CN108911956A - It is a kind of to crack the purifying technique of by-product in the condensation reaction - Google Patents
It is a kind of to crack the purifying technique of by-product in the condensation reaction Download PDFInfo
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
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Abstract
The purifying technique of by-product in the condensation reaction is cracked the present invention provides a kind of, the purification in preparation and condensation reaction including organic fraction, the preparation of organic fraction：Isophorone is prepared 3, the product generated during 5- xylenol is successively washed, removes pyroreaction and lightness-removing column, the NaOH solution that concentration is 5% is subjected to mixing at a temperature of 30-40 DEG C with the front-end volatiles of lightness-removing column react phenolic substances therein with alkali to generate the sodium phenolate being soluble in the aqueous phase and insoluble in the organic phase of water phase, split-phase acquisition organic phase is organic fraction after organic phase is washed at normal temperature；Purification in condensation reaction：Organic fraction and acetone, water and catalyst are subjected to Michael's addition in the reactor and elimination reaction generates isophorone, mixture after reaction is extracted into mesitylene and isophorone successively by de- light, de- light, de- light, the de- processing again of third step decompression of second step normal pressure of first step normal pressure and removing impurities processing in atmospheric distillation tower.
Description
Technical field
The invention belongs to purifying technique, it is more particularly to a kind of cracking by-product mesitylene and isopropylidene acetone is being condensed
Purifying technique in reaction.
Background technique
Isophorone (Isophorone, ISO) is the product of condensation of acetone, chemical name：3,5,5- trimethyl -2- hexamethylene
- 1 ketone of alkene, molecular formula：C9H14O, molecular weight：138.21, appearance colorless or light yellow transparent liquid have higher, low
Hygroscopicity, solvability, dispersibility, good leveling property are the good solvents of high molecular material, can dissolve nitrocellulose, third
Olefin(e) acid ester, alkyd resin, polyester and epoxy resin etc..Due to its have it is unsaturated with structure, double bond can further occurrence it is anti-
The staple products such as alcohol, acid, amine, ester and isocyanates should be generated, are had in the industry such as plastics, pesticide, medicine, coating extensive
Purposes.
3,5- xylenol is white crystal.Molecular formula is C8H10O, molecular weight 122.17, fusing point：63-66 DEG C, boiling
Point：222 DEG C, density：0.968, CAS 108-68-9, is dissolved in water and ethyl alcohol.For phenolic resin processed, medicine, insecticide,
Dyestuff and explosive；It is the intermediate for preparing carbamate insecticides methiocarb, it may also be used for production rubber accelerator is prevented always
Agent, drug, fragrance, phenolic resin etc. also serve as steel rolling cold rolling oil additive, can extend cold-rolled lubricating oil service life；For giving birth to
Produce insecticide, rubber accelerator, anti-aging agent, drug, fragrance, phenolic resin etc..Steel rolling cold rolling oil additive is also served as, can be prolonged
Long cold-rolled lubricating oil service life.
Isophorone aromatisation preparation 3,5-dimethylphenol reaction process is mainly to pass through the route progress of two competitions
's.One of process is the phenolic ketone rearrangement process after isophorone demethanation, mainly generates 3,5-dimethylphenol；It is another
Process be isophorone decomposable process, this process can be generated a variety of by-products have 1,3,5- trimethylbenzenes, meta-xylene,
Toluene, metacresol, diacetone alcohol, Mesityl oxide, acetone etc..
It is as follows that isophorone aromatisation prepares 3,5-dimethylphenol reaction equation：
First condensation generates diacetone alcohol to acetone in the presence of highly basic, and then dehydration generates isopropylidene acetone, then contracts with acetone
Conjunction, cyclisation, dehydration obtain isophorone, and the selectivity and conversion ratio of the process are all relatively low.Have both at home and abroad a large amount of special
Benefit, documents and materials study its reaction mechanism, have also done a large amount of full and accurate careful works to the optimization of parameters of technique process
Make.
