CN111377802A - Preparation method and system of sec-butyl alcohol - Google Patents

Preparation method and system of sec-butyl alcohol Download PDF

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Publication number
CN111377802A
CN111377802A CN201811606166.2A CN201811606166A CN111377802A CN 111377802 A CN111377802 A CN 111377802A CN 201811606166 A CN201811606166 A CN 201811606166A CN 111377802 A CN111377802 A CN 111377802A
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sec
tower
butyl alcohol
water
butyl acetate
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王伟华
刘郁东
黄能武
孙李林
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Hunan Zhongchuang Chemical Co Ltd
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Hunan Zhongchuang Chemical Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/095Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C07C29/82Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by azeotropic distillation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/86Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment

Abstract

The invention provides a preparation method of sec-butyl alcohol, which comprises the steps of sending a mixture obtained after hydrolysis reaction into a sec-butyl alcohol azeotropic rectifying tower for separation, extracting a mixed material containing sec-butyl alcohol, sec-butyl acetate and water from the upper side line of the sec-butyl alcohol azeotropic rectifying tower, sending the mixed material into a multistage extraction tower, adding an extractant freezing water, obtaining a water phase containing sec-butyl alcohol at the bottom of the tower, sending the water phase at the bottom of the tower into a liquid separation tank after extraction, and obtaining an oil phase of sec-butyl alcohol at the upper layer of the liquid separation tank; and (3) feeding the oil phase of the sec-butyl alcohol obtained from the upper layer of the liquid separation tank into a sec-butyl alcohol refining tower for refining, adding entrainer water, and obtaining a high-purity product sec-butyl alcohol from the tower bottom. According to the invention, the sec-butyl acetate and the sec-butyl alcohol are effectively separated, the yield of the sec-butyl alcohol obtained after separation is up to more than 99.5%, and the once-through yield of the sec-butyl alcohol is greatly improved from the original 50% to more than 85%.

Description

Preparation method and system of sec-butyl alcohol
Technical Field
The invention relates to a method and a system for preparing sec-butyl alcohol, in particular to a method and a system for preparing sec-butyl alcohol by hydrolyzing sec-butyl acetate.
Background
Sec-butyl alcohol (SBA), also known as sec-butyl alcohol, methyl ethyl methanol, sec-butyl alcohol, 2-butyl alcohol, is a colorless, transparent, flammable liquid with a wine-like odor. SBA is industrially used as a solvent, is used as a cosolvent with methanol, can be used as a component for improving the octane number of gasoline, and can also be used for producing plasticizers, mineral processing agents, herbicides, sec-butyl esters and the like, but the most important application is the production of methyl ethyl ketone, which accounts for about 90% of the total consumption. Currently, the industrially mature methods include an indirect n-butene hydration method and a direct n-butene hydration method. The traditional process for preparing sec-butyl alcohol is an indirect sulfuric acid hydration method, and the process comprises 4 working procedures of esterification, hydrolysis, rectification and dilute acid concentration. The process has low requirement on the purity of the raw material n-butene, the steam cracking C4 fraction and the refinery C4 fraction can be used as raw materials, the reaction condition is mild, and the process is simple and mature. The method has the disadvantages of large consumption of sulfuric acid and caustic soda, serious pollution, low reaction selectivity, high unit consumption of n-butene, high production cost, serious equipment corrosion, need of using acid-resistant materials and the like. The direct hydration method is to prepare SBA by directly hydrating n-butene under supercritical conditions by using acidic cation exchange resin or heteropoly acid as a catalyst. The technological process has no consumption of sulfuric acid, no acid neutralizing step, no corrosion to apparatus, no waste water generation and SBA selectivity up to 99%. The method has the defects that the single-pass conversion rate of the n-butene is low, only about 6 percent, the requirements on raw materials are strict, the C4 raw material used in the direct hydration process is likely to be directly hydrated into SBA under high conversion rate if the n-butene content is more than 90 percent, and the engineering cost is increased due to the low conversion rate and high circulation rate if the B-B fraction with low n-butene content is directly reacted, so the method needs to firstly carry out extractive distillation or separation by using a molecular sieve and pre-purification so as to achieve the purpose of reducing the production cost to the maximum extent.
Chinese patent 201110268440.1 discloses a method for preparing sec-butyl alcohol, which comprises the following steps: adding sec-butyl acetate and lower alcohol into a catalytic rectifying tower to perform transesterification reaction in the presence of a transesterification catalyst, and collecting sec-butyl alcohol from a tower bottom, wherein the lower alcohol is C1-C3 alcohol. The method has the advantages of simple process, low requirement on production equipment, easily obtained raw materials and low energy consumption, thereby reducing the production cost; in addition, acetic acid is not needed to be used as a raw material, so that the corrosion of equipment and the environmental pollution are reduced. In the method, the sec-butyl acetate is reacted more completely by adding excessive methanol, but the method does not disclose a method for separating methanol from methyl acetate, sec-butyl alcohol and sec-butyl acetate, and meanwhile, the reaction time is long, and the method is not suitable for industrial production.
