CN105111079A - Method and device for separating acetic acid sec-butyl ester and sec-butyl alcohol - Google Patents
Method and device for separating acetic acid sec-butyl ester and sec-butyl alcohol Download PDFInfo
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Abstract
The invention provides a method and device for separating acetic acid sec-butyl ester and sec-butyl alcohol. The method comprises the steps that 1, a mixture of the acetic acid sec-butyl ester and the sec-butyl alcohol is put into an extraction rectifying tower, an extraction agent is added, after extraction rectifying separation is performed, the acetic acid sec-butyl ester is steamed out from the tower top and condensed, then part of the acetic acid sec-butyl ester is used for reflux, part of the acetic acid sec-butyl ester is extracted to obtain the acetic acid sec-butyl ester, and a mixture of the sec-butyl alcohol and the extraction agent falls into the tower bottom; 2, the mixture of the sec-butyl alcohol and the extraction agent is extracted out from the tower bottom and then put into a solvent concentration tower, the sec-butyl alcohol is steamed out from the tower top and then condensed, then part of the sec-butyl ester is put into the solvent concentration tower for reflux, part of the sec-butyl ester is extracted to obtain the sec-butyl ester, and the extraction agent falls into the tower bottom; 3, the extraction agent is extracted out from the tower bottom and then returns to the extraction rectifying tower for cyclic utilization. According to the method, the problem that in the prior art, the acetic acid sec-butyl ester and the sec-butyl alcohol are difficult to separate is solved, the purity of the separated acetic acid sec-butyl ester is above 99 percent, and the purity of the separated sec-butyl ester is above 99.9 percent; meanwhile, the energy consumption of the separation process is low, the procedures are simple, and operation is easy.
Description
Technical field
The present invention relates to method and the device of the secondary butyl ester of a kind of separating acetic acid and sec-butyl alcohol, particularly relate to a kind of method and the device that adopt the secondary butyl ester of extraction rectifying method separating acetic acid from sec-butyl acetate and sec-butyl alcohol mixture and sec-butyl alcohol.
Background technology
Sec-butyl alcohol (SBA), also known as the second butanols, methylethyl methyl alcohol, butyl alcohol-sec, 2-butanols, is a kind of water white inflammable liquid, has similar smell vinous.SBA is industrially used as solvent, does cosolvent with methyl alcohol, can, as the component improving gasoline octane rating, also can be used for producing softening agent, dressing agent, weedicide, secondary butyl ester etc., but methylethylketone is produced in topmost application, accounts for 90% of total flow.The method of current industrial comparative maturity has n-butene indirect hydration method and n-butene direct hydration method.The traditional technology preparing sec-butyl alcohol is sulfuric acid indirect hydration method, and this technological process comprises esterification, hydrolysis, rectifying and diluted acid concentrate 4 operations.This technique is not high to the purity requirement of raw material n-butene, and steam cracking C 4 fraction and refining plant C 4 cut all can be raw material, and reaction conditions relaxes, and technique is simple, ripe.Shortcoming to consume a large amount of sulfuric acid and caustic soda, and seriously polluted, reaction preference is lower, and the unit consumption of n-butene is higher, and production cost is high, and equipment corrosion is serious, needs to use acidproof material etc.Direct hydration method is under postcritical condition, uses acidic cation-exchange resin or heteropolyacid to make catalyzer, obtains SBA by n-butene direct hydration.This technological process does not consume sulfuric acid, anacidity neutralization procedure, and without equipment corrosion, generate without a large amount of waste water, SBA selectivity is up to 99%.Weak point is that n-butene per pass conversion is low, only about 6%, stricter to ingredient requirement, the C4 raw material that direct hydration technique uses if n-butene content is greater than 90%, then may be SBA at direct hydration under high conversion, if the B-B level cut direct reaction that n-butene content is lower, understand because of its low conversion rate, cycling rate is high and increase engineering cost, therefore because first carrying out extractive distillation or with molecular sieving, purifying to reach the object reducing production cost to greatest extent in advance.
A kind of preparation method of sec-butyl alcohol is disclosed in Chinese invention patent 201110268440.1, the method comprises: under the existence of transesterification catalyst, sec-butyl acetate and low-carbon alcohol are added in catalytic rectifying tower and carry out transesterification reaction, sec-butyl alcohol is collected from tower reactor, wherein, described low-carbon alcohol is the alcohol of C1-C3.Method described in this invention, technique is simple, and require lower to production unit, raw material is easy to get, and energy consumption is low, thus reduces production cost; And, without the need to using acetic acid to make raw material, reduce equipment corrosion and environmental pollution.In the method, sec-butyl acetate is made to react comparatively complete by adding excessive methyl alcohol, but in the method and the separation method of unexposed methyl alcohol and ritalin, sec-butyl alcohol and sec-butyl acetate.
