CN108863793A - A kind of preparation method of isopropyl acetate - Google Patents
A kind of preparation method of isopropyl acetate Download PDFInfo
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- CN108863793A CN108863793A CN201810500561.6A CN201810500561A CN108863793A CN 108863793 A CN108863793 A CN 108863793A CN 201810500561 A CN201810500561 A CN 201810500561A CN 108863793 A CN108863793 A CN 108863793A
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- isopropyl acetate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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Abstract
The invention discloses a kind of preparation methods of isopropyl acetate, including propylene and acetic acid, and catalytic synthesis is completed in fixed bed reactors；The preheated rear feeding lightness-removing column of mixture after reaction, isopropyl acetate, water, propylene are from overhead extraction, after condensation, it will be in isopropyl acetate infinite reflux to lightness-removing column, condensed water outlet, propylene is discharged in the form of fixed gas, the mixture of acetic acid and isopropyl acetate by tower reactor produce and by with react after mixture heat exchange after be sent into product knockout tower；Acetic acid and isopropyl acetate separate in product knockout tower, tower top material condensation rear portion is back in knockout tower, a part is produced as isopropyl acetate product, acetic acid is by tower reactor side take-off and is back to fixed bed reactors and recycles, and C9 alkene and C12 alkene are removed as heavy constituent by tower reactor.Isopropyl acetate preparation method of the invention has the advantages that reaction condition is mild, product separation process is simple and low energy consumption.
Description
Technical field
The present invention relates to the technical field of compound more particularly to a kind of preparation methods of isopropyl acetate.
Background technique
Isopropyl acetate is colourless transparent liquid, have fruit aroma, be allow as defined in Chinese GB2760-86 using
One of flavorant.Since it is with effumability, can with most immiscible organic solvents such as alcohol, ketone, ether, therefore it is referred to as omnipotent
Solvent.It is mainly used as coating, solvent for printing inks, industrial dehydrating agent, extractant and perfume composition in drug production etc..
Traditional isopropyl acetate production technology is to be esterified acetic acid and isopropanol under concentrated sulfuric acid catalyst effect
Reaction, then using processes such as separation, neutralization, precipitating and rectifying, obtains isopropyl acetate product.But there are equipment for the technique
The problems such as seriously corroded, side reaction are more, product separation is complicated, wastewater treatment is difficult, high production cost.
In recent years, it is increasingly paid close attention to by people using the new process of propylene and acetic acid catalysis synthesis of acetic acid isopropyl ester, with
Traditional alkyd esterification technique gradually replaces tradition compared to having many advantages, such as that production cost is low, pollution-free, reaction condition is mild
Technique is widely used.
Chinese patent CN1483717A discloses a kind of synthesis technology of isopropyl acetate and its preparation method of catalyst,
Its technique is：It is reacted under conditions of gas-liquid-solid reaction using fixed bed reactors using solid catalyst,
Solid catalyst includes modified resin catalyst, silica gel load heteropolyacid catalyst, silica gel load phosphoric acid catalyst and superpower
Acid catalyst, reaction temperature are 80 DEG C -125 DEG C, propylene pressure 0.8-1.4MPa, and acetic acid feed air speed is 1.0-2.8h-1,
Propylene feed air speed is 80-108h-1, and acetic acid and propylene molar ratio are 1:1.05-1.8；The invention further includes that carried heteropoly acid is urged
The preparation method of agent, modified resin catalyst, super acidic catalyst etc..
Chinese patent CN102757341A discloses a kind of preparation method of isopropyl acetate, using contain low concentration propylene
Catalysis drying gas (including catalytic cracking, catalytic pyrolysis and thermal cracker) be raw material, utilize multiple fixed bed reactors series connection
Reaction system is entered acetic acid by first reactor, and dry gas share split by a certain percentage enters each reactor, in reaction temperature
130-200 DEG C, pressure 2.0-3.0MPa, the molar ratio 1.3-4.4 of acetic acid and propylene, propylene weight (hourly) space velocity (WHSV) 0.1-0.37h-
Under conditions of 1, is contacted with solid acid catalyst and be converted into isopropyl acetate.
