CN106242942A - The method for continuously synthesizing of a kind of 1 chlorobutane and the equipment of production thereof - Google Patents
The method for continuously synthesizing of a kind of 1 chlorobutane and the equipment of production thereof Download PDFInfo
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- CN106242942A CN106242942A CN201610808650.8A CN201610808650A CN106242942A CN 106242942 A CN106242942 A CN 106242942A CN 201610808650 A CN201610808650 A CN 201610808650A CN 106242942 A CN106242942 A CN 106242942A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
- C07C17/386—Separation; Purification; Stabilisation; Use of additives by distillation with auxiliary compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses method for continuously synthesizing and the production equipment thereof of a kind of 1 chlorobutane, hydrochloric acid desorption tower is entered after being preheated by preheated for concentrated hydrochloric acid device, stripped rear tower reactor obtains dilute hydrochloric acid, part enters the bottom of hydrochloric acid desorption tower after reboiler produces azeotropic vaporization, tower top obtains the hydrogen chloride gas of bulk purity more than 99%, go with n-butyl alcohol hybrid reaction after, azeotropic distillation obtains 1 chlorobutane.Production equipment includes hydrochloric acid desorption tower, and the upper inlet of hydrochloric acid desorption tower is communicated with concentrated hydrochloric acid storage tank by preheater, and the tower reactor of hydrochloric acid desorption tower thermal medium inlet with reboiler and preheater respectively connects, the lower inlet of the outlet hydrochloric acid desorption tower of reboiler；The top exit of hydrochloric acid desorption tower connects reactive distillation column by mixing duct；Described mixing duct also connects n-butyl alcohol storage tank.The present invention, for the continuous synthesis of 1 chlorobutane, maintains the balance of reaction system, and energy consumption is low, product purity is high, product yield is high.
Description
Technical field
The present invention relates to technical field of organic synthesis, be specifically related to the continuous synthesis technology of a kind of 1-chlorobutane.
Background technology
1-chlorobutane has another name called n-butyl chloride, chloro-normal butane, and it is a kind of important fine chemical product, can be used for medicine
Intermediate, solvent, promoter etc..The method of synthesis 1-chlorobutane has thionyl chloride chloridising, phosphorus oxychloride or five chlorethoxyfos
Chloridising, hydrogen chloride gas pressurization chloridising, hydrogen chloride gas catalytic chlorination process, concentrated hydrochloric acid chloridising, concentrated hydrochloric acid catalytic chlorination
Method, concentrated hydrochloric acid pressurization chloridising etc..
The production of some halogenated hydrocarbons directly carries out halogenating reaction with halogen, and halogenating reaction, in addition to generating halogenated hydrocarbons, goes back by-product
Hydrogen halides, such as alkane, the chlorination of aromatic hydrocarbons, meeting by-product hydrogen chloride gas, also has some halogenating reactions, enters with halogenated hydrocarbons with hydrogen halides
Line replacement reacts, also by-product hydrogen halides, such as chlorohydrocarbon and hydrogen fluoride reaction, generates while fluorohydrocarbon also by-product hydrogen chloride, secondary
Product hydrogen chloride gas is cheap, therefore, with hydrogen chloride or concentrated hydrochloric acid for raw material production 1-chlorobutane, has cost of material low,
The advantage of low cost.
N-butyl alcohol and hcl reaction are in addition to generating 1-chlorobutane, and also water generates, the continuous synthesis technique of 1-chlorobutane
Challenge is how that the water that water reaction generated or raw material salt acid band enter is removed in reaction system, keep the thing of reaction system
Material balance, and hydrogen chloride is soluble in water, under reaction condition, n-butyl alcohol dissolubility in water is the biggest, and alcohol is anti-with halogen acids effect
The reaction that should generate halogenated hydrocarbons is reversible reaction, and hydrogen chloride is relatively slow with n-butyl alcohol reaction rate, by molecular balance condition
Restriction, reactant cannot be completely consumed, and under generic condition when removing the water in reaction system, hydrogen chloride and n-butyl alcohol are also
Can remove with water, cause supplies consumption high, waste water is high containing acid, and content of organics is high, waste water difficult treatment, and production cost is high
Problem.