A kind of method that 2-butyl acetate catalytic hydrolysis produces sec-butyl alcohol is disclosed in Chinese invention patent 201210125734.3, the method comprises the following steps: take 2-butyl acetate as raw material, be fixed a continuous catalysis hydrolysis, catalyzer adopts commercially available phenylethylene cation exchange resin catalyst, be loaded in the calandria type fixed bed continuous print pipe of series connection, described series connection is calandria type fixed bed comprises multiple duplicate shell and tube reactor, raw material 2-butyl acetate and water enter shell and tube reactor, under catalyst action, continuous catalysis hydrolysis reaction generates sec-butyl alcohol crude product, again through refining obtained high purity sec-butyl alcohol.The method overcome the shortcoming that sec-butyl alcohol low conversion rate is produced in the reaction of butylene direct hydration, transformation efficiency is greater than 95%, has opened up the novelty teabag of 2-butyl acetate, has solved product overloading problem.But in the method, do not relate to being separated of sec-butyl acetate and sec-butyl alcohol, meanwhile, refining for product sec-butyl alcohol, is only just separated the sec-butyl alcohol obtained with the mixture stratification of water.In the method, due in this reaction, transformation efficiency is more than 95%, do not reach 100%, therefore, the sec-butyl alcohol that responseless sec-butyl acetate can obtain with hydrolysis reaction and unreacted unnecessary water form ternary azeotropic and steam to tower top, simultaneously, water all has certain meltage in sec-butyl alcohol and sec-butyl acetate, good separating effect can not be reached by simple stratification, a certain amount of sec-butyl acetate of content and water in sec-butyl alcohol after separation, the sec-butyl alcohol purity obtained can't be very high, simultaneously, because sec-butyl alcohol has certain solubleness in water, solubleness when 30 DEG C in water is 18%, if be separated by stratification, a large amount of sec-butyl alcohols will be taken away in waste water, such and uneconomical.
Disclose a kind of method of synthesizing sec-butyl alcohol in Chinese invention patent 201210230912.9, the method comprises with 2-butyl acetate and methyl alcohol for raw material, and produce sec-butyl alcohol by transesterify, by product is ritalin.The transformation efficiency of the 2-butyl acetate of this invention can reach 50%-90%, and the yield of sec-butyl alcohol can reach 50%-90%, has that speed of reaction is fast, transformation efficiency is high, selectivity is high, reaction conditions is gentle, to the remarkable advantage such as the corrosion of equipment is little.But the not open method be separated reaction product in this invention, the transformation efficiency of reaction and yield are also on the low side, and reacted product component is complicated, are separated comparatively difficulty.
Disclose a kind of method utilizing catalyzing cation exchange resin to synthesize sec-butyl alcohol in Chinese invention patent 201210349454.0, it is catalyzer that the method comprises with Zeo-karb, and sec-butyl acetate and methyl alcohol are Material synthesis sec-butyl alcohol.The catalyzing cation exchange resin activity of the present invention's employing is high, and selectivity is good, and transformation efficiency can reach 35%-50%, and Zeo-karb is little to equipment corrosion, easily reclaims and reuses, long service life.Also the separation method of after product is not openly reacted in this invention.
The catalytic rectification process of a kind of ester-interchange method synthesis sec-butyl alcohol is disclosed in Chinese invention patent 201210349731.8, with 2-butyl acetate and methyl alcohol for raw material, it is characterized in that technique is carried out as follows: 1) 2-butyl acetate and methyl alcohol pump into catalytic rectifying tower from the upper and lower of conversion zone respectively, in 2-butyl acetate and the methyl alcohol conversion zone in the middle part of catalytic rectifying tower, adverse current is to transmission of heat by contact mass transfer, transesterification reaction is carried out under reacting section catalyst effect, condensation after the rear light constituent ritalin of reaction and methyl alcohol steam from tower top after rectifying section concentrate, part phlegma is back to catalytic rectifying tower, another part condensate pump is to methyl esters rectifying tower concentrate, catalytic rectifying tower tower kettle product is sec-butyl alcohol, methyl alcohol and a small amount of 2-butyl acetate, methanol rectifying tower is entered after pump extraction, 2) ritalin of catalytic rectifying tower overhead extraction and methyl alcohol mixed liquor enter in the middle part of methyl esters rectifying tower, and after being separated, the ritalin of tower top and methanol azeotrope are back to methyl esters rectifying tower top through a condenser condenses part, another part extraction, the methyl alcohol of high density at the bottom of tower returns to catalytic rectifying tower conversion zone bottom as part material recycled, 3) catalytic rectifying tower tower reactor Produced Liquid enters methanol rectifying tower by middle part and is separated, light constituent methyl alcohol at tower top through condenser condenses, a part is back to methanol rectification column overhead, another part extraction returns to catalytic rectifying tower conversion zone bottom as part material recycled, and tower reactor still liquid sec-butyl alcohol and a small amount of 2-butyl acetate are purified to sec-butyl alcohol treating tower through pump, 4) sec-butyl alcohol of methanol rectifying tower tower reactor extraction and a small amount of 2-butyl acetate enter sec-butyl alcohol treating tower by middle part after pump pressurization, the highly purified sec-butyl alcohol steam of tower top is after condenser condenses, a part is back to sec-butyl alcohol treating tower tower top, and another part extraction obtains sec-butyl alcohol product, the 2-butyl acetate of minute quantity and sec-butyl alcohol mixed solution are by tower reactor extraction.The remarkable advantage of this invention is: take Zeo-karb as catalyzer, realizes serialization synthesis sec-butyl alcohol, simplify technical process, reduce production energy consumption and material consumption, improve transesterification reaction transformation efficiency in conjunction with catalytic rectification process.Be specially: (1) 2-butyl acetate and methanol oxidation synthesize sec-butyl alcohol and separating substances is carried out in catalytic rectifying tower simultaneously, sepn process and reaction process are mutually promoted, effective raising reaction conversion ratio and yield, simultaneous reactions heat is fully utilized and reduces energy consumption of rectification; (2) catalytic distillation is adopted can to realize large-scale continuous prodution, constant product quality; (3) in continuous catalyzing rectifying tower, reaction is only carried out in conversion zone, and in conversion zone, the residence time of material is little, and potential byproduct reaction is few, good product quality; (4) adopt the reactive distillation processes of basic catalyst, needing in reaction process, add a large amount of methyl alcohol affects reactive distillation processes normal running to avoid catalyzer to separate out.And continuous catalyzing rectifying technique adopts Zeo-karb to be catalyzer, urge equipment corrosion little, and packet form is tied up in catalyst loading employing, not easy to wear and broken, catalyst life is long, and without the need to being reclaimed by modes such as evaporations, technique is simple.In this invention, methyl esters rectifying tower is separated the mixture that the overhead product obtained is methyl alcohol and ritalin, be not separated completely, and in sec-butyl alcohol treating tower, because sec-butyl alcohol and 2-butyl acetate can form azeotrope, the boiling point of azeotrope differs with the boiling point of sec-butyl alcohol only has 0.1 DEG C, so, in this tower, sec-butyl alcohol and 2-butyl acetate can not well separate by common rectifying mode, substantially can not get the sec-butyl alcohol of 100% purity.