Chinese patent 201210125734.3 discloses a method for producing sec-butyl alcohol by catalytic hydrolysis of sec-butyl acetate, which comprises the following steps: taking sec-butyl acetate as a raw material, carrying out fixed bed continuous catalytic hydrolysis, filling the catalyst into a continuous tube of a serial tubular fixed bed by adopting a commercial styrene series cation exchange resin catalyst, wherein the serial tubular fixed bed comprises a plurality of identical tubular reactors, feeding the raw material sec-butyl acetate and water into the tubular reactors, carrying out continuous catalytic hydrolysis reaction under the action of the catalyst to generate a crude sec-butyl alcohol product, and refining to obtain the high-purity sec-butyl alcohol. The method overcomes the defect of low conversion rate of sec-butyl alcohol prepared by direct hydration reaction of butylene, the conversion rate is more than 95 percent, the new application of sec-butyl acetate is developed, and the problem of product overstock is solved. However, the method does not relate to the separation of sec-butyl acetate and sec-butyl alcohol, and only the obtained mixture of sec-butyl alcohol and water is kept stand for layering and is separated for the purification of the sec-butyl alcohol product. In the method, because the conversion rate is more than 95% and does not reach 100% in the reaction, unreacted sec-butyl acetate can form ternary azeotropic distillation with sec-butyl alcohol obtained by hydrolysis reaction and unreacted excess water to the tower top, meanwhile, water has a certain amount of dissolution in the sec-butyl alcohol and the sec-butyl acetate, a good separation effect cannot be achieved through simple standing and layering, the purity of the obtained sec-butyl alcohol is not very high due to a certain amount of sec-butyl acetate and water in the separated sec-butyl alcohol, and meanwhile, because the sec-butyl alcohol has a certain solubility in water, the solubility in water at 30 ℃ is 18%, if separation is carried out through standing and layering, a large amount of sec-butyl alcohol is taken away from waste water, so that the method is not economical.
Chinese patent 201210230912.9 discloses a method for synthesizing sec-butyl alcohol, which comprises using sec-butyl acetate and methanol as raw materials, producing sec-butyl alcohol by ester exchange, and using methyl acetate as byproduct. The conversion rate of the sec-butyl acetate can reach 50-90%, the yield of the sec-butyl alcohol can reach 50-90%, and the method has the remarkable advantages of high reaction rate, high conversion rate, high selectivity, mild reaction conditions, small corrosion to equipment and the like. However, this invention does not disclose a method for separating the reaction product, and the conversion rate and yield of the reaction are low, and the product components after the reaction are complicated and difficult to separate.
Chinese invention patent 201210349454.0 discloses a method for synthesizing sec-butyl alcohol by cation exchange resin catalysis, which comprises using cation exchange resin as catalyst, sec-butyl acetate and methanol as raw materials to synthesize sec-butyl alcohol. The cation exchange resin adopted by the invention has high catalytic activity and good selectivity, the conversion rate can reach 35-50%, the cation exchange resin has little corrosion to equipment, is easy to recycle and reuse, and has long service life. This invention also does not disclose a method for separating the product after the reaction.
The invention patent 201210349731.8 discloses a catalytic rectification process for synthesizing sec-butyl alcohol by ester exchange method, which takes sec-butyl acetate and methanol as raw materials and is characterized in that the process comprises the following steps: 1) sec-butyl acetate and methanol are respectively pumped into a catalytic rectifying tower from the upper part and the lower part of a reaction section, the sec-butyl acetate and the methanol are reversely flowed to contact heat transfer and mass transfer in the reaction section at the middle part of the catalytic rectifying tower, ester exchange reaction is carried out under the action of a catalyst at the reaction section, light components of methyl acetate and methanol after reaction are evaporated from the top of the tower after being concentrated by a rectifying section and then condensed, one part of condensate is refluxed to the catalytic rectifying tower, the other part of condensate is pumped to the methyl ester rectifying tower for concentration, products at the bottom of the catalytic rectifying tower are sec-butyl alcohol, methanol and a small amount of sec-butyl acetate, and the products are pumped out and then enter the methanol rectifying tower; 2) mixed liquid of methyl acetate and methanol extracted from the top of the catalytic rectifying tower enters the middle part of a methyl ester rectifying tower, and after separation, a part of methyl acetate and methanol azeotrope at the top of the tower is condensed by a condenser and flows back to the top of the methyl ester rectifying tower, and the other part of methyl acetate and methanol azeotrope is extracted; the methanol with high concentration at the tower bottom returns to the lower part of the reaction section of the catalytic rectifying tower to be used as part of raw materials for recycling; 3) the method comprises the following steps that (1) liquid produced in a tower kettle of a catalytic rectifying tower enters a methanol rectifying tower from the middle part to be separated, light component methanol is condensed by a condenser at the tower top, one part of the light component methanol flows back to the tower top of the methanol rectifying tower, the other part of the light component methanol is returned to the lower part of a reaction section of the catalytic rectifying tower to be used as part of raw materials for circulating and applying, and sec-butyl alcohol in the tower kettle liquid and a small amount of sec-butyl acetate are pumped to a sec-butyl; 4) sec-butyl alcohol and a small amount of sec-butyl acetate which are extracted from the bottom of the methanol rectifying tower enter a sec-butyl alcohol refining tower from the middle part after being pressurized by a pump, high-purity sec-butyl alcohol steam at the top of the tower is condensed by a condenser, one part of the high-purity sec-butyl alcohol steam flows back to the top of the sec-butyl alcohol refining tower, and the other part of the high-purity sec-butyl alcohol steam is extracted to obtain a sec-butyl; and a very small amount of mixed solution of sec-butyl acetate and sec-butyl alcohol is extracted from a tower bottom. The invention has the following remarkable advantages: the cation exchange resin is used as a catalyst, and the catalytic rectification technology is combined to realize continuous synthesis of sec-butyl alcohol, so that the process flow is simplified, the production energy consumption and material consumption are reduced, and the conversion rate of ester exchange reaction is improved. The method specifically comprises the following steps: (1) the sec-butyl acetate and methanol are catalytically synthesized into sec-butyl alcohol, and the separation of substances is carried out in the catalytic rectifying tower at the same time, the separation process and the reaction process are mutually promoted, the reaction conversion rate and the yield are effectively improved, and meanwhile, the reaction heat is fully utilized, so that the rectifying energy consumption is reduced; (2) large-scale continuous production can be realized by adopting catalytic rectification, and the product quality is stable; (3) in the continuous catalytic rectifying tower, the reaction is only carried out in the reaction section, the retention time of materials in the reaction section is short, the reaction of potential byproducts is less, and the product quality is good; (4) in the reaction rectification process adopting the alkaline catalyst, a large amount of methanol needs to be added in the reaction process to avoid the influence of the precipitation of the catalyst on the normal operation of the reaction rectification process. The continuous catalytic rectification process adopts cation exchange resin as a catalyst, so that catalytic equipment is low in corrosivity, the catalyst is filled in a bundled bag form and is not easy to wear and break, the service life of the catalyst is long, the catalyst is not required to be recovered in modes of evaporation and the like, and the process is simple. In the invention, the overhead product obtained by separating the methyl ester rectifying tower is a mixture of methanol and methyl acetate and is not completely separated, but in the sec-butyl alcohol refining tower, as sec-butyl alcohol and sec-butyl acetate can form an azeotrope, the boiling point of the azeotrope is 99.6 ℃, and the boiling point of sec-butyl alcohol is 99.5 ℃, sec-butyl alcohol and sec-butyl acetate can not be well separated in the tower, and the purity of the sec-butyl alcohol with 100 percent can not be basically obtained.