Chinese patent CN1069018A discloses " a kind of method producing chloro-normal butane ", the method use n-butyl alcohol and
Hydrochloric acid is raw material, not extra catalyst, continuous production of n-butyl chloride under normal pressure.N-butyl alcohol and hydrochloric acid are continuously added to reactor
In, react at 98～105 DEG C, after the gaseous mixture condensed device condensation that reactor steams, enter sequence of constant boiling and rectification tower, control
Sequence of constant boiling and rectification column overhead temperatures processed is 68 ± 1 DEG C, and the azeotropic mixture of 1-chlorobutane and water steams from tower top, and condensed and layering removes water
After chloro-normal butane crude product, then through washing, obtain chlorobutane finished product after rectification, at the bottom of sequence of constant boiling and rectification tower tower, mixture is in tower reactor
Inside being divided into two-layer, upper strata is made up of unreacted n-butyl alcohol and acid water, and lower floor is by substantial amounts of water and n-butyl alcohol and a small amount of hydrochloric acid
Composition, upper strata is allowed to return reactor and continues reaction, and lower floor enters azeotropic device, and the azeotropic mixture of n-butyl alcohol and water returns again to reactor
Continue reaction.The method, owing to reactor conversion per pass is low, the unreacted n-butyl alcohol in sequence of constant boiling and rectification tower bottom upper strata and acidity
Water circular response, contains the water of 70% in Repeat-heating, and raw material hydrochloric acid, this part water is also required to by boiling removal reaction
Still carrys out the material balance in guarantee system, thus maintains and produce continuously, causes energy consumption higher, and azeotropic device reclaims n-butyl alcohol and water,
Due to hydrogen chloride easily easy water, hydrochloric acid boiling point is higher than water, azeotropic device cannot hydrogen chloride in efficient recovery water, cause at the bottom of azeotropic device
In the waste water of portion's discharge, acid concentration is high, and hydrogen chloride consumes height, and waste water processes and needs substantial amounts of alkali to neutralize.
Chinese patent CN101475440A discloses " a kind of method of continuous production of n-butyl chloride ", and the method is with chlorination
Hydrogen and n-butyl alcohol are raw material, not the method for continuous production of n-butyl chloride, the method and patent under extra catalyst normal pressure
CN1069018A uses azeotropic to move water technology, utilizes n-butyl alcohol and the feature of water azeotropic, and the water azeotropic making reaction generate goes out instead
Answering system, thus keep reaction system material balance, it is ensured that being carried out continuously of production, it replaces hydrochloric acid with hydrogen chloride gas, no
Need the water azeotropic of 70% in hydrochloric acid is gone out reaction system, a large amount of steam consumption can be reduced compared with patent CN1069018A, fall
Low energy consumption, but with hydrogen chloride gas as raw material, when hydrogen chloride gas purity is low, a large amount of noble gases and impurity bring reactant into
System, and for a long time can affect the properly functioning of production in system inner product.And owing to the aggregate velocity of 1-chlorobutane is relatively slow, in distillation column
In bottom azeotropic water out, containing n-butyl alcohol and hydrogen chloride, and hydrochloric acid boiling point is higher than water, the positive fourth in the recyclable water of stripper
Alcohol, but cannot hydrogen chloride in efficient recovery water, cause hydrogen chloride to consume height, wastewater pH is low, difficult treatment.
Disclosing in Chinese patent CN104326863A " preparation method of a kind of 1-chlorobutane ", the method is sub-with dimethyl
Sulfone is catalyst, prepares 1-chlorobutane with hydrogen chloride and n-butyl alcohol for raw material, and the 1st still is by after catalyst, hydrochloric acid, n-butyl alcohol mixing
Carrying out chlorination reaction and produce 1-chlorobutane, limit border ring is distilled, and steams the terminal as reaction without any fraction, and gained is the most anti-
Answer the concentration of the HCl being passed through again in residual liquid in hydrogen chloride raising reaction residue, and then apply mechanically in next batch, unless after applying mechanically
The yield of 1-chlorobutane is less than 90%, and GC purity is less than 99.5%, and this preparation method is batch technology, owing to product has water
Generating, during applying mechanically, product water can accumulate in reactor, and number of times is applied mechanically in impact, owing to being limited by molecular balance, and set
High with determining alcohol in the still residual liquid of final discharge after terminating, acid concentration is high, and waste water is the most disposable, and Batch Process manipulation strength is big,
Utilization rate of equipment and installations is low, is difficult to realize automated production.
Due to halogenating reaction technique itself, some chloridization process are intermittently operated, and the hydrogen chloride of reaction by-product is deposited
Discontinuously, the feature of instability of flow, by-product hydrogen chloride there is also the feature that purity is low, have impact on the continuous conjunction of 1-chlorobutane
Become, and affect stablizing of product quality.
Summing up above several synthesis techniques, there are the following problems: with hydrochloric acid as raw material, and in hydrochloric acid, the water of about 70% needs phase
Become removal reaction system, and the latent heat of water is relatively big, causes energy consumption of reaction too high；With hydrogen chloride gas as raw material, hydrogen chloride purity
Time low, noble gas causes rectification efficiency low in the accumulation of reactive distillation system, and rectification yield and purity are low；Use n-butyl alcohol azeotropic
Moving water technology, the extent of reaction of n-butyl alcohol and hydrogen chloride is low, and unreacted hydrogen cloride concentration is high, cannot when n-butyl alcohol separates with water
Hydrogen chloride in efficient recovery water, causes hydrogen chloride content in waste water high, does not meets cleaning and produce principle.