Disclose a kind of device synthesizing sec-butyl alcohol in Chinese invention patent 201210278743.6, described device comprises reactive distillation column, ritalin rectifying tower, vaporizer, methanol rectifying tower, sec-butyl alcohol treating tower, some condensers and some pipelines for being connected.This invention additionally provides the method adopting this device to synthesize secondary butyl ester.The method of the device synthesis sec-butyl alcohol adopting this invention to provide, for continuous reaction rectification method, effectively can improve reaction conversion ratio, reduce production energy consumption, have that selectivity is high, corrodibility is little, the advantage of the easily separated purification of product, continuous prodution can be realized, ensure constant product quality.In this invention, flow process is longer, and the ritalin product obtained is thick ester product, and massfraction is about 82%, purity is low, and in sec-butyl alcohol treating tower, because sec-butyl alcohol and 2-butyl acetate can form azeotrope, the boiling point of azeotrope differs with the boiling point of sec-butyl alcohol only has 0.1 DEG C, so, in this tower, sec-butyl alcohol and 2-butyl acetate can not well separate, and substantially can not get highly purified sec-butyl alcohol.
Summary of the invention
The object of the invention is to overcome in existing isolation technique, sec-butyl acetate and sec-butyl alcohol are difficult to be separated, the problem that separation purity is low, provide method and the device of a kind of high efficiency separation sec-butyl acetate and sec-butyl alcohol, sec-butyl acetate purity after separation is more than 99%, the purity of the sec-butyl alcohol after separation reaches 99.99%, meets the demand of downstream methyl ethyl ketone plant.
To achieve these goals, according to a first aspect of the invention, provide the method for the secondary butyl ester of a kind of separating acetic acid and sec-butyl alcohol, the method comprises:
(1) mixture of sec-butyl acetate and sec-butyl alcohol is sent into extractive distillation column, add extraction agent, after separation of extractive distillation, sec-butyl acetate steams from tower top and refluxes through condensation rear section, part extraction obtains sec-butyl acetate, and the mixture of sec-butyl alcohol and extraction agent then falls into tower reactor;
(2) mixture of sec-butyl alcohol and extraction agent sends into solvent concentration tower after extracting out at the bottom of tower, and send into solvent concentration tower after sec-butyl alcohol steams from tower top through condensation rear section and reflux, obtain product sec-butyl alcohol after part extraction, extraction agent falls into tower reactor;
(3) extraction agent turns back to extractive distillation column after extracting out at the bottom of tower and carries out recycle.
In the present invention, because sec-butyl acetate and sec-butyl alcohol form azeotrope, the boiling point of azeotrope is 99.6 DEG C, and the boiling point of sec-butyl alcohol is 99.5 DEG C, and both boiling points only differ 0.1 DEG C, by simple conventional distillation, is difficult to both to be separated.In the present invention, the mode that have employed extracting rectifying is separated this mixture, obtains good separating effect, and the high purity 99.99% of the secondary butyl ester after separation can meet the requirement of downstream methyl ethyl ketone plant to raw material completely.
In the present invention, described extraction agent for can dissolve each other with sec-butyl alcohol, not with sec-butyl alcohol and sec-butyl acetate generation azeotropic and boiling point solvent of (such as 120-180 DEG C) more than 120 DEG C.It can be alcohols, be preferably monohydroxy-alcohol or dibasic alcohol, such as: Pentyl alcohol, n-hexyl alcohol, n-Octanol, sec-octyl alcohol, nonanol-, positive certain herbaceous plants with big flowers alcohol, phenylcarbinol, tetrahydrofurfuryl alcohol, ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,3-butyleneglycol, 2,3-butanediol, 1,5-PD, tetramethylethylene glycol.In the present invention, in order to strengthen the solvability of sec-butyl alcohol in extraction agent, being preferably the alcohols containing two hydroxyls and dibasic alcohol, being more preferably ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,3 butylene glycol, 2,3-butanediol, 1,5-pentanediol, tetramethylethylene glycol, more preferably ethylene glycol, 1,2-PD, 1,3-PD.In the present invention, extraction agent should be the solvent larger with sec-butyl acetate polarity spectrum, and stable in properties, can not react with sec-butyl alcohol and sec-butyl acetate in sepn process, self also not react simultaneously.
In the present invention, in order to obtain efficient extracting and separating effect, control energy consumption, the add-on of extraction agent needs to control in suitable scope simultaneously.In the present invention, the mass ratio of the mixture of described extraction agent and sec-butyl acetate and sec-butyl alcohol is 0.05-20:1, is preferably 0.05-18:1, be more preferably 0.1-18:1, be more preferably 0.1-15:1, be more preferably 0.1-12:1, be more preferably 0.1-10:1, more preferably 0.2-10:1, is more preferably 0.5-10:1, is more preferably 0.5-8:1, more preferably 0.5-5:1, being more preferably 1-5:1, is more preferably 1-3:1, more preferably 1-2:1.
