyde, acetaldehyde.
1,3-BDO cut light tower: the material after adding hydrogen is after filtering to isolate hydrogenation catalyst, using essence
Evaporate de- light crude product 1,3 butylene glycol obtained after separation.Wherein, taking off the pressure gently separated is 35KPa.Tower top temperature is 51 DEG C.Tower
Kettle temperature degree is 145 DEG C.The tower uses stainless steel cloth filler, side entry feed.
Referring to table 2, table 2 is the de- light rear crude product 1 of cut light tower, 3- fourth two in 2 preparation process of the utility model embodiment
The data of alcohol outlet continuous sampling.
Referring to table 2, table 2 is the data of continuous sampling in 2 preparation process of the utility model embodiment
Table 2
1,3 butylene glycol product purification:
1,3-BDO product: after removing light component material enters thin film evaporator evaporation removing acetic acid sodium salt, steam
It is directly entered 1,3-BDO product rectifying column (Second distillation column), tower top further removes light component impurity, tower reactor removing weight
Composition impurity, side take-off 1,3-BDO product.
Wherein, product stuffing rectification column be 4 sections of fillers, every section 4 meters of height, tower top pressure 1KPa.Tower top temperature is 105
℃.Bottom temperature is 128 DEG C.The tower uses stainless steel cloth filler, side entry feed, and side line goes out product.
The 1,3-BDO product prepared to the utility model embodiment 2 detects, 1, the 3- fourth after refinement treatment
The purity of glycol is more than or equal to 99.5%, and total recovery is 90%~95%, and coloration is less than 5.
The highly selective production system for preparing 1,3 butylene glycol of one kind provided by the utility model has been carried out in detail above
Introduction, specific case used herein is expounded the principles of the present invention and embodiment, above embodiments
Explanation be merely used to help understand the method and its core concept of the utility model, including best mode, and but also this
Any technical staff in field can practice the utility model, including any device or system of manufacture and use, and implement to appoint
The method what is combined.It should be pointed out that for those skilled in the art, not departing from the utility model principle
Under the premise of, several improvements and modifications can be made to this utility model, these improvement and modification also fall into the utility model
In scope of protection of the claims.The range of the utility model patent protection is defined by the claims, and may include ability
Field technique personnel it is conceivable that other embodiments.If these other embodiments, which have, is not different from claim literal table
The structural element stated, or if they include the equivalent structural elements with the character express of claim without essence difference, that
These other embodiments should also be included in the scope of the claims.
Claims (10)
1. a kind of production system of 1,3-BDO, which is characterized in that including micro passage reaction；
With in the pipeline that is connected of micro passage reaction outlet and device；
With in the pipeline and device exports the hydrogenation reaction kettle that is connected.
2. production system according to claim 1, which is characterized in that the channel diameter of the micro passage reaction be 5~
25mm；
The shell sizes of the micro passage reaction are 100~800mm；
The pipe range of the micro passage reaction is 50~30000mm.
3. production system according to claim 1, which is characterized in that the micro passage reaction includes single hose microchannel
Reactor or shell and tube micro passage reaction；
Acetaldehyde solution and catalyst are sent into the tube side of the micro passage reaction.
4. production system according to claim 1, which is characterized in that the system also includes pipe-line mixers；
The pipe-line mixer is provided with acetaldehyde solution import and catalyst inlet；
The outlet of the pipe-line mixer is connected with the import of the micro passage reaction.
5. production system according to claim 1, which is characterized in that the system also includes stuffing rectification columns；
In the pipeline and outlet of device is connected with the feed inlet of the stuffing rectification column, the tower top of the stuffing rectification column
It exports the import being connected with the import of the micro passage reaction to be connected, the tower reactor outlet of the stuffing rectification column and plus hydrogen
Reaction kettle is connected.
6. production system according to claim 5, which is characterized in that the number of segment of the stuffing rectification column is 2~5 sections；
Every section of bed stuffing height of the stuffing rectification column is 2~5 meters.
7. production system described in any one according to claim 1~6, which is characterized in that the system also includes lightness-removing column,
Thin film evaporator and Second distillation column.
8. production system according to claim 7, which is characterized in that the outlet of the hydrogenation reaction kettle and the lightness-removing column
Side line import be connected, the outlet of the tower reactor of the lightness-removing column is connected with the import of the thin film evaporator；
The Second distillation column is stuffing rectification column.
9. production system according to claim 7, which is characterized in that the number of segment of the Second distillation column is 3~6 sections；
Every section of bed stuffing height of the Second distillation column is 3~6 meters；
The Second distillation column is exported with sideline product.
10. production system according to claim 7, which is characterized in that the steam (vapor) outlet of the thin film evaporator with it is described
The side line import of Second distillation column is connected.
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| CN201821197092.7U CN208883742U (en) | 2018-07-26 | 2018-07-26 | A kind of production system of 1,3 butylene glycol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111704532A (en) * | 2020-07-02 | 2020-09-25 | 中国天辰工程有限公司 | Method for removing acetaldehyde in 3-hydroxybutyraldehyde crude product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111704532A (en) * | 2020-07-02 | 2020-09-25 | 中国天辰工程有限公司 | Method for removing acetaldehyde in 3-hydroxybutyraldehyde crude product |
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