Summary of the invention
First to be solved by this invention technical problem is that: the deficiency existed for prior art, it is provided that one is passed through
First produce the hydrogen chloride gas of purity more than 99%, then carry out reactive distillation with n-butyl alcohol, and move water by azeotropic distillation, protect
Hold the material balance of reaction system, maintain the company of synthetic reaction stable system and product purity is high, yield is high 1-chlorobutane
Continuous synthetic method.
Second to be solved by this invention technical problem is that: the deficiency existed for prior art, it is provided that a kind of 1-chlorine
The continuous synthesis equipment of butane, this equipment uses hydrochloric acid desorption tower first to produce the hydrogen chloride gas of purity more than 99%, enters back into
Reactive distillation column and n-butyl alcohol carry out reactive distillation, maintain the material balance of reaction system, maintain synthetic reaction stable system
And the product purity that obtains is high, yield is high.
For solving above-mentioned first technical problem, the technical scheme is that
The method for continuously synthesizing of a kind of 1-chlorobutane, using concentrated hydrochloric acid and n-butyl alcohol is raw material, blended reaction and azeotropic
Rectification obtains 1-chlorobutane, and concentrated hydrochloric acid the most also includes that a desorption step, described desorption step include:
Enter from the tower top of hydrochloric acid desorption tower after 25～35wt% concentrated hydrochloric acid preheated devices preheatings, stripped after from hydrochloric acid
Desorption tower tower reactor obtains the dilute hydrochloric acid of 18～21wt%, and part enters under hydrochloric acid desorption tower after reboiler produces azeotropic vaporization
Portion, in uphill process with tower top decline concentrated hydrochloric acid carry out mass transfer and heat transfer, hydrochloric acid desorption tower top obtain bulk purity 99% with
On hydrogen chloride gas, go and n-butyl alcohol hybrid reaction.
As the technical scheme of a kind of improvement, described hybrid reaction and azeotropic distillation include step:
The hydrogen chloride gas ejected from hydrochloric acid desorption tower, enters reaction with n-butyl alcohol in mixing duct jointly after mixing
Bottom the tower reactor of rectifying column, the bottom temperature of control reactive distillation column, at 95～115 DEG C, controls the tower top temperature of reactive distillation column
At 68～70 DEG C, the 1-chlorobutane of reaction generation and water are from reactive distillation top of tower azeotropic out.
Described reactive distillation, n-butyl alcohol and hydrogen chloride gas molar ratio are 1:0.95～1.15, further preferably
For 1:1～1.05；Described reactive distillation column bottom temperature more preferably 105～110 DEG C, the most preferably 106
～108 DEG C.
As the technical scheme of a kind of improvement, after reactive distillation top of tower azeotropic 1-chlorobutane out and water are condensed
Entering chlorobutane bypass channel, upper oil phase after layering enters chlorobutane storage tank, the 1-chlorobutane part in chlorobutane storage tank
Pressurized backflow is returned reactive distillation column and is carried out azeotropic shifting water, and the 1-chlorobutane generated with reaction and water are from reactive distillation top of tower altogether
Boiling is out.1-chlorobutane capacity of returns is 1～10 times of raw material n-butyl alcohol addition.
As the technical scheme improved further, it is transmitted back to reaction by pressurized for the 1-chlorobutane part in chlorobutane storage tank
Rectifying column carry out azeotropic move water time, by be transmitted back to the tower top of reactive distillation column, top, middle part, bottom one at or many places.
As the preferred technical scheme of one, another part 1-chlorobutane in chlorobutane storage tank is transported to rectification system
System, obtains purity after rectification and is more than 95% more than 99.5wt%, levels of n-butanol less than 0.05wt%, 1-chlorobutane yield
1-chlorobutane product.
As the technical scheme of a kind of improvement, the still liquid of the tower reactor accumulation of described reactive distillation column is admitted to n-butyl ether distillation
Tower distills, and the 1-chlorobutane mixed gas that n-butyl ether overhead steams returns again to reactive distillation column tower reactor and continues anti-
Should.Described n-butyl ether distillation column, bottom temperature controls at 90～140 DEG C.
As the technical scheme of a kind of improvement, stripped after another part dilute hydrochloric acid of obtaining from hydrochloric acid desorption tower tower reactor,
After described preheater removes pre-Thickish hot hydrochloric acid, entering dilute hydrochloric acid storage tank, conveying goes absorbing hydrogen chloride gas to produce concentration the most again
The concentrated hydrochloric acid raw material of 25～35wt%, it is achieved that the zero-emission of hydrochloric acid.