In the present invention, the tower top temperature of described extractive distillation column is 90-130 DEG C, be preferably 92-128 DEG C, be more preferably 95-125 DEG C, be more preferably 95-125 DEG C, be more preferably 98-122 DEG C, be more preferably 100-120 DEG C, be more preferably 102-118 DEG C, be more preferably 105-115 DEG C, more preferably 108-112 DEG C; Tower top pressure is normal pressure; Reflux ratio is 0.5-10:1, is preferably 0.8-10:1, is more preferably 0.8-8:1, is more preferably 1-8:1, be more preferably 1-6:1, be more preferably 1-5:1, be more preferably 1.2-5:1, be more preferably 1.5-5:1, be more preferably 1.5-4:1, be more preferably 1.5-3:1, more preferably 1.5-2:1.
In the present invention, the tower top temperature of described solvent concentration tower is 80-120 DEG C, is preferably 82-118 DEG C, be more preferably 85-115 DEG C, be more preferably 88-112 DEG C, be more preferably 90-110 DEG C, be more preferably 92-108 DEG C, be more preferably 95-105 DEG C, more preferably 95-102 DEG C; Tower top pressure is normal pressure; Reflux ratio is 0.1-10:1, is preferably 0.1-9:1, is more preferably 0.1-8:1, be more preferably 0.2-8:1, be more preferably 0.5-8:1, be more preferably 0.5-7:1, be more preferably 0.5-6:1, be more preferably 0.5-5:1, be more preferably 0.5-4:1, be more preferably 0.6-4:1, be more preferably 0.6-3:1, be more preferably 0.8-3:1, be more preferably 0.8-2:1, more preferably 1-2:1.
In the present invention, in order to reduce the load of extractive distillation column, after described sec-butyl acetate and the preheating of sec-butyl alcohol mixture, send into extractive distillation column.In the present invention, the materials at bottom of tower of extractive distillation column and the mixture of sec-butyl acetate and sec-butyl alcohol can be utilized to carry out heat exchange, also the materials at bottom of tower of solvent concentration tower and the mixture of sec-butyl acetate and sec-butyl alcohol can be utilized to carry out heat exchange, or extractive distillation column and the material at the bottom of solvent concentration tower tower carry out heat exchange with the mixture of sec-butyl acetate and sec-butyl alcohol simultaneously.
In the present invention, preferably, in described sec-butyl acetate and the mixture of sec-butyl alcohol, the mass content of sec-butyl acetate is 10-90%, is preferably 15-85%, be more preferably 20-80%, be more preferably 25-75%, be more preferably 30-70%, be more preferably 35-65%, be more preferably 40-60%, more preferably 45-55%; The mass content of sec-butyl alcohol is 10-90%, is preferably 15-85%, is more preferably 20-80%, is more preferably 25-75%, be more preferably 30-70%, be more preferably 35-65%, be more preferably 40-60%, more preferably 45-55%.In the present invention, except sec-butyl acetate and sec-butyl alcohol in separated charging, also optionally containing a small amount of light constituent C4.
In the present invention, described sec-butyl acetate and the mixture of sec-butyl alcohol, the mixture that can be obtained by transesterification reaction for sec-butyl acetate and alcohol is through initial gross separation, the mixture obtained after unreacted unnecessary alcohol is separated with product acetic ester, also the mixture that can be sec-butyl acetate be obtained by hydrolysis reaction is through initial gross separation, by the mixture obtained after the separated from acetic acid obtained after unreacted excessive water and hydrolysis, due in reaction process, self decomposition can be there is in part sec-butyl acetate, obtain acetic acid product and C4, because C4 has certain solubleness in sec-butyl acetate, therefore, also containing a small amount of C4 component in the sec-butyl acetate obtained through initial gross separation after mixing after hydrolyzing and the material of sec-butyl alcohol.This mixture can be such as the tower kettle product obtained after sec-butyl acetate and low carbon alcohol transesterification reaction in Chinese patent 201110268440.1, or the 2-butyl acetate catalytic hydrolysis of Chinese patent 201210125734.3 produces the sec-butyl alcohol product obtained in the method for sec-butyl alcohol, or the sec-butyl alcohol product that disclosed in Chinese patent 201210349454.0, a kind of method utilizing catalyzing cation exchange resin to synthesize sec-butyl alcohol obtains, or utilize the sec-butyl alcohol crude product (entering the product before sec-butyl alcohol treating tower) that the device synthesizing sec-butyl alcohol disclosed in Chinese invention patent 201210278743.6 is produced.
In the present invention, preferably, the sec-butyl acetate Returning reacting system of described extractive distillation column overhead extraction carries out recycle.
In the present invention, preferably, extractive distillation column is sent into after the extraction agent extracted out at the bottom of described solvent concentration tower tower and the heat exchange of extractive distillation column materials at bottom of tower.
In the present invention, preferably, extractive distillation column is sent into after the extraction agent extracted out at the bottom of described solvent concentration tower tower and the mixture heat exchange of sec-butyl acetate and sec-butyl alcohol.
According to another aspect of the present invention, provide a kind of from sec-butyl acetate and the mixture separation sec-butyl acetate of sec-butyl alcohol and the device of sec-butyl alcohol, it comprises extractive distillation column and solvent concentration tower, extractive distillation column and solvent concentration tower comprise overhead condenser and return tank and bottom reboiler separately, the import of extractive distillation column connects the mixture feeding line of sec-butyl acetate and sec-butyl alcohol, and the tower bottom outlet pipeline of extractive distillation column connects the import of solvent concentration tower.
Preferably, the tower bottom outlet pipeline of solvent concentration tower and extractive distillation column tower bottom outlet pipeline carry out heat exchange in an intermediate heat.
Preferably, solvent concentration tower tower bottom outlet pipeline with the heat exchange of extractive distillation column tower bottom outlet pipeline after further with mixture feeding line heat exchange in another interchanger of sec-butyl acetate and sec-butyl alcohol.