From the point of view of the data reported at present, isophorone is generated during raw material preparation 3,5-dimethylphenol equal
Patent and documents and materials are reported not yet for the application of trimethylbenzene and isopropylidene acetone in condensation of acetone reaction, this respect
Further investigation be in space state.
It can be seen that generating the mesitylene and isopropylidene acetone two generated during 3,5-dimethylphenol to aromatisation
Kind byproduct is applied to condensation of acetone and prepares isophorone technical study with positive meaning, passes through the reasonably optimizing of technique
Both it had been able to achieve the yield of auxiliary material made full use of or reaction can be properly increased, there is significant economic significance.
Summary of the invention
The object of the present invention is to provide a kind of purifying technique of the higher cracking by-product of reaction yield in the condensation reaction.
According to an aspect of the invention, there is provided a kind of purifying technique of cracking by-product in the condensation reaction, including
Including
The preparation of organic fraction：Isophorone is prepared to the washed acquisition of product generated during 3,5- xylenol
Wash organic phase, will washing organic phase carried out in weight-removing column it is de- handle to obtain de- heavy organic phase again, by de- heavy organic phase de- light
It carries out taking off in tower and gently handles to obtain de- light kettle liquid and the de- light front-end volatiles for refining 3,5-dimethylphenol, be 5% by concentration
NaOH solution obtains organic fraction with the organic phase for taking off light front-end volatiles and react generation after washing；
Purification in condensation reaction：Organic fraction and acetone, process water and catalyst are subjected to Michael in the reactor
Addition and elimination reaction generate isophorone, and the mixture after reaction is carried out to the first step in atmospheric distillation tower and is taken off without heat source
It gently handles to obtain first step removing product, it is de- light that first step removing product is continued the progress second step normal pressure in atmospheric distillation tower
Handle second step takes off light kettle liquid, second step is taken off into light kettle liquid and carries out that third step decompression is de- gently to be handled in vacuum rectification tower
Third step takes off light kettle liquid, by third step take off light kettle liquid carried out in weight-removing column it is de- handle to obtain de- heavy Produced Liquid again, it is described de- to adopt again
The heavy constituent content of liquid is not higher than 2% out,
De- heavy Produced Liquid is subjected to removing impurities processing in removing impurities tower, is not higher than 120 DEG C in kettle temperature, top is 90-100 DEG C warm, very
Removing impurities front-end volatiles are acquired under conditions of reciprocal of duty cycle -0.09Mpa, pressure difference 6-8Kpa, as the raw material for extracting isopropylidene acetone or directly
It is used as compounded organic solvent, at 120-125 DEG C of kettle temperature, 100-105 DEG C, vacuum degree -0.095Mpa, pressure difference 6- of top temperature
Under the conditions of 8Kpa, the fraction that main component is mesitylene is extracted, at 130-150 DEG C of kettle temperature, 110-120 DEG C of top temperature,
Under the conditions of vacuum degree -0.098Mpa, pressure difference 6-8Kpa, the fraction that main component is isophorone is extracted.
In some embodiments, the organic fraction is free of phenolic substances, is liquid under room temperature, main matter component is pressed
Mass percent is isopropylidene acetone 32-34%, mesitylene 48-51%, other components 15-20%, and other components include third
Ketone 8-11%, diacetone alcohol 3-4%, water 2%, other 2-3%, the other components include acetone 8-11%, diacetone alcohol 3-
4%, water 2%, other 2-3%.
In some embodiments, the second step normal pressure takes off raw material of the light overhead extraction object as condensation reaction, institute
State raw material of the de- light gained overhead extraction object of third step decompression as condensation reaction.
In some embodiments, isopropylidene acetone is added during preparing isophorone.
In some embodiments, the flow-rate ratio 9 of acetone and organic fraction:1~8:1, the feed rate of process water according to
The 15-20% of total mass flow controls makeup water stream amount, and catalyst is the KOH solution of 30% concentration, and dosage is total mass flow
0.1%, 180-185 DEG C of reaction temperature, reaction pressure 1.8-2.2Mpa, residence time 30-45min.