Chinese patent CN106800509A discloses a kind of method for producing isopropyl acetate, the gas including that will contain propane
Material carries out de- light reaction under the action of de- light catalyst, obtains the first product containing propylene；Again by described containing propylene
One product and acetic acid carry out contactless heat exchange, and after pressurized, without heating, it is anti-that addition is carried out under the action of addition catalyst
It answers, obtains isopropyl acetate.
Reaction process condition is different in above-mentioned patent disclosure, differs from one another and advantage, but does not refer to reaction
The separation process of product afterwards.
Chinese patent CN104744248B discloses a kind of method for preparing isopropyl acetate by propylene and acetic acidreaction, packet
It includes feeding fixed bed reactors after mixing inert component with propylene and acetic acid to react, the mixture after reaction is sent into de- weight
Component tower removes heavy constituent, and acetic acid is back to reaction system by side take-off and is recycled, the tower top of de-heavy oil column
Product is further separated after cut light tower is sent into condensation, and the overhead product of cut light tower is through condensing rear portion
It is back to tower top to flow back, a part is back to reaction system and is recycled, and isopropyl acetate product passes through tower bottom side
Line extraction.This method has effectively recycled unreacted propylene feedstocks by introducing inert component.
United States Patent (USP) US005384426 discloses a kind of technical process of effectively preparation high-purity isopropyl acetate, usually
The catalyst used is acid cation exchange resin, reaction can gas phase, liquid phase, can also be gas-liquid mixing phase, n (acetic acid): n
(propylene)=1: 2.The separating technology of isopropyl acetate involved in this method, by flashing, the isolated purity of multitower rectifying is
99.9% isopropyl acetate product, while acetic acid is back to reaction system and is recycled.This method separating technology process phase
To complexity, separating energy consumption is higher.
Summary of the invention
The purpose of the present invention is to provide a kind of reaction conditions, and acetic acid mild, that product separation process is simple and low energy consumption is different
The preparation method of propyl ester.
In order to solve the above technical problems, the technical solution adopted by the present invention is that：A kind of preparation method of isopropyl acetate, packet
It includes：
(1) propylene and acetic acid complete catalytic synthesis in fixed bed reactors, and mixture mainly includes master after reaction
Acetic acid product isopropyl ester, by-product isopropanol, isopropyl ether, water, C6 alkene, C9 alkene and C12 alkene and unreacted propylene；
(2) the preheated rear feeding lightness-removing column of mixture after reacting, isopropyl acetate, water, propylene pass through from overhead extraction
After condensation, by isopropyl acetate infinite reflux to lightness-removing column, condensed water outlet, propylene is discharged in the form of fixed gas, acetic acid and second
The mixture of isopropyl propionate by tower reactor produce and by with react after mixture heat exchange after be sent into product knockout tower；
(3) acetic acid and isopropyl acetate separate in product knockout tower, and tower top material condensation rear portion is back to separation
In tower, a part is produced as isopropyl acetate product, and acetic acid is by tower reactor side take-off and is back to fixed bed reactors circulation
It utilizes, C9 alkene and C12 alkene are removed as heavy constituent by tower reactor.
Preferably, catalytic synthesis condition described in step (1) is：Reaction temperature is 30-110 DEG C, reaction pressure
Molar ratio for 0.5-2.5MPa, acetic acid and propylene is 1.0-10.0.
It is furthermore preferred that the catalytic synthesis condition is：Reaction temperature is 50-85 DEG C, reaction pressure 0.65-
The molar ratio of 1.75MPa, acetic acid and propylene are 2.0-8.0.
Preferably, catalysts are cation exchange resin catalyst, heteropolyacid catalyst, solid acid in step (1)
Catalyst.
It is furthermore preferred that the catalysts are acid cation exchange resin catalyst.