Preferably, the tower bottom outlet pipeline of solvent concentration tower, being connected water cooler with extractive distillation column tower bottom outlet pipeline and sec-butyl acetate further with after the mixture feeding line heat exchange of sec-butyl alcohol, then connects extractive distillation column.
Method provided by the invention successfully solves sec-butyl acetate and sec-butyl alcohol in prior art and is difficult to the difficult problem be separated, and the sec-butyl acetate purity after separation is more than 99%, and sec-butyl alcohol purity is more than 99.9%, simultaneously, sepn process energy consumption is low, and flow process is simple, easily operates.
Accompanying drawing explanation
Fig. 1 is the schema of the method for the secondary butyl ester of separating acetic acid of the present invention and sec-butyl alcohol.
Wherein 1 is the mixture of sec-butyl acetate and sec-butyl alcohol, 2 is intermediate heats, 3 is water coolers, 4 is extractive distillation columns, 5 is extractive distillation column bottom reboilers, 6 is extractive distillation column overhead condensers, 7 is extractive distillation column return tank of top of the tower, 8 is extractive distillation column trim the top of column, 9 is extractive distillation column overhead extraction product sec-butyl acetates, 10 is rich solvents at the bottom of extractive distillation column tower, 11 is intermediate heat at the bottom of extractive distillation column and solvent concentration tower tower, 12 is lean solvent at the bottom of solvent concentration tower tower, 13 is solvent concentration tower, 14 is solvent concentration tower bottom reboiler, 15 is solvent concentration tower overhead condenser, 16 is solvent concentration tower return tank of top of the tower, 17 is solvent concentration tower trim the top of column, 18 is solvent concentration tower overhead extraction product sec-butyl alcohol.
Embodiment
Further illustrate the present invention by the following examples.But the present invention is not limited by the following examples, in the scope not departing from purport of the present invention, can make a variety of changes the present invention, these changes still comprise within the scope of the invention.
Embodiment 1
Extractive distillation column 4 is sent into the speed of 10t/h by after the mixture preheating containing sec-butyl acetate and sec-butyl alcohol, wherein, this mixture carries out the reacted tower reactor mixture of catalytic distillation from sec-butyl acetate and methyl alcohol, the content 50% of sec-butyl acetate, the content 50% of sec-butyl alcohol, the temperature of mixture material is 140 DEG C, by extraction agent 1, ammediol sends into extractive distillation column 4 with the speed of 40t/h (solvent ratio is for 4), the tower top temperature of extractive distillation column is 125 DEG C, tower top pressure is normal pressure, reflux ratio is 2:1, after separation of extractive distillation, the speed extraction that sec-butyl acetate steams with 5t/h after condensation from tower top obtains sec-butyl acetate 9, the mixture (rich solvent) of sec-butyl alcohol and extraction agent is extracted out with the speed of 45t/h and is sent into solvent concentration tower 13 afterwards at the bottom of tower, the tower top temperature of solvent concentration tower is 115 DEG C, tower top pressure is normal pressure, reflux ratio is 2:1, after condensation, product sec-butyl alcohol 18 is obtained with the extraction of 5t/h speed after sec-butyl alcohol steams from tower top, extract out after extraction agent (at the bottom of solvent concentration tower tower lean solvent 12) is extracted out with the speed of 40t/h at the bottom of tower and at the bottom of extractive distillation column tower after carrying out heat exchange with the mixture of sec-butyl acetate and sec-butyl alcohol again after rich solvent (at the bottom of extractive distillation column tower rich solvent 10) carries out heat exchange and carry out water-cooled, then recycle is carried out on the top sending into extractive distillation column 4.
Get extractive distillation column overhead extraction material sec-butyl acetate and solvent concentration tower overhead extraction material sec-butyl alcohol is analyzed, extractive distillation column overhead extraction material sec-butyl acetate consist of sec-butyl acetate 99.25wt%, solvent concentration tower overhead extraction product sec-butyl alcohol consist of sec-butyl alcohol 99.95wt%.
Embodiment 2
Extractive distillation column 4 is sent into the speed of 10t/h by after the mixture preheating containing sec-butyl acetate and sec-butyl alcohol, wherein, this mixture carries out the reacted tower reactor mixture of catalytic distillation from sec-butyl acetate and ethanol, the content 10% of sec-butyl acetate, the content 90% of sec-butyl alcohol, the temperature of mixture material is 120 DEG C, extraction agent ethylene glycol is sent into extractive distillation column 4 with the speed of 200t/h (solvent ratio is for 20), the tower top temperature of extractive distillation column is 107 DEG C, tower top pressure is normal pressure, reflux ratio is 0.5:1, after separation of extractive distillation, the speed extraction that sec-butyl acetate steams with 1t/h after condensation from tower top obtains sec-butyl acetate 9, the mixture (rich solvent) of sec-butyl alcohol and extraction agent is extracted out with the speed of 209t/h and is sent into solvent concentration tower 13 afterwards at the bottom of tower, the tower top temperature of solvent concentration tower is 100 DEG C, tower top pressure is normal pressure, reflux ratio is 0.5:1, after condensation, product sec-butyl alcohol 18 is obtained with the extraction of 9t/h speed after sec-butyl alcohol steams from tower top, extract out after extraction agent is extracted out with the speed of 200t/h at the bottom of tower and at the bottom of extractive distillation column tower after carrying out heat exchange with the mixture of sec-butyl acetate and sec-butyl alcohol again after rich solvent carries out heat exchange and carry out water-cooled, then recycle is carried out on the top sending into extractive distillation column 4.