In some embodiments, de- light without heat source to the first step of reaction solution using 180-185 DEG C of reaction heat, it is described
The first step takes off without heat source gently to be carried out in atmospheric distillation tower, and kettle temperature is 120-130 DEG C, and top temperature is 55-57 DEG C, the product of removing
Mainly acetone and water, wherein acetone is 95-98%, all returns to condensation reaction process and uses as raw material.
In some embodiments, the de- light continuation of the second step normal pressure carries out in atmospheric distillation tower, controls tower top temperature
56~60 DEG C of degree, the valve opening by adjusting heating steam control produced quantity, and micro-positive pressure in tower, tower reactor and tower top pressure difference are 6
~8Kpa, controls tower reactor content of acetone≤5% by 70~80 DEG C of bottom temperature, and content of acetone is reachable in the material of overhead extraction
90% all of the above returns to condensation reaction process and uses as raw material.
In some embodiments, the third step decompression takes off carries out in vacuum rectification tower, and control vacuum rectification tower is true
Between reciprocal of duty cycle -0.05-0.06Mpa, 56~80 DEG C of tower top temperature, 70~100 DEG C of bottom temperature, pressure difference is in 6~8Kpa, control
Tower reactor content of acetone≤1%, content of acetone all returns to condensation reaction processes up to 80-85% and makees in the material of overhead extraction
For raw material use.
In some embodiments, mesitylene rectification and purification：Mesitylene in crude product tank is sent into rectifying column in kettle
Warm 120-130 DEG C, top temperature 105-110 DEG C, vacuum degree -0.098Mpa under the conditions of pressure difference 6-8Kpa, pass through and adjust reflux ratio general
Mesitylene of the content higher than 98% extracts, and obtains mesitylene finished product.
Its advantages are：Aromatisation is generated the mesitylene and different generated during 3,5- xylenol by the present invention
Two kinds of byproducts of propylidene acetone are applied to the technique that condensation of acetone prepares isophorone, can be real by the reasonably optimizing of technique
Existing auxiliary material makes full use of the yield that can also properly increase reaction, has significant economic significance.
Detailed description of the invention
Fig. 1 is that a kind of process of the purifying technique of cracking by-product of one embodiment of the present invention in the condensation reaction is shown
It is intended to.
Specific embodiment
3,5-dimethylphenol will be used wider and wider as a kind of highly important fine chemical product, and with different Buddhist
Your ketone is the production technology that raw material prepares that 3,5- xylenol is a kind of very convenient and efficient by catalytic pyrolysis.Different Fo Er
Ketone can occur to crack dehydration generation mesitylene at high temperature, while isophorone itself can be decomposed to form isopropylidene third
Ketone, both by-products total content shared in cracking process is lower, generally as industrial by-products be collected without
Deeply utilize.The organic fraction that the present invention is had use value the by-product by the processing of certain procedures, then again
It is added to acetone liquid phase condensations to prepare in isophorone technique, realizes making full use of for supplementary material.
Fig. 1 schematically shows the purification work of the cracking by-product of one embodiment of the present invention in the condensation reaction
Skill.As shown in Figure 1, the purifying technique of cracking by-product in the condensation reaction includes the preparation and condensation reaction of organic fraction
In purification.
The definition of organic fraction：It will be produced during catalytic pyrolysis prepares 3,5- xylenol using isophorone as raw material
What raw all products obtained after " washing-takes off the de- light-alkalization-washing split-phase of weight-" processing is rich in isopropylidene acetone and equal front three
The organic phase mixed liquor of benzene by-product is known as the signified organic fraction of the present invention.The organic fraction is characterized in without phenolic material
Matter is liquid under room temperature, and main matter component is isopropylidene acetone 32-34%, mesitylene 48- by mass percentage
51%, other components 15-20%, other components include acetone 8-11%, diacetone alcohol 3-4%, water 2%, other 2-3%.