The Chinese invention patent 201210278743.6 discloses a device for synthesizing sec-butyl alcohol, which comprises a reaction rectifying tower, a methyl acetate rectifying tower, an evaporator, a methanol rectifying tower, a sec-butyl alcohol refining tower, a plurality of condensers and a plurality of pipelines for connection. The invention also provides a method for synthesizing sec-butyl ester by using the device. The method for synthesizing sec-butyl alcohol by adopting the device provided by the invention is a continuous reaction rectification method, can effectively improve the reaction conversion rate and reduce the production energy consumption, has the advantages of high selectivity, small corrosivity and easy separation and purification of products, can realize continuous production and ensures the stable quality of the products. In the invention, the flow is long, the obtained methyl acetate product is a crude ester product, the mass fraction is about 82%, and the purity is low, but in a sec-butyl alcohol refining tower, sec-butyl alcohol and sec-butyl acetate can form an azeotrope, the boiling point of the azeotrope is 99.6 ℃, and the boiling point of sec-butyl alcohol is 99.5 ℃, so that sec-butyl alcohol and sec-butyl acetate cannot be well separated in the tower, and high-purity sec-butyl alcohol cannot be basically obtained.
Chinese invention patent 201510725722.8 discloses a method for preparing sec-butyl alcohol, which comprises: (1) mixing sec-butyl acetate with water, feeding the mixture into a hydrolysis reactor, and performing hydrolysis reaction to obtain a mixture of sec-butyl alcohol, water and sec-butyl acetate; (2) the mixture after reaction is sent to the lower part of a deacidification tower, and the separated acetic acid falls into the bottom of the tower; (3) and (2) feeding the mixture of the sec-butyl acetate and the sec-butyl alcohol into a sec-butyl alcohol refining tower, simultaneously adding azeotropic agent water, evaporating an azeotrope of water, the sec-butyl acetate and part of the sec-butyl alcohol to the tower top, condensing and then circulating the azeotrope to a reaction system, wherein most of the sec-butyl alcohol falls into the tower bottom, and extracting the sec-butyl alcohol from the tower bottom to obtain the product sec-butyl alcohol. Although the separation step in the method is simpler, the sec-butyl acetate, the sec-butyl alcohol and water can form a ternary azeotrope, and the content of the sec-butyl acetate in the material from the reaction system is higher, so that the content of the sec-butyl acetate in the oil phase after the separation of the mixture from the top of the deacidification tower is higher, after the oil phase enters the refining tower, the sec-butyl acetate, the sec-butyl alcohol and the water are subjected to azeotropic distillation to cause a large amount of sec-butyl alcohol to be distilled from the top of the tower, so that the sec-butyl alcohol obtained from the bottom of the tower is less, the yield of the sec-butyl alcohol is lower, meanwhile, a large amount of sec-butyl alcohol cannot be effectively separated, the circulating amount of the whole sec-butyl alcohol device is larger due to the cyclic utilization of the sec-butyl alcohol entering the reaction system or the deacidification tower, so that the energy consumption is greatly increased, is a technical problem to be solved by the existing device for preparing sec-butyl alcohol by hydrolyzing sec-butyl acetate.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of sec-butyl alcohol, which comprises the following steps:
(1) mixing sec-butyl acetate with water, sending the mixture into a hydrolysis reactor, and carrying out hydrolysis reaction under the hydrolysis condition to obtain a mixture of sec-butyl alcohol, water, acetic acid and sec-butyl acetate;
(2) sending a mixture of sec-butyl alcohol, water, acetic acid and sec-butyl acetate obtained after reaction into a sec-butyl alcohol azeotropic rectifying tower for separation, evaporating the mixture of sec-butyl acetate, sec-butyl alcohol and water from the tower top, refluxing an oil phase obtained after condensation and delamination, preferably, fully refluxing the oil phase obtained from the tower top, more preferably discharging irregular impurities, and enabling the mixture of acetic acid and part of sec-butyl acetate to fall into the tower bottom;
(3) extracting a mixture of acetic acid and part of sec-butyl acetate at the bottom of a sec-butyl alcohol azeotropic distillation tower, feeding the mixture into a sec-butyl acetate recovery tower, adding entrainer water for azeotropic distillation, obtaining a mixture of sec-butyl acetate and water at the top of the tower, preferably returning the mixture of the sec-butyl acetate and the water obtained at the top of the tower to a hydrolysis reactor for reaction, obtaining high-purity acetic acid at the bottom of the tower, and preferably returning the high-purity acetic acid obtained at the bottom of the tower to an addition reactor of a sec-butyl acetate preparation device for recycling;
(4) extracting a mixed material containing sec-butyl alcohol, sec-butyl acetate and water from the upper side line of a sec-butyl alcohol azeotropic rectifying tower, feeding the mixed material into a multistage extraction tower, adding extractant chilled water, obtaining an oil phase of the sec-butyl acetate at the top of the multistage extraction tower, preferably returning the oil phase of the sec-butyl acetate obtained at the top of the multistage extraction tower to a hydrolysis reactor for reaction, obtaining a water phase containing the sec-butyl alcohol at the bottom of the multistage extraction tower, extracting the water phase at the bottom of the multistage extraction tower, feeding the water phase into a liquid separation tank, obtaining the oil phase of the sec-butyl alcohol at the upper layer of the liquid separation tank, obtaining the water phase containing a small amount of the sec-butyl alcohol at the lower layer of the liquid;