For solving above-mentioned second technical problem, the technical scheme is that
The synthesis device that the continuous synthesis of a kind of 1-chlorobutane is used, including:
Hydrochloric acid desorption tower, the upper inlet of described hydrochloric acid desorption tower is communicated with concentrated hydrochloric acid storage tank, described salt by preheater
The tower reactor thermal medium inlet with reboiler and described preheater respectively of acid desorption tower connects, the outlet institute of described reboiler
State the lower inlet of hydrochloric acid desorption tower；
The top exit of described hydrochloric acid desorption tower connects reactive distillation column by mixing duct；Described mixing duct also connects
N-butyl alcohol storage tank；
The tower top outlet of described reactive distillation column has been sequentially communicated condenser, chlorobutane bypass channel and chlorobutane storage tank.
As the technical scheme of a kind of improvement, the thermal medium outlet of described preheater is communicated with dilute hydrochloric acid storage tank；Described chlorine
Butane storage tank by reflux pump be respectively communicated with the tower top of described reactive distillation column, top, middle part, bottom one at or many places.
As the technical scheme of a kind of improvement, described chlorobutane storage tank is also communicated with chlorobutane rectifier unit；Described neoprene
Alkane bypass channel is also communicated with waste water storage tank.
As the technical scheme of a kind of improvement, described dilute hydrochloric acid storage tank connection multistage absorption circulating tank；Described waste water storage tank
Connect the most end one-level absorption cycle tank of described multistage absorption circulating tank.
As the technical scheme of a kind of improvement, the outlet at bottom of described reactive distillation column is communicated with also by residual liquid delivery pump
N-butyl ether distillation column, the tower top outlet of described n-butyl ether distillation column connects the tower reactor of described reactive distillation column.Reactive distillation column tower
Other side reaction products such as the n-butyl ether that the end produces are higher due to boiling point, can accumulate in reactive distillation column tower reactor, defeated by residual liquid
Sending pump that reactive distillation tower reactor residual liquid is sent into n-butyl ether distillation column, n-butyl ether distillation column carries out distillation procedure, the 1-that tower top steams
The mixed gas such as chlorobutane, n-butyl alcohol, hydrogen chloride, water return again to reactive distillation column tower reactor and continue reaction, reduce butyl ether discharge band
The n-butyl alcohol walked and hydrogen chloride, reduce supplies consumption, and distillation terminates to discharge after remaining butyl ether recycles or processes.
Owing to have employed technique scheme, the invention has the beneficial effects as follows:
The present invention is with hydrochloric acid as raw material, by entering the tower top of hydrochloric acid desorption tower, tower after being preheated by preheated for concentrated hydrochloric acid device
Still part dilute hydrochloric acid enters the bottom of hydrochloric acid desorption tower after reboiler produces azeotropic vaporization, declines with tower top in uphill process
Concentrated hydrochloric acid carries out mass transfer and heat transfer, and hydrochloric acid desorption tower top obtains the hydrogen chloride gas of bulk purity more than 99%, by salt acidolysis
Inhaling operation and obtain high-purity hydrogen chloride, decreasing the water brought in hydrochloric acid needs the problem of vaporization removal reaction system, reduces
Energy consumption of reaction, reduces hydrochloric acid supplies consumption, the diluted acid absorption capable of circulation gas containing hydrogen chloride after hydrochloric acid desorption, it is achieved hydrochloric acid zero
Discharge, hydrogen chloride absorption may utilize containing hydrogen chloride 0～the hydrogen chloride tail gas of 100%, the hydrogen chloride of available halogenating reaction by-product,
Stripped hydrogen cloride concentration being brought up to more than 99%, solve hydrogen chloride purity low, noble gas accumulates impact in system
The problem of reactive distillation stable operation.
The present invention utilize 1-chlorobutane azeotropic move water technology, by the middle part of the tower top of reactive distillation column, tower top, tower,
At the one of tower bottom, reactor etc. or many places add 1-chlorobutane and carry out azeotropic shifting water, reduce the positive fourth that reactive distillation column ejects
Alcohol and hydrogen chloride, reduce reaction and consume, improve product purity.
The present invention, by increasing n-butyl ether distillation column, solves the high-boiling components such as n-butyl ether and accumulates shadow in reactive distillation column tower reactor
Ring the problem that stable reaction is run, be recovered by distillation the hydrogen chloride in n-butyl ether residual liquid and n-butyl alcohol, reduce 1-chlorobutane
The supplies consumption of synthesis, reduces production cost.
Accompanying drawing explanation
The present invention is further described with embodiment below in conjunction with the accompanying drawings.