The preparation of organic fraction：Isophorone is prepared to the washed acquisition of product generated during 3,5- xylenol
Wash organic phase, will washing organic phase carried out in weight-removing column it is de- handle to obtain de- heavy organic phase again, by de- heavy organic phase de- light
It carries out taking off in tower and gently handles to obtain de- light kettle liquid and the de- light front-end volatiles for refining 3,5-dimethylphenol, be 5% by concentration
NaOH solution obtains organic fraction with the organic phase for taking off light front-end volatiles and react generation after washing.Specifically organic grade
The acquisition process divided：All productions will be generated during catalytic pyrolysis prepares 3,5- xylenol using isophorone as raw material
Object is washed-de- weight-can be obtained by after de- light-alkalization-washing-acidification split-phase rich in isopropylidene acetone and mesitylene
Mixture.
Washing process：By reaction product (the isopropylidene acetone 0.4-0.8%, mesitylene of isophorone at high temperature
1.0-1.5%, isophorone 2.0-5.0%, 3,5- xylenol 90-94%, other components 1.0-3.0%) in process water
98-102 DEG C of washing temperature of washing control, pressure≤0.05Mpa, PH=9-10, directly in scrubbing tower after washing are carried out under effect
It is middle to carry out continuous split-phase processing, obtain upper organic phase be sent into it is de- in next step handle again, and catalyst is rich in the water phase of lower layer
Processing is collected into the dedicated recovery process of catalyst.
De- weight process：The organic phase that scrubbing tower upper layer obtains is carried out generating in removing high-temperature reaction process in weight-removing column
Residue and the substances such as carbon distribution, which is 140-160 DEG C of kettle temperature, pushes up warm 120-130 DEG C, vacuum degree-
0.085Mpa.The organic matter of weight-removing column top extraction fully enters in lightness-removing column to be handled again.
Take off light process：By the organic matter that weight-removing column top produces carried out in lightness-removing column rectifying respectively obtain tower top front-end volatiles and
Kettle liquid two parts substance, the technological parameter of lightness-removing column are 130-140 DEG C of tower reactor, 100-110 DEG C of tower top, vacuum degree-
0.085Mpa.The front-end volatiles of lightness-removing column top extraction mainly have the low-boiling fractions such as isopropylidene acetone, mesitylene and phenols, should
It needs to carry out phenol removal containing phenolic substances in fraction.Tower bottoms main component after taking off gently is 3,5- xylenol
Crude product, the crude product subsequently enter subtractive process and extract 3,5-dimethylphenol finished product.
Alkalization：Mix making wherein with the front-end volatiles of lightness-removing column at a temperature of 30-40 DEG C with the NaOH solution of 5% concentration
Phenolic substances reacted with alkali generate sodium phenolate be soluble in the aqueous phase, it is counter after the acidified split-phase of the water phase that phenolic substances is precipitated, will be precipitated
Phenolic substances be sent into 3,5- xylenol subtractive process.And organic phase not soluble in water is washed.
Wash split-phase：It is purified, will be obtained after alkalization due to containing a small amount of free alkali needs in previous step organic phase
To organic phase washed at normal temperature after split-phase, otherwise removal free alkali will lead to the blistering of subsequent material and a variety of pairs
Reaction, generates uncontrollable danger.Organic phase after washing split-phase is organic fraction.The main content of organic fraction is about in 80-
85% or so needs not move through depths reason, and organic fraction mix with acetone directly as raw material to put into condensation reaction
In.