Preferably, 110-140 DEG C of lightness-removing column tower top temperature described in step (2), tower top pressure 0.35-0.65MPa, tower
155-175 DEG C of bottom temperature, tower bottom pressure 0.36-0.66MPa, ester infinite reflux.
Preferably, product described in step (3) separates 82-97 DEG C of column overhead temperatures, tower top pressure -10-30KPa, tower
115-130 DEG C of bottom temperature, tower bottom pressure 0-40KPa, reflux ratio 1.0-5.0.
Preferably, in the lightness-removing column, water and isopropyl acetate, C6 alkene form azeotropic mixture and steam to tower top, described
It further include one of by-product isopropanol, isopropyl ether, C6 alkene or a variety of in isopropyl acetate, by condensed isopropyl acetate
Ester infinite reflux can reduce tower top acid content, and controlling acid content in fixed gas can take off condensed water outlet less than 100ppm
Except the free water in system, to control isopropyl acetate product water content no more than 0.04 weight %.
Preferably, 99.0 weight %-99.9 of the isopropyl acetate product purity weight of the product knockout tower overhead extraction
% is measured, hydrocarbon content is less than 1 weight %.
Preferably, the propylene feedstocks concentration is 90.0 weight %-99.9 weight %, further includes third in propylene feedstocks
One of alkane, ethane, butane are a variety of.
The preparation method of isopropyl acetate of the invention, can will be from de- light since the temperature of product knockout tower is lower than lightness-removing column
The acetic acid of tower tower reactor extraction and the mixture of isopropyl acetate and the reaction mixture after catalytic synthesis carry out heat exchange, make
Thermal energy effective use in system；Since the pressure of product knockout tower is lower than lightness-removing column, the mixing that can produce lightness-removing column tower reactor
Object further saves plant energy consumption from being depressed into product knockout tower, reduces production cost.
Method of the invention under mild reaction conditions, by propylene and acetic acid catalysis synthesis of acetic acid isopropyl ester；Passing through will
Mixture after reaction obtains isopropyl acetate product, and will recycle after separated from acetic acid by lightness-removing column and product separation separation
It utilizes, simplifies product separating technique process, reduce production energy consumption；It is condensed by passing through lightness-removing column top production, by second
The mode of fixed gas direct emission is stripped of unreacted propylene by isopropyl propionate infinite reflux, and is solved in fixed gas containing acid
Bring pipeline corrosion and Environmental Safety problem, by way of discharging condensed water, the water being effectively stripped of in system is reduced
Influence of the water impurity to subsequent product separating technology and product quality.
Detailed description of the invention
Fig. 1 is the process flow chart of the method for the present invention.
In attached drawing：1 fixed bed reactors, 2 lightness-removing columns, 3 product knockout towers, 4 heat exchangers, 21 lightness-removing column return wires, 22 rows
Waterline, 23 fixed gas takeoff lines, 31 product knockout tower return wires, 32 products extraction line, 33 circulation acetic acid produce line, 34 heavy constituents
Produce line
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, but do not constitute limiting the scope of the invention.
With reference to attached drawing 1, the present invention provides a kind of processes for producing isopropyl acetate, specifically include following steps：
(1) propylene and acetic acid complete catalytic synthesis in fixed bed reactors 1, and mixture mainly includes master after reaction
Acetic acid product isopropyl ester, by-product isopropanol, isopropyl ether, water, propylene polymer (C6 alkene, C9 alkene and C12 alkene etc.) and
Unreacted propylene.
(2) mixture after reacting is sent into lightness-removing column 2 after the preheating of heat exchanger 4, and isopropyl acetate, water, propylene are from tower top
Extraction, after condensation, by isopropyl acetate by 21 infinite reflux to lightness-removing column of return wire, condensed water is by outside pipeline 22
Row, propylene are discharged in the form of fixed gas via pipeline 23, and the mixture of acetic acid and isopropyl acetate, which is produced by tower reactor and passed through, to be changed
Hot device 4 with react after mixture heat exchange after be sent into product knockout tower 3；
(3) acetic acid and isopropyl acetate separate in product knockout tower, and tower top material condensation rear portion is returned through pipeline 31
It flow in knockout tower, a part is produced as isopropyl acetate product by pipeline 32, and acetic acid is produced and returned by tower reactor side line 33
It is recycled to fixed bed reactors 1, C9 alkene and C12 alkene are removed as heavy constituent by tower reactor pipeline 34.