(5) feeding the oil phase of the sec-butyl alcohol obtained from the upper layer of the liquid separation tank into a sec-butyl alcohol refining tower for refining, adding entrainer water (the amount of the added water at least enables sec-butyl acetate in the material to be subjected to azeotropic distillation to the tower top), obtaining a mixture of sec-butyl acetate, sec-butyl alcohol and water at the tower top, condensing and layering, refluxing one part of the oil phase, preferably returning the other part of the oil phase to a hydrolysis reactor for reaction, preferably returning the water phase to the sec-butyl alcohol refining tower for recycling, and obtaining a high-purity product sec-butyl alcohol at the tower bottom of the sec-butyl alcohol refining tower.
In the invention, the hydrolysis reactor, the azeotropic distillation tower, the sec-butyl acetate recovery tower, the multistage extraction tower and the sec-butyl alcohol refining tower are all provided with water inlet pipelines, and the water to be added is preferably desalted water. The water inlet pipelines of the entrainer rectifying tower, the sec-butyl alcohol refining tower and the sec-butyl acetate recovery tower are all arranged at the middle upper part of the tower, can be arranged on the feed pipelines of all the towers, can be arranged on the top return pipeline of each tower, or are directly arranged at the lower part of the top return tank.
In the invention, the water phase of the mixture of sec-butyl acetate, sec-butyl alcohol and water obtained from the top of the sec-butyl alcohol azeotropic distillation tower after condensation and layering is preferably returned to the hydrolysis reactor for recycling, or returned to the sec-butyl alcohol azeotropic distillation tower for recycling, or returned to the hydrolysis reactor partially, and returned to the sec-butyl alcohol azeotropic distillation tower partially for recycling. The water phase returned to the hydrolysis reactor can directly pass through a sec-butyl acetate feeding pipeline of the hydrolysis reactor, can also return through a water inlet pipeline of the hydrolysis reactor, and can return to the water phase of the sec-butyl alcohol azeotropic distillation tower through a middle upper water inlet pipeline, a tower top reflux pipeline or a tower middle feeding pipeline.
In the invention, researches show that the lower the temperature, the higher the solubility of sec-butyl alcohol in water and the lower the solubility of sec-butyl acetate in water, and the higher the temperature, the lower the solubility of sec-butyl alcohol in water and the higher the solubility of sec-butyl acetate in water. The solubility of the sec-butyl alcohol in water decreases with increasing temperature, and increases with decreasing temperature, and the solubility of the sec-butyl acetate in water is just opposite to that of the sec-butyl alcohol. Under the condition of normal temperature (20 ℃), the solubility of the sec-butyl acetate in water is 0.62%, the solubility of the sec-butyl alcohol in water is 12.5%, and when the temperature is reduced to be below 10 ℃, even to be below 5 ℃, the solubility of the sec-butyl acetate in water is 0.21%, and the solubility of the sec-butyl alcohol in water is increased to be 29.2%. The solubility of sec-butanol in water when the temperature reached 70 ℃ was 6.5%.
In the invention, the mixed material containing sec-butyl alcohol, sec-butyl acetate and water is extracted from the upper side line of the sec-butyl alcohol azeotropic distillation tower, cooled to 5-10 ℃ and then sent into a multistage extraction tower. The mixture containing sec-butyl alcohol, sec-butyl acetate and water entering the multistage extraction tower is cooled in advance, multistage extraction can be better carried out on the mixture and chilled water in the extraction tower, and the sec-butyl alcohol and the sec-butyl acetate can be better separated.
In the present invention, the temperature of the chilled water is 1 to 5 ℃, preferably 2 to 5 ℃, more preferably 3 to 5 ℃, and still more preferably 3 to 4 ℃. In order to ensure the extraction effect of the chilled water, the amount of chilled water needs to be controlled. In the invention, the mass ratio of the chilled water to the mixed material containing sec-butyl alcohol, sec-butyl acetate and water extracted from the upper side line of the sec-butyl alcohol azeotropic rectifying tower is controlled to be 1.0-5.0:1, preferably 1.0 to 4.5: 1, more preferably 1.0 to 4.0:1, more preferably 1.0 to 3.5: 1, more preferably 1.0 to 3.0:1, more preferably 1.0 to 2.5: 1, more preferably 1.0 to 2.0:1, more preferably 1.2 to 1.8:1, more preferably 1.4 to 1.6: 1.
in the invention, the multistage extraction tower is a countercurrent extraction tower, and the effect of countercurrent extraction is better than that of concurrent extraction. The number of extraction stages of the extraction column is set to 3 to 10 stages, preferably 3 to 9 stages, preferably 3 to 8 stages, preferably 3 to 7 stages, more preferably 4 to 7 stages, and further preferably 4 to 6 stages.