Fig. 1 is the structural representation of synthesis device of the present invention.
In figure, 1, concentrated hydrochloric acid storage tank；2, concentrated hydrochloric acid feed pump；3, preheater；4, hydrochloric acid desorption tower；5, reboiler；6, dilute
Salt acid storage tank；7, surge tank；8, mixing duct；9, n-butyl alcohol storage tank；10, n-butyl alcohol feed pump；11, reactive distillation column；12, cold
Condenser；13, chlorobutane bypass channel；14, chlorobutane storage tank；15, waste water storage tank；16, reflux pump；17, chlorobutane delivery pump；18、
Residual liquid delivery pump；19, n-butyl ether distillation column；20. dilute hydrochloric acid delivery pumps.
Detailed description of the invention
Below in conjunction with the accompanying drawings and embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate this
Bright rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, art technology
The present invention can be made various changes or modifications by personnel, and these equivalent form of values fall within the application appended claims equally and limited
Fixed scope.
Embodiment 1
Enter from the tower top of hydrochloric acid desorption tower after preheated for 30wt% concentrated hydrochloric acid device is preheated, stripped after from hydrochloric acid desorption
Tower tower reactor obtains the dilute hydrochloric acid of 20wt%, and part enters the bottom of hydrochloric acid desorption tower after reboiler produces azeotropic vaporization, rises
During with tower top decline concentrated hydrochloric acid carry out mass transfer and heat transfer, hydrochloric acid desorption tower top obtains the hydrogen chloride of bulk purity 99.3%
Gas, after mixing in mixing duct with the n-butyl alcohol come from n-butyl alcohol storage tank bottom the common tower reactor entering reactive distillation column,
The bottom temperature of control reactive distillation column is at 110 DEG C, and the tower top temperature of control reactive distillation column is at 68 DEG C, from reactive distillation tower top
Portion's azeotropic 1-chlorobutane out and water condensed after enter chlorobutane bypass channel, upper oil phase after layering enters chlorobutane
Storage tank, the pressurized backflow of 1-chlorobutane part in chlorobutane storage tank is returned reactive distillation column and is carried out azeotropic shifting water, generates with reaction
1-chlorobutane and water from rectifying column top azeotropic out.Another part 1-chlorobutane in chlorobutane storage tank is transported to rectification
System, obtains 1-chlorobutane product after rectification.
Embodiment 2
Enter from the tower top of hydrochloric acid desorption tower after 25～35wt% concentrated hydrochloric acid preheated devices preheatings, stripped after from hydrochloric acid
Desorption tower tower reactor obtains the dilute hydrochloric acid of 19wt%, and part enters the bottom of hydrochloric acid desorption tower after reboiler produces azeotropic vaporization,
The concentrated hydrochloric acid declined with tower top in uphill process carries out mass transfer and heat transfer, and hydrochloric acid desorption tower top obtains the chlorine of bulk purity 99.5%
Change hydrogen, after mixing in mixing duct with the n-butyl alcohol come from n-butyl alcohol storage tank at the bottom of the common tower reactor entering reactive distillation column
Portion, n-butyl alcohol and hydrogen chloride gas molar ratio are 1:1, and the bottom temperature of control reactive distillation column, at 105 DEG C, controls reaction
The tower top temperature of rectifying column, at 69 DEG C, enters neoprene after reactive distillation top of tower azeotropic 1-chlorobutane out and water are condensed
Alkane bypass channel, upper oil phase after layering enters chlorobutane storage tank, according to the backflow that 1-chlorobutane is raw material n-butyl alcohol 5 times
Amount, goes back to by the pressurized backflow of 1-chlorobutane part in chlorobutane storage tank to the tower top of reactive distillation column, top, middle part, bottom
Many places carry out azeotropic and move water, and the 1-chlorobutane generated with reaction and water are from rectifying column top azeotropic out.In chlorobutane storage tank
Another part 1-chlorobutane is transported to distillation system, obtains 1-chlorobutane product after rectification.