Preferably, catalytic synthesis condition is in the present invention：Reaction temperature is 30-110 DEG C, preferably 50-85 DEG C；Reaction
Pressure is 0.5-2.5MPa, preferably 0.65-1.75MPa；The molar ratio of acetic acid and propylene is 1.0-10.0, preferably 2.0-8.0.
Specifically, in one embodiment, catalysts can be cation resin catalyzing agent, heteropolyacid catalyst,
Preferred acidic cation resin catalyzing agent.
In lightness-removing column of the present invention, water and isopropyl acetate, C6 alkene will form azeotropic mixture and steams to tower top, described
Isopropyl acetate in further include one of by-product isopropanol, isopropyl ether, C6 alkene or a variety of, condensed acetic acid is different
Propyl ester infinite reflux can reduce tower top acid content, control acid content in fixed gas and be less than 100ppm, condensed water is passed through pipeline 22
Outlet, can free water in removing system, can control isopropyl acetate product water content to be not more than 0.04 weight %.
In one embodiment of the invention, 110-140 DEG C of lightness-removing column tower top temperature, tower top pressure 0.35-0.65MPa,
155-175 DEG C of column bottom temperature, tower bottom pressure 0.36-0.66MPa, ester infinite reflux.
In another embodiment of the invention, product separates 82-97 DEG C of column overhead temperatures, tower top pressure -10-30KPa, tower
115-130 DEG C of bottom temperature, tower bottom pressure are less than 0-40KPa, reflux ratio 1.0-5.0.
Specifically, the 99.20 weight %-99.95 weight % of isopropyl acetate product purity of product knockout tower overhead extraction.
Method of the invention is applicable to the propylene feedstocks that density of propylene is 90.0 weight %-99.9 weight %, and propylene is former
It further include one of propane, ethane, butane or a variety of in material.
Since the temperature of product knockout tower, pressure are below lightness-removing column, the acetic acid and acetic acid that will be produced from lightness-removing column tower reactor
The mixture of isopropyl ester is depressed into product knockout tower after carrying out heat exchange with the reaction mixture after catalytic synthesis certainly
It is interior, can effectively save plant energy consumption, reduce production cost.
Embodiment 1
Propylene (propane of the propylene of 90.7 weight %, 9.3 weight %) is mixed with acetic acid raw material be added it is anti-to fixed bed
It answers in device, the synthesis of acetic acid isopropyl ester under cation exchange resin catalyst effect, reaction condition is：30 DEG C of reaction temperature, instead
Answer pressure 0.5MPa, the molar ratio of acetic acid and propylene is 1.0.Mixture after reaction is sent into lightness-removing column to be divided after preheating
From lightness-removing column operating condition is：140 DEG C of lightness-removing column tower top temperature, tower top pressure 0.65MPa, 175 DEG C of column bottom temperature, tower bottom pressure
Power 0.66MPa, top gaseous phase extraction, by isopropyl acetate infinite reflux to lightness-removing column, remove condensed water, not instead after condensation
The propylene and propane answered with fixed gas formed discharge, by the mixture of the acetic acid produced by tower reactor and isopropyl acetate with react after
Enter product knockout tower from force feed after mixture heat exchange.Product knockout tower tower top material condenses rear portion and flows back as tower, and one
It is allocated as product extraction, acetic acid is by tower reactor side take-off and is back to fixed bed reactors and recycles, and removes heavy hydrocarbon by tower reactor
Component, product knockout tower operating condition：97 DEG C of tower top temperature, tower top pressure 30KPa, 130 DEG C of column bottom temperature, tower bottom pressure
40KPa, reflux ratio 5.0.Isolated isopropyl acetate product purity is 99.20 weight %, 0.75 weight % of hydrocarbon content, water
0.04 weight % of content, other 0.01 weight %.Acid content 98ppm in fixed gas.