Get extractive distillation column overhead extraction material sec-butyl acetate and solvent concentration tower overhead extraction material sec-butyl alcohol is analyzed, extractive distillation column overhead extraction material sec-butyl acetate consist of sec-butyl acetate 99.32wt%, solvent concentration tower overhead extraction product sec-butyl alcohol consist of sec-butyl alcohol 99.96wt%.
Embodiment 3
Extractive distillation column 4 is sent into the speed of 10t/h by after the mixture preheating containing sec-butyl acetate and sec-butyl alcohol, wherein, this mixture carries out the reacted tower reactor mixture of catalytic distillation from sec-butyl acetate and methyl alcohol, the content 20% of sec-butyl acetate, the content 80% of sec-butyl alcohol, the temperature of mixture material is 110 DEG C, by extraction agent 1, 2-propylene glycol sends into extractive distillation column 4 with the speed of 100t/h (solvent ratio is for 10), the tower top temperature of extractive distillation column is 110 DEG C, tower top pressure is normal pressure, reflux ratio is 0.8:1, after separation of extractive distillation, the speed extraction that sec-butyl acetate steams with 2t/h after condensation from tower top obtains sec-butyl acetate 9, the mixture (rich solvent) of sec-butyl alcohol and extraction agent is extracted out with the speed of 108t/h and is sent into solvent concentration tower 13 afterwards at the bottom of tower, the tower top temperature of solvent concentration tower is 90 DEG C, tower top pressure is normal pressure, reflux ratio is 0.8:1, after condensation, product sec-butyl alcohol 18 is obtained with the extraction of 8t/h speed after sec-butyl alcohol steams from tower top, extract out after extraction agent is extracted out with the speed of 100t/h at the bottom of tower and at the bottom of extractive distillation column tower after carrying out heat exchange with the mixture of sec-butyl acetate and sec-butyl alcohol again after rich solvent carries out heat exchange and carry out water-cooled, then recycle is carried out on the top sending into extractive distillation column 4.
Get extractive distillation column overhead extraction material sec-butyl acetate and solvent concentration tower overhead extraction material sec-butyl alcohol is analyzed, extractive distillation column overhead extraction material sec-butyl acetate consist of sec-butyl acetate 99.34wt%, solvent concentration tower overhead extraction product sec-butyl alcohol consist of sec-butyl alcohol 99.94wt%.
Embodiment 4
Extractive distillation column 4 is sent into the speed of 10t/h by after the mixture preheating containing sec-butyl acetate and sec-butyl alcohol, wherein, this mixture carries out the reacted tower reactor mixture of catalytic distillation from sec-butyl acetate and methyl alcohol, the content 40% of sec-butyl acetate, the content 60% of sec-butyl alcohol, the temperature of mixture material is 130 DEG C, by extraction agent 1, 3-butyleneglycol sends into extractive distillation column 4 with the speed of 10t/h (solvent ratio is for 1), the tower top temperature of extractive distillation column is 117 DEG C, tower top pressure is normal pressure, reflux ratio is 5:1, after separation of extractive distillation, the speed extraction that sec-butyl acetate steams with 4t/h after condensation from tower top obtains sec-butyl acetate 9, the mixture (rich solvent) of sec-butyl alcohol and extraction agent is extracted out with the speed of 16t/h and is sent into solvent concentration tower 13 afterwards at the bottom of tower, the tower top temperature of solvent concentration tower is 110 DEG C, tower top pressure is normal pressure, reflux ratio is 5:1, after condensation, product sec-butyl alcohol 18 is obtained with the extraction of 6t/h speed after sec-butyl alcohol steams from tower top, extract out after extraction agent is extracted out with the speed of 10t/h at the bottom of tower and at the bottom of extractive distillation column tower after carrying out heat exchange with the mixture of sec-butyl acetate and sec-butyl alcohol again after rich solvent carries out heat exchange and carry out water-cooled, then recycle is carried out on the top sending into extractive distillation column 4.
Get extractive distillation column overhead extraction material sec-butyl acetate and solvent concentration tower overhead extraction material sec-butyl alcohol is analyzed, extractive distillation column overhead extraction material sec-butyl acetate consist of sec-butyl acetate 99.42wt%, solvent concentration tower overhead extraction product sec-butyl alcohol consist of sec-butyl alcohol 99.96wt%.
Embodiment 5
Extractive distillation column 4 is sent into the speed of 10t/h by after the mixture preheating containing sec-butyl acetate and sec-butyl alcohol, wherein, the mixture that this mixture is obtained by hydrolysis reaction from sec-butyl acetate is through initial gross separation, by the mixture obtained after the separated from acetic acid obtained after unreacted excessive water and hydrolysis, the content 60% of sec-butyl acetate, the content 40% of sec-butyl alcohol, the temperature of mixture material is 105 DEG C, by extraction agent 2, 3-butyleneglycol sends into extractive distillation column 4 with the speed of 5t/h (solvent ratio is for 0.5), the tower top temperature of extractive distillation column is 95 DEG C, tower top pressure is normal pressure, reflux ratio is 6:1, after separation of extractive distillation, the speed extraction that sec-butyl acetate steams with 6t/h after condensation from tower top obtains sec-butyl acetate 9, the mixture (rich solvent) of sec-butyl alcohol and extraction agent is extracted out with the speed of 9t/h and is sent into solvent concentration tower 13 afterwards at the bottom of tower, the tower top temperature of solvent concentration tower is 85 DEG C, tower top pressure is normal pressure, reflux ratio is 6:1, after condensation, product sec-butyl alcohol 18 is obtained with the extraction of 4t/h speed after sec-butyl alcohol steams from tower top, extract out after extraction agent is extracted out with the speed of 5t/h at the bottom of tower and at the bottom of extractive distillation column tower after carrying out heat exchange with the mixture of sec-butyl acetate and sec-butyl alcohol again after rich solvent carries out heat exchange and carry out water-cooled, then recycle is carried out on the top sending into extractive distillation column 4.