Purification in condensation reaction：Organic fraction and acetone, water and catalyst are subjected to Michael's addition in the reactor
Isophorone is generated with elimination reaction, the mixture after reaction is carried out to the first step in atmospheric distillation tower without the de- light place of heat source
First step removing product is managed to obtain, first step removing product is continued to carry out the de- light processing of second step normal pressure in atmospheric distillation tower
Second step takes off light kettle liquid, second step is taken off into light kettle liquid and carries out the de- light third that handles to obtain of third step decompression in vacuum rectification tower
Step takes off light kettle liquid, and third step is taken off light kettle liquid and carries out de- handling to obtain de- heavy Produced Liquid, the de- heavy Produced Liquid again in weight-removing column
Heavy constituent content be not higher than 2%,
De- heavy Produced Liquid is subjected to removing impurities processing in removing impurities tower, is not higher than 120 DEG C in kettle temperature, top is 90-100 DEG C warm, very
Removing impurities front-end volatiles are acquired under conditions of reciprocal of duty cycle -0.09Mpa, pressure difference 6-8Kpa, as the raw material for extracting isopropylidene acetone or directly
It is used as compounded organic solvent, at 120-125 DEG C of kettle temperature, 100-105 DEG C, vacuum degree -0.095Mpa, pressure difference 6- of top temperature
Under the conditions of 8Kpa, the fraction that main component is mesitylene is extracted, at 130-150 DEG C of kettle temperature, 110-120 DEG C of top temperature,
Under the conditions of vacuum degree -0.098Mpa, pressure difference 6-8Kpa, the fraction that main component is isophorone is extracted.
The organic fraction will carry out carrying out Michael's addition in reactor in next step and be disappeared together with acetone, water and catalyst
Except reaction generates isophorone, which is " de- light-de- weight-removing impurities-rectifying of condensation reaction-".Pass through the process flow
Obtain finished product mesitylene.
Explanation to condensation reaction：First first occurred reaction is third during preparing isophorone due to condensation of acetone
Ketone condensation generates diacetone alcohol, and then diacetone alcohol is dehydrated to form isopropylidene acetone again, and third step isopropylidene acetone and acetone contract
Symphysis is at isophorone, and the amount of isopropylidene acetone is to determine the key factor of isophorone amount in the reaction process, therefore from mixed
The conversion ratio of the reaction can be effectively improved by closing the isopropylidene acetone supplemented in object, simultaneously because mesitylene structure is steady
Surely it cannot participate in reaction, but the diluting effect of solvent can be played, promote the progress of the reaction；Another aspect condensation of acetone
A certain amount of mesitylene can also be generated in the process by preparing isophorone, and the amount of this part mesitylene is about during normal production
This two-part mesitylene is obtained mesitylene finished product as material stream carries out Enrichment purification by 0.2-0.5%.
Condensation reaction：The flow-rate ratio 9 of acetone and organic fraction:1~8:1, the feed rate of process water is according to total mass flow
15-20% control makeup water stream amount, catalyst is the KOH solution of 30% concentration, and dosage is that total mass flow 0.1% is
Can, 180-185 DEG C of reaction temperature, reaction pressure 1.8-2.2Mpa, residence time 30-45min.It is anti-according to process conditions as above
The content that should terminate later reaction solution is acetone 74.59%, isopropylidene acetone 6.33%, diacetone alcohol 0.88%, mesitylene
0.96%, isophorone 12.99%, heavy constituent 2.23%, other components 2.02%, moisture content 19.34%, PH=9-10 should
Reaction solution is light yellow transparent liquid.
Light process is taken off to be carried out in three steps：
The first step is de- light without heat source：It is carried out using reaction heat (180-185 DEG C) to the primary de- light of reaction solution, this takes off light mistake
Journey carries out in atmospheric distillation tower, and kettle temperature is 120-130 DEG C (kettle temperature is higher the reason is that reacting liquid temperature is higher), and top temperature is
55-57 DEG C, the product of process removing is mainly acetone and water, and wherein acetone is 95-98%, all returns to condensation reaction work
Sequence is used as raw material.Kettle liquid discharges content as acetone 48%, isopropylidene acetone 12.95%, mesitylene 1.96%, dipropyl
Keto-alcohol 1.83%, isophorone 26.57%, heavy constituent 4.56%, other 4.13%.
Second step normal pressure is de- light：Since the content of acetone in first step kettle liquid is still higher therefore the process continues in normal pressure
It is carried out in rectifying column, controls 56~60 DEG C of tower top temperature, the valve opening by adjusting heating steam controls produced quantity, in tower
Micro-positive pressure, tower reactor and tower top pressure difference are 6~8Kpa, and 70~80 DEG C of bottom temperature, which is tower reactor content of acetone
≤ 5%.Content of acetone returns to condensation reaction process as raw material up to 90% all of the above and uses in the material of overhead extraction.