Embodiment 2
By propylene (propylene of 93.51 weight %, the propane of 4.06 weight %, 1.51 weight % ethane, 0.92 weight %
Butane) addition is mixed with acetic acid raw material in fixed bed reactors, synthesis of acetic acid is different under the effect of heteropoly acid resin catalyst
Propyl ester, reaction condition are：110 DEG C of reaction temperature, reaction pressure 2.5MPa, the molar ratio of acetic acid and propylene is 10.0.It will reaction
Mixture is sent into lightness-removing column after preheating and is separated afterwards, and lightness-removing column operating condition is：110 DEG C of lightness-removing column tower top temperature, tower
Pressure on top surface 0.35MPa, 155 DEG C of column bottom temperature, tower bottom pressure 0.36MPa, top gaseous phase extraction is after condensation, by isopropyl acetate
In ester infinite reflux to lightness-removing column, condensed water is removed, unreacted propylene, propane and ethane discharges in the form of fixed gas, will be by
The mixture of the acetic acid of tower reactor extraction and isopropyl acetate with react after from force feed enter product knockout tower after mixture heat exchange.Product
Knockout tower tower top material condense rear portion as tower flow back, a part as product extraction, acetic acid by tower reactor side take-off simultaneously
It is back to fixed bed reactors to recycle, heavy hydrocarbon component, product knockout tower operating condition is removed by tower reactor：Tower top temperature 82
DEG C, tower top pressure -10KPa, 115 DEG C of column bottom temperature, tower bottom pressure 0KPa, reflux ratio 1.0.Isolated isopropyl acetate produces
Product purity is 99.50 weight %, 0.47 weight % of hydrocarbon content, 0.02 weight % of water content, other 0.01 weight %.In fixed gas
Acid content 91ppm.
Embodiment 3
Propylene (propane of the propylene of 99.53 weight %, 0.47 weight %) is mixed into addition to fixed bed with acetic acid raw material
In reactor, the synthesis of acetic acid isopropyl ester under cation exchange resin catalyst effect, reaction condition is：50 DEG C of reaction temperature,
The molar ratio of reaction pressure 0.65MPa, acetic acid and propylene is 2.0.Will reaction after mixture by preheating after be sent into lightness-removing column into
Row separation, lightness-removing column operating condition are：120 DEG C of lightness-removing column tower top temperature, tower top pressure 0.50MPa, 165 DEG C of column bottom temperature, tower
Bottom pressure 0.56MPa, top gaseous phase extraction, by isopropyl acetate infinite reflux to lightness-removing column, remove condensed water after condensation,
Unreacted propylene, propane are discharged in the form of fixed gas, by the mixture of the acetic acid and isopropyl acetate that are produced by tower reactor with
Enter product knockout tower from force feed after mixture heat exchange after reaction.Product knockout tower tower top material condenses rear portion and returns as tower
Stream, a part are produced as product, and acetic acid is by tower reactor side take-off and is back to fixed bed reactors and recycles, and are taken off by tower reactor
Except heavy hydrocarbon component, product knockout tower operating condition：90 DEG C of tower top temperature, tower top pressure 10KPa, 122 DEG C of column bottom temperature, tower bottom pressure
Power 20KPa, reflux ratio 3.0.Isolated isopropyl acetate product purity is 99.92 weight %, 0.07 weight % of hydrocarbon content, nothing
Water, other 0.01 weight %.Acid content 87ppm in fixed gas.