In the invention, in order to achieve a certain separation precision, the theoretical plate number of the sec-butyl alcohol azeotropic distillation tower is set to be 40-60, preferably 40-55, more preferably 40-50, and even more preferably 45-50. Because the materials after multistage extraction are adopted for separation, the content of sec-butyl alcohol in the materials at the bottom of the tower after multistage extraction is greatly improved, the content of sec-butyl acetate is greatly reduced, and the separation of sec-butyl alcohol is more facilitated, so that the circulation volume of the whole separation system is greatly reduced, the energy consumption of the whole separation system is greatly reduced, and the cost is saved. Meanwhile, before a multistage extraction tower is not arranged, when a material containing sec-butyl acetate, sec-butyl alcohol and water extracted from a sec-butyl alcohol azeotropic distillation tower is sent to a sec-butyl alcohol refining tower, the concentration of the material is limited, the material can be sent to the sec-butyl alcohol refining tower only if the content of the material is more than 55%, the product sec-butyl alcohol can be extracted from the bottom of the sec-butyl alcohol refining tower, if the concentration of the material is lower than the concentration, the sec-butyl alcohol can be completely distilled to the top of the tower due to azeotropic distillation, basically no product can be extracted from the bottom of the tower, and the material cannot be effectively separated from the sec-butyl alcohol refining tower. The concentration of the materials fed into the multistage extraction tower is not specially required, so that the separation requirement on the sec-butyl alcohol azeotropic distillation tower is reduced, and the theoretical plate number of the tower can be reduced by about 10 compared with the original operation condition. Meanwhile, the content of sec-butyl alcohol does not need to be increased to a certain degree in the mixed material of sec-butyl acetate, sec-butyl alcohol and water collected from the side line of the tower top, and the tower can carry out total reflux, so that the operation requirement on the tower is reduced. Because of the enrichment of C8 hydrocarbons in the system, occasional contaminant discharges may be preferred from the reflux drum at the top of the column to reduce C8 hydrocarbons in the column.
In the invention, sec-butyl acetate (SBAC), sec-butyl alcohol (SBA) and water (H)2O) can form ternary azeotrope, and the azeotropic ratio of the three is SBAC: SBA: h2O=32:45:23The azeotropic temperature is 86.0 ℃, the sec-butyl alcohol and water can form binary azeotrope, the azeotrope comprises 32 percent of water and 68 percent of sec-butyl alcohol, and the azeotropic temperature is 88.5 ℃. Thus, in this system, it is desirable to control the entry of sec-butyl acetate (SBAC), sec-butyl alcohol (SBA) and water (H) into the finishing column2O), the lower the amount of the sec-butyl acetate in the mixture is, the more favorable the separation of the sec-butyl alcohol is, and the higher the amount of the sec-butyl alcohol obtained by separation is, therefore, the amount of the water in the system is the minimum to ensure that the sec-butyl acetate (SBAC), the sec-butyl alcohol (SBA) and the water (H) enter a refining tower2O) of the mixture of the second butyl acetate and the second butyl acetate is the amount of water which is distilled off from the top of the tower in an azeotropic way.
In order to better separate the sec-butyl alcohol from the aqueous solution, the aqueous phase containing the sec-butyl alcohol from the bottom of the multistage extraction tower can carry out multistage heat exchange before being sent to the liquid separation tank, the material can exchange heat with the material at the top of the sec-butyl alcohol azeotropic distillation tower and then exchange heat with the material at the bottom of the sec-butyl alcohol azeotropic distillation tower, can exchange heat with the material at the top of the sec-butyl alcohol refining tower and then exchange heat with the material at the bottom of the sec-butyl alcohol refining tower, and can also directly exchange heat with steam and then be sent to the liquid separation tank. The liquid separation tank can be provided with a heating coil so as to control the temperature of the liquid separation tank and better separate the sec-butyl alcohol from the aqueous solution. The temperature of the liquid separation tank is controlled to be 40-90 ℃, preferably 50-90 ℃, more preferably 60-90 ℃, more preferably 70-90 ℃, and further preferably 70-80 ℃.
In the present invention, the hydrolysis conditions of step (1) include: the temperature of the hydrolysis reactor is 75-150 ℃, preferably 80-130 ℃, more preferably 85-125 ℃, and further preferably 90-120 ℃; the reaction pressure is 0.6 to 1.5MPa, preferably 0.8 to 1.3MPa, more preferably 0.8 to 1.25MPa, and still more preferably 0.8 to 1.2 MPa.
In step (1), the molar ratio of water to ester is 1.05-8:1, preferably 1.2-4:1, and more preferably 1.2-2: 1.
In the step (3), in the sec-butyl acetate recovery tower, the molar ratio of the content of the sec-butyl acetate in the mixture feed of the acetic acid at the bottom of the sec-butyl alcohol azeotropic distillation tower and part of the sec-butyl acetate to the water addition amount of the entrainer water is 2-8:1, preferably 3-5:1, and more preferably 4: 1.
In the step (5), the amount of water added into the sec-butyl alcohol refining tower is the amount of water required for azeotropic distillation of all sec-butyl acetate from the tower top in the oil phase of the sec-butyl alcohol obtained from the upper layer of the liquid separation tank.
In the invention, the tower top pressure of the sec-butyl alcohol azeotropic distillation tower is normal pressure, and the tower top temperature is 80-100 ℃, preferably 82-98 ℃, and further preferably 85-92 ℃.