Kettle liquid discharges content as acetone 2%, isopropylidene acetone 24.4%, mesitylene 3.69%, diacetone alcohol 3.47%, different Fo Er
Ketone 50.07%, heavy constituent 8.59%, other 7.78%.
Third step decompression is de- light：The process carries out in vacuum rectification tower, for the volatilization for reducing the light components such as acetone, control
Between rectifying tower vacuum degree -0.05-0.06Mpa, 56~80 DEG C of tower top temperature, 70~100 DEG C of bottom temperature, pressure difference 6~
8Kpa, the key point in course are by tower reactor content of acetone≤1%.Content of acetone is up to 80-85% in the material of overhead extraction
Condensation reaction process is all returned to use as raw material.Kettle liquid discharge content be acetone 0.6%, isopropylidene acetone 24.76%,
Mesitylene 3.74%, diacetone alcohol 3.52%, isophorone 50.78%, heavy constituent 8.71%, other 7.89%.
De- weight process：Material after taking off gently enters in weight-removing column under -0.085Mpa vacuum condition, bottom temperature 160-
190 DEG C, 110-130 DEG C of tower top, pressure difference 2-3Kpa, the key control point of the process is by the heavy constituent total content of overhead extraction liquid
Not higher than 2%.Overhead extraction material content is acetone 0.64%, isopropylidene acetone 26.57%, mesitylene 4.01%, dipropyl
Keto-alcohol 3.8%, isophorone 54.51%, heavy constituent 2%, other 8.47%.Tower reactor is mainly residue and tar as solid waste
Processing.
Removing impurities process：The function of removing impurities tower is to realize the primary separation of each component material, obtains four kinds of different fractions difference
It is front-end volatiles, mesitylene crude product, isophorone crude product and tails (kettle is residual), the process is in a gap rectifying column
It carries out, multi-component separation is realized according to the parameter of the different adjustment tower of fraction.
(1) front-end volatiles collection process：120 DEG C are not higher than in kettle temperature, top is 90-100 DEG C, vacuum degree -0.09Mpa warm, pressure difference
Under the conditions of 6-8Kpa, the fraction that main component is isopropylidene acetone is extracted, the content of the fraction is acetone 2.08%, different
Propylidene acetone 82.02%, diacetone alcohol 12.34%, mesitylene 0.78% and other components 2.78%.The front-end volatiles can be made
To extract the raw material of isopropylidene acetone or being used directly as compounded organic solvent.
(2) mesitylene fraction collection process：At 120-125 DEG C of kettle temperature, 100-105 DEG C of top temperature, vacuum degree-
Under the conditions of 0.095Mpa, pressure difference 6-8Kpa, the fraction that main component is mesitylene is extracted, the content of the fraction is
Isopropylidene acetone 12.05%, mesitylene 54.37%, isophorone 8.13%, other 25.45%.Equal three in the component
Toluene has reached 50% or more and has a further purification condition, the fraction fully enter in mesitylene crude product tank then into
Row rectification and purification obtains mesitylene finished product.
(3) isophorone crude product fraction collection process：At 130-150 DEG C of kettle temperature, 110-120 DEG C of top temperature, vacuum degree-
Under the conditions of 0.098Mpa, pressure difference 6-8Kpa, the fraction that main component is isophorone is extracted, the content of the fraction is
Isopropylidene acetone 0.97%, mesitylene 0.29%, isophorone 93.72%, heavy constituent 0.37% and other 4.65%, should
Fraction obtains the raw material of isophorone finished product as next step purification, and the further purifying technique of the fraction is not chatted in this patent
And in range.