Embodiment 4
Propylene (propane of the propylene of 99.90 weight %, 0.01 weight %) is mixed into addition to fixed bed with acetic acid raw material
In reactor, the synthesis of acetic acid isopropyl ester under cation exchange resin catalyst effect, reaction condition is：85 DEG C of reaction temperature,
The molar ratio of reaction pressure 1.75MPa, acetic acid and propylene is 8.0.Will reaction after mixture by preheating after be sent into lightness-removing column into
Row separation, lightness-removing column operating condition are：120 DEG C of lightness-removing column tower top temperature, tower top pressure 0.35MPa, 160 DEG C of column bottom temperature, tower
Bottom pressure 0.36MPa, top gaseous phase extraction, by isopropyl acetate infinite reflux to lightness-removing column, remove condensed water after condensation,
Unreacted propylene, propane are discharged in the form of fixed gas, by the mixture of the acetic acid and isopropyl acetate that are produced by tower reactor with
Enter product knockout tower from force feed after mixture heat exchange after reaction.Product knockout tower tower top material condenses rear portion and returns as tower
Stream, a part are produced as product, and acetic acid is by tower reactor side take-off and is back to fixed bed reactors and recycles, and are taken off by tower reactor
Except heavy hydrocarbon component, product knockout tower operating condition：88 DEG C of tower top temperature, tower top pressure 1KPa, 122 DEG C of column bottom temperature, tower bottom pressure
Power 9KPa, reflux ratio 2.0.Isolated isopropyl acetate product purity be 99.95 weight %, 0.04 weight % of hydrocarbon content,
It is anhydrous, other 0.01 weight %.Acid content 89ppm in fixed gas.
Embodiment 5
By propylene (propylene of 98.82 weight %, the propane of 1.15 weight %, 0.03 weight % ethane) and acetic acid raw material
Mixing is added to fixed bed reactors, the synthesis of acetic acid isopropyl ester under cation exchange resin catalyst effect, reaction condition
For：75 DEG C of reaction temperature, reaction pressure 1.55MPa, the molar ratio of acetic acid and propylene is 4.0.Mixture is by pre- after reacting
It is sent into lightness-removing column after heat to be separated, lightness-removing column operating condition is：130 DEG C of lightness-removing column tower top temperature, tower top pressure 0.55MPa,
170 DEG C of column bottom temperature, tower bottom pressure 0.56MPa, top gaseous phase extraction is light to taking off by isopropyl acetate infinite reflux after condensation
In tower, remove condensed water, unreacted propylene, propane, ethane discharge in the form of fixed gas, by the acetic acid produced by tower reactor with
The mixture of isopropyl acetate with react after from force feed enter product knockout tower after mixture heat exchange.Product knockout tower tower top material is cold
Solidifying rear portion flows back as tower, and a part is produced as product, and acetic acid is by tower reactor side take-off and is back to fixed bed reaction
Device recycles, and removes heavy hydrocarbon component, product knockout tower operating condition by tower reactor：90 DEG C of tower top temperature, tower top pressure 10KPa,
124 DEG C of column bottom temperature, tower bottom presses 20KPa, reflux ratio 2.0.Isolated isopropyl acetate product purity is 99.86 weights
Measure %, hydrocarbon content 0.12 weight %, anhydrous, other 0.02 weight %.Acid content 95ppm in fixed gas.
Embodiment 6
By propylene (propylene of 95.83 weight %, the propane of 3.10 weight %, 0.75 weight % ethane, 0.32 weight %
Butane) addition is mixed with acetic acid raw material in fixed bed reactors, synthesize second under cation exchange resin catalyst effect
Isopropyl propionate, reaction condition are：40 DEG C of reaction temperature, reaction pressure 2.0MPa, the molar ratio of acetic acid and propylene is 6.0.It will be anti-
Mixture is sent into lightness-removing column after preheating and is separated after answering, and lightness-removing column operating condition is：130 DEG C of lightness-removing column tower top temperature,
Tower top pressure 0.45MPa, 165 DEG C of column bottom temperature, tower bottom pressure 0.46MPa, top gaseous phase extraction is different by acetic acid after condensation
In propyl ester infinite reflux to lightness-removing column, condensed water is removed, unreacted propylene, propane, ethane discharges in the form of fixed gas, will be by
The mixture of the acetic acid of tower reactor extraction and isopropyl acetate with react after from force feed enter product knockout tower after mixture heat exchange.Product
Knockout tower tower top material condense rear portion as tower flow back, a part as product extraction, acetic acid by tower reactor side take-off simultaneously
It is back to fixed bed reactors to recycle, heavy hydrocarbon component, product knockout tower operating condition is removed by tower reactor：Tower top temperature 95
DEG C, tower top pressure 25KPa, 125 DEG C of column bottom temperature, tower bottom pressure 35KPa, reflux ratio 3.0.Isolated isopropyl acetate product
Purity is 99.76 weight %, hydrocarbon content 0.20 weight %, anhydrous, other 0.04 weight %.Acid content 95ppm in fixed gas.