Embodiment 3
Enter from the tower top of hydrochloric acid desorption tower after preheated for 32wt% concentrated hydrochloric acid device is preheated, stripped after from hydrochloric acid desorption
Tower tower reactor obtains the dilute hydrochloric acid of 20wt%, and part dilute hydrochloric acid, after described preheater removes pre-Thickish hot hydrochloric acid, enters dilute hydrochloric acid storage tank,
Conveying goes absorbing hydrogen chloride gas to produce the concentrated hydrochloric acid raw material of concentration 32wt% the most again；Another part dilute hydrochloric acid produces through reboiler
Entering the bottom of hydrochloric acid desorption tower after raw azeotropic vaporization, the concentrated hydrochloric acid declined with tower top in uphill process carries out mass transfer and heat transfer,
Hydrochloric acid desorption tower top obtains the hydrogen chloride gas of bulk purity 99.5%, with the n-butyl alcohol come from n-butyl alcohol storage tank at mixing duct
In after mixing bottom the common tower reactor entering reactive distillation column, n-butyl alcohol and hydrogen chloride gas molar ratio are 1:1.02, control
The bottom temperature of reactive distillation column processed is at 106 DEG C, and the tower top temperature of control reactive distillation column is at 70 DEG C, from reactive distillation top of tower
Azeotropic 1-chlorobutane out and water condensed after enter chlorobutane bypass channel, upper oil phase after layering enters chlorobutane storage
Groove, according to the capacity of returns that 1-chlorobutane is raw material n-butyl alcohol 6 times, by the pressurized backflow of 1-chlorobutane part in chlorobutane storage tank
Return the tower top of reactive distillation column, top, middle part, the many places of bottom carry out azeotropic and move water, the 1-chlorobutane generated with reaction and water
From rectifying column top azeotropic out.Another part 1-chlorobutane in chlorobutane storage tank is transported to distillation system, after rectification
Obtain 1-chlorobutane product.The still liquid of the tower reactor accumulation of described reactive distillation column is admitted to n-butyl ether distillation column and distills, just
The 1-chlorobutane mixed gas that butyl ether overhead steams returns again to reactive distillation column tower reactor and continues reaction.Described n-butyl ether
Distillation column, bottom temperature controls at 120 DEG C.
Embodiment 4
Enter from the tower top of hydrochloric acid desorption tower after preheated for 35wt% concentrated hydrochloric acid device is preheated, stripped after from hydrochloric acid desorption
Tower tower reactor obtains the dilute hydrochloric acid of 21wt%, and part dilute hydrochloric acid, after described preheater removes pre-Thickish hot hydrochloric acid, enters dilute hydrochloric acid storage tank,
Conveying goes absorbing hydrogen chloride gas to produce the concentrated hydrochloric acid raw material of concentration 35wt% the most again；Another part dilute hydrochloric acid produces through reboiler
Entering the bottom of hydrochloric acid desorption tower after raw azeotropic vaporization, the concentrated hydrochloric acid declined with tower top in uphill process carries out mass transfer and heat transfer,
Hydrochloric acid desorption tower top obtains the hydrogen chloride gas of bulk purity 99.6%, with the n-butyl alcohol come from n-butyl alcohol storage tank at mixing duct
In after mixing bottom the common tower reactor entering reactive distillation column, n-butyl alcohol and hydrogen chloride gas molar ratio are 1:1.05, control
The bottom temperature of reactive distillation column processed is at 112 DEG C, and the tower top temperature of control reactive distillation column is at 70 DEG C, from reactive distillation top of tower
Azeotropic 1-chlorobutane out and water condensed after enter chlorobutane bypass channel, upper oil phase after layering enters chlorobutane storage
Groove, according to the capacity of returns that 1-chlorobutane is raw material n-butyl alcohol 8 times, by the pressurized backflow of 1-chlorobutane part in chlorobutane storage tank
Return the tower top of reactive distillation column, top, middle part, the many places of bottom carry out azeotropic and move water, the 1-chlorobutane generated with reaction and water
From rectifying column top azeotropic out.Another part 1-chlorobutane in chlorobutane storage tank is transported to distillation system, after rectification
Obtain 1-chlorobutane product.The still liquid of the tower reactor accumulation of described reactive distillation column is admitted to n-butyl ether distillation column and distills, just
The 1-chlorobutane mixed gas that butyl ether overhead steams returns again to reactive distillation column tower reactor and continues reaction.Described n-butyl ether
Distillation column, bottom temperature controls at 130 DEG C.
Comparative example 1
Comparative example 1 is to use the tower of the concentrated hydrochloric acid direct dereaction rectifying column of 35wt% with the difference of embodiment 4
Still, with n-butyl alcohol directly rectification after the tower reactor of reactive distillation column is reacted.
1-chlorobutane purity, yield and steam consumption situation that the method for embodiment 1-4 and comparative example 1 prepares are shown in
Table 1.