Get extractive distillation column overhead extraction material sec-butyl acetate and solvent concentration tower overhead extraction material sec-butyl alcohol is analyzed, extractive distillation column overhead extraction material sec-butyl acetate consist of sec-butyl acetate 99.36wt%, solvent concentration tower overhead extraction product sec-butyl alcohol consist of sec-butyl alcohol 99.92wt%.
Embodiment 6
Extractive distillation column 4 is sent into the speed of 10t/h by after the mixture preheating containing sec-butyl acetate and sec-butyl alcohol, wherein, the mixture that this mixture is obtained by hydrolysis reaction from sec-butyl acetate is through initial gross separation, by the mixture obtained after the separated from acetic acid obtained after unreacted excessive water and hydrolysis, the content 80% of sec-butyl acetate, the content 20% of sec-butyl alcohol, the temperature of mixture material is 150 DEG C, by extraction agent 1, 5-pentanediol sends into extractive distillation column 4 with the speed of 1t/h (solvent ratio is for 0.1), the tower top temperature of extractive distillation column is 130 DEG C, tower top pressure is normal pressure, reflux ratio is 8:1, after separation of extractive distillation, the speed extraction that sec-butyl acetate steams with 8t/h after condensation from tower top obtains sec-butyl acetate 9, the mixture (rich solvent) of sec-butyl alcohol and extraction agent is extracted out with the speed of 3t/h and is sent into solvent concentration tower 13 afterwards at the bottom of tower, the tower top temperature of solvent concentration tower is 120 DEG C, tower top pressure is normal pressure, reflux ratio is 8:1, after condensation, product sec-butyl alcohol 18 is obtained with the extraction of 2t/h speed after sec-butyl alcohol steams from tower top, extract out after extraction agent is extracted out with the speed of 1t/h at the bottom of tower and at the bottom of extractive distillation column tower after carrying out heat exchange with the mixture of sec-butyl acetate and sec-butyl alcohol again after rich solvent carries out heat exchange and carry out water-cooled, then recycle is carried out on the top sending into extractive distillation column 4.
Get extractive distillation column overhead extraction material sec-butyl acetate and solvent concentration tower overhead extraction material sec-butyl alcohol is analyzed, extractive distillation column overhead extraction material sec-butyl acetate consist of sec-butyl acetate 99.46wt%, solvent concentration tower overhead extraction product sec-butyl alcohol consist of sec-butyl alcohol 99.97wt%.
Embodiment 7
Extractive distillation column 4 is sent into the speed of 10t/h by after the mixture preheating containing sec-butyl acetate and sec-butyl alcohol, wherein, the mixture that this mixture is obtained by hydrolysis reaction from sec-butyl acetate is through initial gross separation, by the mixture obtained after the separated from acetic acid obtained after unreacted excessive water and hydrolysis, the content 90% of sec-butyl acetate, the content 10% of sec-butyl alcohol, the temperature of mixture material is 100 DEG C, extraction agent tetramethylethylene glycol is sent into extractive distillation column 4 with the speed of 0.5t/h (solvent ratio is for 0.05), the tower top temperature of extractive distillation column is 90 DEG C, tower top pressure is normal pressure, reflux ratio is 10:1, after separation of extractive distillation, the speed extraction that sec-butyl acetate steams with 9t/h after condensation from tower top obtains sec-butyl acetate 9, the mixture (rich solvent) of sec-butyl alcohol and extraction agent is extracted out with the speed of 1.5t/h and is sent into solvent concentration tower 13 afterwards at the bottom of tower, the tower top temperature of solvent concentration tower is 80 DEG C, tower top pressure is normal pressure, reflux ratio is 10:1, after condensation, product sec-butyl alcohol 18 is obtained with the extraction of 1t/h speed after sec-butyl alcohol steams from tower top, extract out after extraction agent is extracted out with the speed of 0.5t/h at the bottom of tower and at the bottom of extractive distillation column tower after carrying out heat exchange with the mixture of sec-butyl acetate and sec-butyl alcohol again after rich solvent carries out heat exchange and carry out water-cooled, then recycle is carried out on the top sending into extractive distillation column 4.
Get extractive distillation column overhead extraction material sec-butyl acetate and solvent concentration tower overhead extraction material sec-butyl alcohol is analyzed, extractive distillation column overhead extraction material sec-butyl acetate consist of sec-butyl acetate 99.18wt%, solvent concentration tower overhead extraction product sec-butyl alcohol consist of sec-butyl alcohol 99.92wt%.
Embodiment 8
Extractive distillation column 4 is sent into the speed of 10t/h by after the mixture preheating containing sec-butyl acetate and sec-butyl alcohol, wherein, this mixture carries out the reacted tower reactor mixture of catalytic distillation from sec-butyl acetate and methyl alcohol, the content 50% of sec-butyl acetate, the content 50% of sec-butyl alcohol, the temperature of mixture material is 115 DEG C, extraction agent n-Octanol is sent into extractive distillation column 4 with the speed of 50t/h (solvent ratio is for 5), the tower top temperature of extractive distillation column is 105 DEG C, tower top pressure is normal pressure, reflux ratio is 1.2:1, after separation of extractive distillation, the speed extraction that sec-butyl acetate steams with 5t/h after condensation from tower top obtains sec-butyl acetate 9, the mixture (rich solvent) of sec-butyl alcohol and extraction agent is extracted out with the speed of 55t/h and is sent into solvent concentration tower 13 afterwards at the bottom of tower, the tower top temperature of solvent concentration tower is 95 DEG C, tower top pressure is normal pressure, reflux ratio is 1.2:1, after condensation, product sec-butyl alcohol 18 is obtained with the extraction of 5t/h speed after sec-butyl alcohol steams from tower top, extract out after extraction agent is extracted out with the speed of 50t/h at the bottom of tower and at the bottom of extractive distillation column tower after carrying out heat exchange with the mixture of sec-butyl acetate and sec-butyl alcohol again after rich solvent carries out heat exchange and carry out water-cooled, then recycle is carried out on the top sending into extractive distillation column 4.