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (10)
1. a kind of preparation method of isopropyl acetate, which is characterized in that including：
(1) propylene and acetic acid complete catalytic synthesis in fixed bed reactors, and mixture mainly includes principal product after reaction
Isopropyl acetate, by-product isopropanol, isopropyl ether, water, C6 alkene, C9 alkene and C12 alkene and unreacted propylene；
(2) the preheated rear feeding lightness-removing column of mixture after reacting, isopropyl acetate, water, propylene are from overhead extraction, by condensation
Afterwards, by isopropyl acetate infinite reflux to lightness-removing column, condensed water outlet, propylene is discharged in the form of fixed gas, and acetic acid and acetic acid are different
The mixture of propyl ester by tower reactor produce and by with react after mixture heat exchange after be sent into product knockout tower；
(3) acetic acid and isopropyl acetate separate in product knockout tower, and tower top material condensation rear portion is back in knockout tower,
A part is produced as isopropyl acetate product, and acetic acid is by tower reactor side take-off and is back to fixed bed reactors and recycles,
C9 alkene and C12 alkene are removed as heavy constituent by tower reactor.
2. a kind of preparation method of isopropyl acetate according to claim 1, it is characterised in that：Described in step (1)
Catalytic synthesis condition is：Reaction temperature is 30-110 DEG C, the molar ratio of reaction pressure 0.5-2.5MPa, acetic acid and propylene
For 1.0-10.0.
3. a kind of preparation method of isopropyl acetate according to claim 2, it is characterised in that：Described catalyzing and synthesizing is anti-
The condition is answered to be：Reaction temperature is 50-85 DEG C, the molar ratio of reaction pressure 0.65-1.75MPa, acetic acid and propylene is 2.0-
8.0。
4. a kind of preparation method of isopropyl acetate according to claim 1 or 2, it is characterised in that：Reaction in step (1)
Catalyst is cation exchange resin catalyst, heteropolyacid catalyst, solid acid catalyst.
5. a kind of preparation method of isopropyl acetate according to claim 4, it is characterised in that：The catalysts are
Acid cation exchange resin catalyst.
6. a kind of preparation method of isopropyl acetate according to claim 1 or 2, it is characterised in that：Described in step (2)
110-140 DEG C of lightness-removing column tower top temperature, tower top pressure 0.35-0.65MPa, 155-175 DEG C of column bottom temperature, tower bottom pressure
0.36-0.66MPa, ester infinite reflux.
7. a kind of preparation method of isopropyl acetate according to claim 6, it is characterised in that：Described in step (3)
Product separates 82-97 DEG C of column overhead temperatures, tower top pressure -10-30KPa, 115-130 DEG C of column bottom temperature, tower bottom pressure 0-
40KPa, reflux ratio 1.0-5.0.
8. a kind of preparation method of isopropyl acetate according to claim 1, it is characterised in that：In the lightness-removing column,
Water and isopropyl acetate, C6 alkene form azeotropic mixture and steam to tower top, further include in the isopropyl acetate by-product isopropanol,
One of isopropyl ether, C6 alkene are a variety of, by condensed isopropyl acetate infinite reflux, can reduce tower top acid content, control
Acid content is less than 100ppm in fixed gas processed, by condensed water outlet, can free water in removing system, to control isopropyl acetate
Ester product water content is not more than 0.04 weight %.