| Project | 1-chlorobutane purity (wt%) | 1-chlorobutane yield (%) | Steam consumption (t) |
| Embodiment 1 | 96.8 | 97.5 | 1.4 |
| Embodiment 2 | 96.5 | 98.1 | 2.3 |
| Embodiment 3 | 97.2 | 98.0 | 2.5 |
| Embodiment 4 | 96.9 | 97.1 | 2.7 |
| Comparative example 1 | 92.3 | 90.1 | 3.4 |
As shown in Figure 1, the synthesis device that the continuous synthesis of a kind of 1-chlorobutane is used, including: be sequentially communicated is dense
Salt acid storage tank 1, concentrated hydrochloric acid feed pump 2, preheater 3 and hydrochloric acid desorption tower 4, the tower reactor of described hydrochloric acid desorption tower 4 respectively with boil again
Device 5 connects with the thermal medium inlet of described preheater 3, and described in the outlet of described reboiler 5, the bottom of hydrochloric acid desorption tower 4 is entered
Mouthful；The thermal medium outlet of described preheater 3 is communicated with dilute hydrochloric acid storage tank 6；The top exit of described hydrochloric acid desorption tower 4 first passes through slow
Entered the tower reactor of reactive distillation column 11 by mixing duct 8 after rushing tank 7；Described mixing duct 8 is also by n-butyl alcohol feed pump 10
Connection n-butyl alcohol storage tank 9；The tower top outlet of described reactive distillation column 11 has been sequentially communicated condenser 12, chlorobutane bypass channel 13 and
Chlorobutane storage tank 14.Described chlorobutane storage tank 14 by reflux pump 16 be respectively communicated with the tower top of described reactive distillation column 11, top,
Middle part, bottom one at or many places.Described chlorobutane storage tank 14 is communicated with chlorobutane rectification dress also by chlorobutane delivery pump 17
Put；Described chlorobutane bypass channel 13 is also communicated with waste water storage tank 15.
As a kind of specific embodiment, described dilute hydrochloric acid storage tank 6 connects multistage absorption by dilute hydrochloric acid delivery pump 20
Circulating tank；Described waste water storage tank 15 connects the most end one-level absorption cycle tank of described multistage absorption circulating tank.
As a kind of specific embodiment, the outlet at bottom of described reactive distillation column 11 is also by residual liquid delivery pump 18 even
Being connected with n-butyl ether distillation column 19, the tower top outlet of described n-butyl ether distillation column 19 connects the tower reactor of described reactive distillation column 11.
Claims (10)
1. a method for continuously synthesizing for 1-chlorobutane, using concentrated hydrochloric acid and n-butyl alcohol is raw material, blended reaction and azeotropic essence
Evaporate and obtain 1-chlorobutane, it is characterised in that concentrated hydrochloric acid the most also includes that a desorption step, described desorption step include:
Enter from the tower top of hydrochloric acid desorption tower after preheated for concentrated hydrochloric acid device is preheated, stripped after obtain from hydrochloric acid desorption tower tower reactor
Dilute hydrochloric acid, part produces through reboiler and enters the bottom of hydrochloric acid desorption tower after azeotropic vaporization, declines with tower top in uphill process
Concentrated hydrochloric acid carry out mass transfer and heat transfer, hydrochloric acid desorption tower top obtains the hydrogen chloride gas of purity more than 99%, go with n-butyl alcohol mix
Close reaction.
The method for continuously synthesizing of a kind of 1-chlorobutane the most as claimed in claim 1, it is characterised in that described hybrid reaction is with common
Boiling rectification includes step:
The hydrogen chloride gas ejected from hydrochloric acid desorption tower, enters reactive distillation with n-butyl alcohol in mixing duct jointly after mixing
Bottom the tower reactor of tower, the bottom temperature of control reactive distillation column, at 95～115 DEG C, controls the tower top temperature of reactive distillation column 68
～70 DEG C, the 1-chlorobutane of reaction generation and water are from reactive distillation top of tower azeotropic out.
The method for continuously synthesizing of a kind of 1-chlorobutane the most as claimed in claim 2, it is characterised in that: from reactive distillation top of tower
Azeotropic 1-chlorobutane out and water condensed after enter chlorobutane bypass channel, upper oil phase after layering enters chlorobutane storage
Groove, the pressurized backflow of 1-chlorobutane part in chlorobutane storage tank is returned reactive distillation column and is carried out azeotropic shifting water, with reaction generation
1-chlorobutane and water are from reactive distillation top of tower azeotropic out.
The method for continuously synthesizing of a kind of 1-chlorobutane the most as claimed in claim 3, it is characterised in that: by chlorobutane storage tank
1-chlorobutane part is pressurized to be transmitted back to reactive distillation column and carries out azeotropic when moving water, be transmitted back to the tower top of reactive distillation column, on
Portion, middle part, bottom one at or many places.
The method for continuously synthesizing of a kind of 1-chlorobutane the most as claimed in claim 3, it is characterised in that: another in chlorobutane storage tank
A part of 1-chlorobutane is transported to distillation system, obtains the purity 1-chlorobutane product more than 99.5wt% after rectification.