(4) tails：After after being purified front-end volatiles, mesitylene fraction and isophorone crude product fraction respectively in tower reactor
The residue that remaining total amount is about 5-8% is that tails is also referred to as that kettle is residual, and the main component of the fraction is isophorone
34.38%, heavy constituent 22.77%, other 42.85%.Although isophorone content is higher in the fraction but conventional rectification process
It has been difficult further to separate, because further the content of compression isophorone can make the residual mobility of the kettle be deteriorated rapidly, has caused
Tails/kettle is residual to be difficult to release from rectifying column, and then is influenced rectifying column and operated normally.
Mesitylene rectification and purification：Mesitylene in crude product tank is sent into rectifying column in 120-130 DEG C of kettle temperature, top temperature
105-110 DEG C, vacuum degree -0.098Mpa, under the conditions of pressure difference 6-8Kpa, by adjust reflux ratio by content be higher than 98% equal three
Toluene extracts, and obtains mesitylene finished product.
Above-described is only some embodiments of the present invention, for those of ordinary skill in the art, is not being taken off
Under the premise of from the invention design, various modifications and improvements can be made, these belong to protection model of the invention
It encloses.
Claims (9)
1. a kind of purifying technique of cracking by-product in the condensation reaction, which is characterized in that including
The preparation of organic fraction：Isophorone is prepared to the washed acquisition washing of the product generated during 3,5- xylenol
Organic phase, will washing organic phase carried out in weight-removing column it is de- handle to obtain de- heavy organic phase again, by de- heavy organic phase in lightness-removing column
Take off and gently handles to obtain de- light kettle liquid and the de- light front-end volatiles for refining 3,5-dimethylphenol, the NaOH for being 5% by concentration
Solution obtains organic fraction with the organic phase for taking off light front-end volatiles and react generation after washing；
Purification in condensation reaction：Organic fraction and acetone, process water and catalyst are subjected to Michael's addition in the reactor
Isophorone is generated with elimination reaction, the mixture after reaction is carried out to the first step in atmospheric distillation tower without the de- light processing of heat source
The first step removes product, by first step removing product continue to carry out in atmospheric distillation tower second step normal pressure it is de- gently handle the
Two steps take off light kettle liquid, by second step take off light kettle liquid carried out in vacuum rectification tower third step decompression it is de- gently handle third step is de- light
Third step is taken off light kettle liquid and carries out de- handling to obtain de- heavy Produced Liquid, the recombination of the de- heavy Produced Liquid again in weight-removing column by kettle liquid
Content is divided to be not higher than 2%,
De- heavy Produced Liquid is subjected to removing impurities processing in removing impurities tower, is not higher than 120 DEG C in kettle temperature, top is 90-100 DEG C warm, vacuum degree-
Removing impurities front-end volatiles are acquired under conditions of 0.09Mpa, pressure difference 6-8Kpa, as the raw material for extracting isopropylidene acetone or directly as multiple
Organic solvent is closed to use, at 120-125 DEG C of kettle temperature, 100-105 DEG C, vacuum degree -0.095Mpa of top temperature, pressure difference 6-8Kpa condition
Under, the fraction that main component is mesitylene is extracted, at 130-150 DEG C of kettle temperature, 110-120 DEG C of top temperature, vacuum degree-
Under the conditions of 0.098Mpa, pressure difference 6-8Kpa, the fraction that main component is isophorone is extracted.
2. the purifying technique of cracking by-product according to claim 1 in the condensation reaction, which is characterized in that described organic
Fraction is free of phenolic substances, is liquid under room temperature, main matter component is isopropylidene acetone 32-34% by mass percentage,
Trimethylbenzene 48-51%, other components 15-20%, other components include acetone 8-11%, diacetone alcohol 3-4%, water 2%, other
2-3%, the other components include acetone 8-11%, diacetone alcohol 3-4%, water 2%, other 2-3%.
3. the purifying technique of cracking by-product according to claim 1 in the condensation reaction, which is characterized in that described second
Step normal pressure takes off raw material of the light overhead extraction object as condensation reaction, the de- light gained overhead extraction object conduct of third step decompression
The raw material of condensation reaction.
4. the purifying technique of cracking by-product according to claim 1 in the condensation reaction, which is characterized in that different preparing
Isopropylidene acetone is added during phorone.