Get extractive distillation column overhead extraction material sec-butyl acetate and solvent concentration tower overhead extraction material sec-butyl alcohol is analyzed, extractive distillation column overhead extraction material sec-butyl acetate consist of sec-butyl acetate 99.54wt%, solvent concentration tower overhead extraction product sec-butyl alcohol consist of sec-butyl alcohol 99.98wt%.
Claims (10)
1. the method for the secondary butyl ester of separating acetic acid and sec-butyl alcohol from the mixture of sec-butyl acetate and sec-butyl alcohol, the method comprises:
(1) mixture of sec-butyl acetate and sec-butyl alcohol is sent into extractive distillation column, add extraction agent, after separation of extractive distillation, sec-butyl acetate steams from extracting rectifying column overhead and refluxes through condensation rear section, part extraction obtains sec-butyl acetate, and the mixture of sec-butyl alcohol and extraction agent then falls into extractive distillation column tower reactor;
(2) mixture of sec-butyl alcohol and extraction agent sends into solvent concentration tower after extracting out at the bottom of extractive distillation column tower, send into solvent concentration tower after sec-butyl alcohol steams from solvent concentration tower tower top to reflux through condensation rear section, obtain product sec-butyl alcohol after part extraction, extraction agent falls into solvent concentration tower tower reactor;
(3) extraction agent turns back to extractive distillation column after extracting out at the bottom of solvent concentration tower tower and carries out recycle.
2. method according to claim 1, is characterized in that: described extraction agent for can dissolve each other with sec-butyl alcohol, insoluble with sec-butyl acetate, not with sec-butyl alcohol and sec-butyl acetate generation azeotropic and the solvent of boiling point more than 120 DEG C;
Preferably, described extraction agent is alcohols, is preferably monohydroxy-alcohol or dibasic alcohol, is more preferably dibasic alcohol, more preferably 1,3-PD, 1,2-PD;
More preferably, the mass ratio of the mixture of described extraction agent and sec-butyl acetate, sec-butyl alcohol is 0.05-20:1, is preferably 0.1-10:1, is more preferably 0.5-5:1, more preferably 1-2:1.
3. method according to claim 1 and 2, is characterized in that: the tower top temperature of described extractive distillation column is 90-130 DEG C, is preferably 95-125 DEG C, is more preferably 100-120 DEG C, more preferably 105-115 DEG C; Tower top pressure is normal pressure; Reflux ratio is 0.5-10:1, is preferably 0.8-8:1, is more preferably 1-6:1, more preferably 1.2-5:1; And/or
The tower top temperature of described solvent concentration tower is 80-120 DEG C, is preferably 85-115 DEG C, is more preferably 90-110 DEG C, more preferably 95-105 DEG C; Tower top pressure is normal pressure; Reflux ratio is 0.1-10:1, is preferably 0.2-8:1, is more preferably 0.5-5:1, more preferably 0.8-2:1.
4. the method according to any one of claim 1-3, is characterized in that: send into extractive distillation column after described sec-butyl acetate and the preheating of sec-butyl alcohol mixture.
5. the method according to any one of claim 1-4, is characterized in that: in described sec-butyl acetate and the mixture of sec-butyl alcohol, the content of sec-butyl acetate is 10-90%, is preferably 20-80%, is more preferably 30-70%, more preferably 40-60%; The content of sec-butyl alcohol is 10-90%, is preferably 20-80%, is more preferably 30-70%, more preferably 40-60%.
6. the method according to any one of claim 1-5, is characterized in that: the sec-butyl acetate Returning reacting system of described extractive distillation column overhead extraction carries out recycle; And/or
Extractive distillation column is sent into after the extraction agent extracted out at the bottom of described solvent concentration tower tower and the heat exchange of extractive distillation column materials at bottom of tower; And/or send into extractive distillation column after the mixture heat exchange of the extraction agent extracted out at the bottom of described solvent concentration tower tower and sec-butyl acetate and sec-butyl alcohol.
7. one kind from sec-butyl acetate and the mixture separation sec-butyl acetate of sec-butyl alcohol and the device of sec-butyl alcohol, it comprises extractive distillation column and solvent concentration tower, extractive distillation column and solvent concentration tower comprise overhead condenser and return tank and bottom reboiler separately, the import of extractive distillation column connects the mixture feeding line of sec-butyl acetate and sec-butyl alcohol, and the tower bottom outlet pipeline of extractive distillation column connects the import of solvent concentration tower.
8. device according to claim 7, wherein, tower bottom outlet pipeline and the extractive distillation column tower bottom outlet pipeline of solvent concentration tower carry out heat exchange in an intermediate heat.
9. the device according to claim 7 or 8, wherein, the tower bottom outlet pipeline of solvent concentration tower with the heat exchange of extractive distillation column tower bottom outlet pipeline after further with mixture feeding line heat exchange in another interchanger of sec-butyl acetate and sec-butyl alcohol.
10. the device according to any one of claim 7-9, wherein, the tower bottom outlet pipeline of solvent concentration tower, being connected water cooler with extractive distillation column tower bottom outlet pipeline and sec-butyl acetate further with after the mixture feeding line heat exchange of sec-butyl alcohol, then connects extractive distillation column.
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