9. a kind of preparation method of isopropyl acetate according to claim 1, it is characterised in that：The product knockout tower
The 99.0 weight %-99.9 weight % of isopropyl acetate product purity of overhead extraction, hydrocarbon content is less than 1 weight %.
10. a kind of preparation method of isopropyl acetate according to claim 1, it is characterised in that：The propylene feedstocks
Concentration is 90.0 weight %-99.9 weight %, further includes one of propane, ethane, butane or a variety of in propylene feedstocks.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114526564A (en) * | 2021-12-31 | 2022-05-24 | 湖南中创化工股份有限公司 | Method and device for recycling latent heat of acetic acid removal tower of isopropyl acetate device based on heat pump system |
| CN114797147A (en) * | 2022-05-16 | 2022-07-29 | 湖南中创化工股份有限公司 | Method and device for recovering tail gas of isopropyl acetate refining tower |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5384426A (en) * | 1992-12-08 | 1995-01-24 | Daicel Chemical Industries, Ltd. | Process for the preparation of isopropyl acetate |
| US5457228A (en) * | 1990-10-31 | 1995-10-10 | Daicel Chemical Industries, Ltd. | Method for producing lower alkyl acetate |
| CN104744248A (en) * | 2013-12-31 | 2015-07-01 | 湖南中创化工股份有限公司 | Method and device for preparing isopropyl acetate through reaction of propylene and acetic acid |
| CN106800509A (en) * | 2015-11-26 | 2017-06-06 | 中国石油化工股份有限公司 | A kind of production method of isopropyl acetate |
| CN106955500A (en) * | 2017-04-05 | 2017-07-18 | 青岛科技大学 | A kind of three tower is thermally integrated the method and device of variable-pressure rectification purifying acetic acid isopropyl ester |
| CN107954866A (en) * | 2017-12-13 | 2018-04-24 | 中国石油大学(华东) | The method and its device of differential pressure heat coupled reaction rectifying synthesis of acetic acid isopropyl ester |
-
2018
- 2018-05-23 CN CN201810500561.6A patent/CN108863793B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5457228A (en) * | 1990-10-31 | 1995-10-10 | Daicel Chemical Industries, Ltd. | Method for producing lower alkyl acetate |
| US5384426A (en) * | 1992-12-08 | 1995-01-24 | Daicel Chemical Industries, Ltd. | Process for the preparation of isopropyl acetate |
| CN104744248A (en) * | 2013-12-31 | 2015-07-01 | 湖南中创化工股份有限公司 | Method and device for preparing isopropyl acetate through reaction of propylene and acetic acid |
| CN106800509A (en) * | 2015-11-26 | 2017-06-06 | 中国石油化工股份有限公司 | A kind of production method of isopropyl acetate |
| CN106955500A (en) * | 2017-04-05 | 2017-07-18 | 青岛科技大学 | A kind of three tower is thermally integrated the method and device of variable-pressure rectification purifying acetic acid isopropyl ester |
| CN107954866A (en) * | 2017-12-13 | 2018-04-24 | 中国石油大学(华东) | The method and its device of differential pressure heat coupled reaction rectifying synthesis of acetic acid isopropyl ester |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114526564A (en) * | 2021-12-31 | 2022-05-24 | 湖南中创化工股份有限公司 | Method and device for recycling latent heat of acetic acid removal tower of isopropyl acetate device based on heat pump system |
| CN114526564B (en) * | 2021-12-31 | 2023-09-29 | 湖南中创化工股份有限公司 | Method and device for recycling latent heat of acetic acid removal tower of isopropyl acetate device based on heat pump system |
| CN114797147A (en) * | 2022-05-16 | 2022-07-29 | 湖南中创化工股份有限公司 | Method and device for recovering tail gas of isopropyl acetate refining tower |
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