The top pressure of the sec-butyl alcohol refining tower is normal pressure, the top temperature is 80-100 ℃, the preferred temperature is 82-95 ℃, the further preferred temperature is 85-90 ℃, and the oil phase reflux ratio is 0.5-10: 1, preferably 1 to 4:1, more preferably 1.2 to 2: 1.
the overhead pressure of the sec-butyl acetate recovery tower is normal pressure, the overhead temperature is 80-95 ℃, preferably 82-95 ℃, more preferably 82-90 ℃, the bottom temperature is 115-120 ℃, preferably 116-119 ℃, more preferably 117-118 ℃, and the overhead reflux ratio is 1-2:1, 1.3-1.7:1, more preferably 1.5: 1.
In the invention, the operation pressure of the multi-stage extraction tower is normal pressure, and the operation temperature is 1-30 ℃, preferably 1-20 ℃, more preferably 1-10 ℃, and further preferably 5-10 ℃.
The invention also provides a sec-butyl alcohol preparation system, which comprises: the device comprises a hydrolysis reactor, a sec-butyl alcohol azeotropic rectifying tower, a sec-butyl acetate recovery tower, a multistage extraction tower, a sec-butyl alcohol refining tower and a liquid separation tank, wherein the hydrolysis reactor is provided with a sec-butyl acetate feeding pipeline and a water feeding pipeline, the outlet of the reactor is connected with the feeding hole of the sec-butyl alcohol azeotropic rectifying tower through a pipeline, the tower top of the sec-butyl alcohol azeotropic rectifying tower is connected with a discharging pipeline of a mixture of sec-butyl acetate, sec-butyl alcohol and water, the tower bottom outlet of the tower is connected with the feeding hole of the sec-butyl acetate recovery tower through a pipeline, the tower top of the sec-butyl acetate recovery tower is connected with the discharging pipeline of the mixture of sec-butyl acetate and water, the tower bottom of the tower is connected with a discharging pipeline of acetic acid, the upper part of the sec-butyl alcohol azeotropic rectifying tower is provided with a side draw outlet, the upper side draw outlet, the top of the secondary butyl alcohol refining tower is connected with a discharge pipeline of a secondary butyl acetate oil phase, an outlet at the bottom of the secondary butyl alcohol refining tower is connected with a feed inlet of a liquid separation tank through a pipeline, the upper part of the liquid separation tank is provided with a discharge pipeline of the secondary butyl alcohol oil phase, the discharge pipeline is connected with a feed inlet of a secondary butyl alcohol refining tower, the top of the secondary butyl alcohol refining tower is provided with a water feeding pipeline, the tower top is provided with a discharge pipeline of a mixture of the secondary butyl acetate, the secondary butyl alcohol and.
The sec-butyl alcohol azeotropic rectifying tower, the sec-butyl acetate recovery tower and the sec-butyl alcohol refining tower respectively comprise a tower top condenser, a reflux tank and a tower bottom reboiler, and the sec-butyl acetate recovery tower and the multistage extraction tower are provided with water feeding pipelines.
In the invention, further, the bottom of the reflux tank at the top of the azeotropic distillation tower also comprises a water outlet pipeline which is connected with a feed pipeline of the reactor. In the invention, the bottom of the reflux tank at the top of the sec-butyl acetate recovery tower is connected with a discharge pipeline which is connected with a reactor feed pipeline. The upper part of the reflux tank at the top of the sec-butyl alcohol refining tower is connected with a discharge pipeline which is connected with a reactor feeding pipeline.
Further, the lower part or the bottom of the liquid separation tank is connected to the multistage extraction column through a water phase outlet pipeline.
According to the invention, the material extracted from the upper side line of the azeotropic distillation tower is separated by adopting the multistage extraction tower and then is sent into the sec-butyl alcohol refining tower, so that the sec-butyl acetate and the sec-butyl alcohol are effectively separated on the basis of not introducing other impurities, the yield of the sec-butyl alcohol obtained after separation is high, the circulation quantity of a device is greatly reduced, the energy consumption of the device is reduced, meanwhile, the operation difficulty of the sec-butyl alcohol azeotropic distillation tower is also reduced, the requirement on the content of the sec-butyl alcohol in the material extracted from the side line is reduced, and the system operation is simpler and more stable. The purity of the sec-butyl alcohol product separated from the bottom of the sec-butyl alcohol refining tower is up to more than 99.5 percent, the once-through yield of the sec-butyl alcohol is greatly improved from the original 50 percent to more than 85 percent, the purity of the acetic acid obtained from the bottom of the sec-butyl acetate recovery tower is also higher and is more than 99.5 percent, the sec-butyl alcohol-free sec-butyl acetate recovery tower does not contain the sec-butyl alcohol, and the catalyst for the reaction is not influenced when the sec-butyl alcohol product is returned to an addition reactor of a sec-butyl acetate preparation device for recycling.
Drawings
FIG. 1 is a schematic view of the apparatus of the present invention.
Detailed Description
The invention is further illustrated by the following examples. However, the present invention is not limited to the following examples, and various changes may be made to the present invention within a range not departing from the gist of the present invention, and these changes are still included in the scope of the present invention.