5. cracking by-product purifying technique in the condensation reaction according to claim 1, which is characterized in that acetone with have
The flow-rate ratio 9 of machine fraction:1~8:1, the feed rate of process water controls makeup water stream amount according to the 15-20% of total mass flow, urges
Agent be 30% concentration KOH solution, dosage be total mass flow 0.1%, 180-185 DEG C of reaction temperature, reaction pressure
Power 1.8-2.2Mpa, residence time 30-45min.
6. the purifying technique of cracking by-product according to claim 1 in the condensation reaction, which is characterized in that utilize 180-
185 DEG C of reaction heat is de- light without heat source to the first step of reaction solution, the first step without heat source it is de- gently in atmospheric distillation tower into
Row, kettle temperature are 120-130 DEG C, and top temperature is 55-57 DEG C, and the product of removing is mainly acetone and water, and wherein acetone is 95-98%,
Condensation reaction process is all returned to use as raw material.
7. the purifying technique of cracking by-product according to claim 1 in the condensation reaction, which is characterized in that described second
The de- light continuation of step normal pressure carries out in atmospheric distillation tower, 56~60 DEG C of tower top temperature is controlled, by the valve for adjusting heating steam
Aperture controls produced quantity, and micro-positive pressure in tower, tower reactor and tower top pressure difference are 6~8Kpa, 70~80 DEG C of bottom temperature, controls tower reactor third
Ketone content≤5%, content of acetone returns to condensation reaction process as raw material up to 90% all of the above in the material of overhead extraction
It uses.
8. the purifying technique of cracking by-product according to claim 1 in the condensation reaction, which is characterized in that the third
Step decompression takes off to be carried out in vacuum rectification tower, is controlled between vacuum rectification tower vacuum degree -0.05-0.06Mpa, and tower top temperature 56~
80 DEG C, 70~100 DEG C of bottom temperature, pressure difference controls tower reactor content of acetone≤1% in 6~8Kpa, third in the material of overhead extraction
Ketone content all returns to condensation reaction process as raw material up to 80-85% and uses.
9. the purifying technique of cracking by-product according to claim 1 in the condensation reaction, which is characterized in that
Mesitylene rectification and purification：Mesitylene in crude product tank is sent into rectifying column in 120-130 DEG C of kettle temperature, top temperature 105-
Under the conditions of pressure difference 6-8Kpa, 98% mesitylene is higher than by adjusting reflux ratio for content by 110 DEG C, vacuum degree -0.098Mpa
It extracts, obtains mesitylene finished product.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50160240A (en) * | 1974-05-15 | 1975-12-25 | ||
| US5352839A (en) * | 1993-09-09 | 1994-10-04 | Aristech Chemical Corporation | Isophorone process |
| CN103435461A (en) * | 2013-07-24 | 2013-12-11 | 河北工业大学 | Production technology for isophorone |
| CN104355969A (en) * | 2014-10-16 | 2015-02-18 | 荣成青木高新材料有限公司 | Preparation method of 3, 5-dimethylphenol |
| CN107573227A (en) * | 2017-08-30 | 2018-01-12 | 中国石油大学(华东) | Acetone vapour phase condensation prepares the device and method of isophorone |
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2018
- 2018-06-20 CN CN201810634690.4A patent/CN108911956B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50160240A (en) * | 1974-05-15 | 1975-12-25 | ||
| US5352839A (en) * | 1993-09-09 | 1994-10-04 | Aristech Chemical Corporation | Isophorone process |
| CN103435461A (en) * | 2013-07-24 | 2013-12-11 | 河北工业大学 | Production technology for isophorone |
| CN104355969A (en) * | 2014-10-16 | 2015-02-18 | 荣成青木高新材料有限公司 | Preparation method of 3, 5-dimethylphenol |
| CN107573227A (en) * | 2017-08-30 | 2018-01-12 | 中国石油大学(华东) | Acetone vapour phase condensation prepares the device and method of isophorone |
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