The method for continuously synthesizing of a kind of 1-chlorobutane the most as claimed in claim 2, it is characterised in that: described reactive distillation column
The still liquid of tower reactor accumulation is admitted to n-butyl ether distillation column and distills, the 1-chlorobutane gaseous mixture that n-butyl ether overhead steams
Body returns again to reactive distillation column tower reactor and continues reaction.
The method for continuously synthesizing of a kind of 1-chlorobutane the most as claimed in claim 1, it is characterised in that: take off from hydrochloric acid after stripped
Inhale another part dilute hydrochloric acid that tower tower reactor obtains, after described preheater removes pre-Thickish hot hydrochloric acid, enter dilute hydrochloric acid storage tank, the most again
Conveying goes absorbing hydrogen chloride gas to produce the concentrated hydrochloric acid raw material of concentration 25～35wt%.
8. the synthesis device that the continuous synthesis of a 1-chlorobutane is used, it is characterised in that including:
Hydrochloric acid desorption tower, the upper inlet of described hydrochloric acid desorption tower is communicated with concentrated hydrochloric acid storage tank by preheater, and described hydrochloric acid takes off
The tower reactor thermal medium inlet with reboiler and described preheater respectively inhaling tower connects, salt described in the outlet of described reboiler
The lower inlet of acid desorption tower；
The top exit of described hydrochloric acid desorption tower connects reactive distillation column by mixing duct；Described mixing duct also connects positive fourth
Alcohol storage tank；
The tower top outlet of described reactive distillation column has been sequentially communicated condenser, chlorobutane bypass channel and chlorobutane storage tank.
The equipment that the continuous synthesis of a kind of 1-chlorobutane the most as claimed in claim 8 is used, it is characterised in that:
The thermal medium outlet of described preheater is communicated with dilute hydrochloric acid storage tank；Described chlorobutane storage tank is respectively communicated with institute by reflux pump
State the tower top of reactive distillation column, top, middle part, bottom one at or many places；The outlet at bottom of described reactive distillation column also by
Residual liquid delivery pump is communicated with n-butyl ether distillation column, and the tower top outlet of described n-butyl ether distillation column connects the tower of described reactive distillation column
Still.
The equipment that the continuous synthesis of a kind of 1-chlorobutane the most as claimed in claim 8 is used, it is characterised in that:
Described chlorobutane storage tank is also communicated with chlorobutane rectifier unit；Described chlorobutane bypass channel is also communicated with waste water storage tank.
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| CN113480401A (en) * | 2021-07-09 | 2021-10-08 | 岳阳隆兴实业有限公司 | Synthesis method of chloro-n-pentane |
| CN113501744A (en) * | 2021-07-09 | 2021-10-15 | 岳阳隆兴实业有限公司 | Synthesis method of chloro-sec-butyl alkane |
| CN113896614A (en) * | 2021-11-08 | 2022-01-07 | 山东绿色海洋化工研究院有限公司 | Method for continuously synthesizing chlorobutane in non-aqueous system |
| CN114213232A (en) * | 2021-12-29 | 2022-03-22 | 江苏清泉化学股份有限公司 | Continuous production method of low-moisture 5-chloro-2-pentanone |
| CN114478182A (en) * | 2022-01-21 | 2022-05-13 | 安徽伟祥新材料有限公司 | Device and method for producing chloralkane series products |
| CN116162014A (en) * | 2022-12-16 | 2023-05-26 | 山东兴文工业技术研究院有限公司 | Method for continuously preparing tert-butyl chloride through micro-channels |
| CN116621674A (en) * | 2023-05-09 | 2023-08-22 | 岳阳隆兴实业有限公司 | Purification method of crude chlorobutane |
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| CN113480401A (en) * | 2021-07-09 | 2021-10-08 | 岳阳隆兴实业有限公司 | Synthesis method of chloro-n-pentane |
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| CN113896614A (en) * | 2021-11-08 | 2022-01-07 | 山东绿色海洋化工研究院有限公司 | Method for continuously synthesizing chlorobutane in non-aqueous system |
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| CN114213232A (en) * | 2021-12-29 | 2022-03-22 | 江苏清泉化学股份有限公司 | Continuous production method of low-moisture 5-chloro-2-pentanone |
| CN114478182A (en) * | 2022-01-21 | 2022-05-13 | 安徽伟祥新材料有限公司 | Device and method for producing chloralkane series products |
| CN116162014A (en) * | 2022-12-16 | 2023-05-26 | 山东兴文工业技术研究院有限公司 | Method for continuously preparing tert-butyl chloride through micro-channels |
| CN116621674A (en) * | 2023-05-09 | 2023-08-22 | 岳阳隆兴实业有限公司 | Purification method of crude chlorobutane |
| CN116621674B (en) * | 2023-05-09 | 2024-05-14 | 岳阳隆兴实业有限公司 | Purification method of crude chlorobutane |
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