As shown in fig. 1, a system for sec-butyl alcohol production comprises: a material mixer 3, a reactor 5, a sec-butyl alcohol azeotropic rectifying tower 7, a sec-butyl acetate recovery tower 16, a multistage extraction tower 25 and a sec-butyl alcohol refining tower 31, wherein the front of the material mixer 3 is provided with a sec-butyl acetate feeding pipeline 1 and a water feeding pipeline 2, the material mixer is connected with the reactor 5 through a pipeline 4, the reactor 5 is provided with a discharge pipeline 6 connected with a middle feeding pipeline of the sec-butyl alcohol azeotropic rectifying tower 7, the top of the sec-butyl alcohol azeotropic rectifying tower 7 is connected with a discharge pipeline of a mixture of sec-butyl acetate, sec-butyl alcohol and water, the bottom of the sec-butyl alcohol azeotropic rectifying tower 7 is connected with a discharge pipeline 14 of acetic acid and sec-butyl acetate, the discharge pipeline 14 is connected with a middle feeding pipeline of the sec-butyl acetate recovery tower 16, the top of the sec-butyl acetate recovery tower 16 is connected with a discharge pipeline of sec-butyl acetate and water, the bottom of the tower is connected with a discharge pipeline 23 of acetic, A discharge pipeline 15 of a mixed material of water and sec-butyl alcohol, wherein the discharge pipeline 15 is connected with a lower feed inlet of a multistage extraction tower 25, the upper part of the multistage extraction tower 25 is connected with a discharge pipeline 26 of a sec-butyl acetate oil phase and is connected with a sec-butyl acetate feed pipeline 1 or a water feed pipeline 2 of a hydrolysis reactor 5, the bottom of the multistage extraction tower 25 is connected with a sec-butyl alcohol water phase discharge pipeline 27, the discharge pipeline 27 is connected with a top feed inlet of a liquid separation tank 28, the upper part of the liquid separation tank 28 is connected with a discharge pipeline 30 of a sec-butyl alcohol oil phase, the lower part or the bottom of the liquid separation tank 28 returns to the multistage extraction tower 25 through a water phase outlet pipeline 29, the discharge pipeline 30 is connected with a feed inlet of a sec-butyl alcohol refining tower 31, the top of the sec-butyl alcohol refining tower 31 is connected with a discharge pipeline.
Wherein, the sec-butyl alcohol azeotropic rectifying tower 7, the sec-butyl acetate recovery tower 16 and the sec-butyl alcohol refining tower 31 respectively comprise overhead condensers (8, 17, 32), reflux tanks (9, 18, 33) and tower bottom reboilers (13, 22, 37), the reflux tanks 9, 18, 33 respectively have reflux pipelines 10, 19, 36 returning to the sec-butyl alcohol azeotropic rectifying tower 7, the sec-butyl acetate recovery tower 16 and the sec-butyl alcohol refining tower 31, and the sec-butyl acetate recovery tower 16 and the multistage extraction tower 25 also comprise water feed pipelines 21, 24.
The bottom of the reflux tank 9 at the top of the sec-butyl alcohol azeotropic distillation tower 7 is also connected with a water phase discharge pipeline 12, the discharge pipeline 12 is connected with the reactor feed pipeline 2, and the upper part of the reflux tank 9 is also connected with an impurity discharge pipeline 11.
The bottom of the reflux tank 18 at the top of the sec-butyl acetate recovery tower 16 is also connected with a water phase discharge pipeline 20, and the discharge pipeline 20 is connected with the reactor feed pipeline 2.
The upper part of the tower top reflux tank 33 of the sec-butyl alcohol refining tower 31 is connected with an oil phase discharge pipeline 35 of sec-butyl acetate, the discharge pipeline 35 is connected with a reactor feed pipeline 1 or 2, and the tower upper part of the tower top reflux tank 33 is also connected with an oil phase discharge pipeline 34 of sec-butyl acetate and is directly connected with a tower upper part reflux opening.
Example 1
Mixing sec-butyl acetate with water, and then sending the mixture into a hydrolysis reactor, wherein the hydrolysis conditions are as follows: the temperature is 100 ℃, the reaction pressure is 1.0MPa, the molar ratio of water to ester is 2:1, a mixture of sec-butyl alcohol, water, acetic acid and sec-butyl acetate is obtained through hydrolysis reaction, the mixture of sec-butyl alcohol, water, acetic acid and sec-butyl acetate obtained after the reaction is sent to a sec-butyl alcohol azeotropic rectifying tower for separation, and the operating conditions of the sec-butyl alcohol azeotropic rectifying tower are as follows: the number of theoretical plates of a sec-butyl alcohol azeotropic rectifying tower is 50, the pressure of the tower top is normal pressure, the temperature of the tower top is 85 ℃, a mixture of sec-butyl acetate, sec-butyl alcohol and water is evaporated from the tower top, the oil phase after condensation and delamination is refluxed, the oil phase obtained from the tower top is totally refluxed, the mixture of acetic acid and part of sec-butyl acetate falls into the tower bottom, the mixture of acetic acid and part of sec-butyl acetate at the tower bottom of the sec-butyl alcohol azeotropic rectifying tower is pumped out and sent into a sec-butyl acetate recovery tower, entrainer water is added for azeotropic rectification, the pressure of the tower top of the sec-butyl acetate recovery tower is normal pressure, the temperature of the tower top is 90 ℃, the temperature of the tower bottom is 115 ℃, the reflux ratio of the tower top is 2:1, the molar ratio of the sec-butyl acetate content to the water addition amount in feeding is 4:1, the mixture of sec-butyl acetate and water is obtained from the tower top, obtaining high-purity acetic acid at the bottom of the tower, returning the high-purity acetic acid obtained at the bottom of the tower to an addition reactor of a sec-butyl acetate preparation device for recycling, pumping a mixed material containing sec-butyl alcohol, sec-butyl acetate and water from the upper side line of a sec-butyl alcohol azeotropic rectifying tower, cooling to 10 ℃, sending the mixed material into a four-stage extraction tower, adding extractant chilled water, wherein the temperature of the chilled water is 2 ℃, and the operating conditions of the four-stage extraction tower are as follows: the pressure of the top of the rectification tower is normal pressure, the temperature is 8 ℃, the mass ratio of the addition amount of freezing water to a mixed material containing sec-butyl alcohol, sec-butyl acetate and water, which is extracted from the upper side line of the sec-butyl alcohol azeotropic rectification tower, is 2:1, the oil phase of the sec-butyl acetate is obtained at the top of the four-stage extraction tower, the oil phase of the sec-butyl acetate obtained at the top of the four-stage extraction tower returns to the hydrolysis reactor for reaction, the water phase containing the sec-butyl alcohol is obtained at the bottom of the rectification tower, the water phase at the bottom of the rectification tower is extracted and sent to the liquid separation tank, the temperature of the liquid separation tank is controlled to be 70 ℃, the oil phase of the sec-butyl alcohol is obtained at the upper layer of the liquid separation tank, the water phase containing a small amount of the sec-butyl alcohol is obtained at the lower layer of the liquid separation tank, the water phase containing a small amount of the, the tower top temperature is 100 ℃, the oil phase reflux ratio is 0.5: 1, obtaining a mixture of sec-butyl acetate, sec-butyl alcohol and water at the tower top, condensing and layering, refluxing one part of an oil phase, returning the other part of the oil phase to a hydrolysis reactor for reaction, preferably returning the water phase to a sec-butyl alcohol refining tower for cyclic utilization, and obtaining a high-purity product, namely sec-butyl alcohol, at the tower bottom of the sec-butyl alcohol refining tower.
Analyzing the tower bottom material of the sec-butyl alcohol refining tower and the tower bottom material of the sec-butyl acetate refining tower, wherein the purity of a sec-butyl alcohol product of the tower bottom material of the sec-butyl alcohol refining tower is 99.68%, the purity of acetic acid of the tower bottom material of the sec-butyl acetate refining tower is 99.56%, and the one-way yield of the sec-butyl alcohol is 87.5% after calculation.
Example 2
Mixing sec-butyl acetate with water, and then sending the mixture into a hydrolysis reactor, wherein the hydrolysis conditions are as follows: the temperature is 150 ℃, the reaction pressure is 1.5MPa, the molar ratio of water to ester is 8:1, a mixture of sec-butyl alcohol, water, acetic acid and sec-butyl acetate is obtained through hydrolysis reaction, the mixture of sec-butyl alcohol, water, acetic acid and sec-butyl acetate obtained after the reaction is sent to a sec-butyl alcohol azeotropic rectifying tower for separation, and the operating conditions of the sec-butyl alcohol azeotropic rectifying tower are as follows: the number of theoretical plates of a sec-butyl alcohol azeotropic rectifying tower is 60, the pressure of the tower top is normal pressure, the temperature of the tower top is 100 ℃, a mixture of sec-butyl acetate, sec-butyl alcohol and water is evaporated from the tower top, the oil phase after condensation and delamination is refluxed, the oil phase obtained from the tower top is refluxed completely, the mixture of acetic acid and part of sec-butyl acetate falls into the tower bottom, the mixture of acetic acid and the sec-butyl acetate at the tower bottom of the sec-butyl alcohol azeotropic rectifying tower is pumped out and sent into a sec-butyl acetate recovery tower, entrainer water is added for azeotropic rectification, the pressure of the tower top of the sec-butyl acetate recovery tower is normal pressure, the temperature of the tower top is 95 ℃, the temperature of the tower bottom is 120 ℃, the reflux ratio of the tower top is 1.8:1, the molar ratio of the sec-butyl acetate content to the water addition amount in the feed is 8:1, the mixture of the sec-butyl acetate and the water is obtained from the, obtaining high-purity acetic acid at the bottom of the tower, returning the high-purity acetic acid obtained at the bottom of the tower to an addition reactor of a sec-butyl acetate preparation device for recycling, extracting a mixed material containing sec-butyl alcohol, sec-butyl acetate and water from the upper side line of a sec-butyl alcohol azeotropic rectifying tower, feeding the mixed material into an eight-stage extraction tower, adding extractant chilled water, wherein the temperature of the chilled water is 3 ℃, and the operating conditions of the eight-stage extraction tower are as follows: the pressure of the top of the extraction tower is normal pressure, the temperature is 20 ℃, the mass ratio of the addition amount of the freezing water to the mixed material containing sec-butyl alcohol, sec-butyl acetate and water, which is extracted from the upper side line of the sec-butyl alcohol azeotropic distillation tower, is 3:1, the oil phase of the sec-butyl acetate is obtained at the top of the eight-stage extraction tower, the oil phase of the sec-butyl acetate obtained at the top of the eight-stage extraction tower returns to the hydrolysis reactor for reaction, the water phase containing the sec-butyl alcohol is obtained at the bottom of the extraction tower, the water phase at the bottom of the extraction tower is extracted and then sent to the liquid separation tank, the temperature of the liquid separation tank is controlled to be 80 ℃, the oil phase of the sec-butyl alcohol is obtained at the upper layer of the liquid separation tank, the water phase containing a small amount of the sec-butyl alcohol is obtained at the lower layer of the liquid separation tank, the water phase containing a small amount of the sec, the tower top temperature is 90 ℃, and the oil phase reflux ratio is 5:1, obtaining a mixture of sec-butyl acetate, sec-butyl alcohol and water at the tower top, condensing and layering, refluxing one part of an oil phase, returning the other part of the oil phase to a hydrolysis reactor for reaction, preferably returning the water phase to a sec-butyl alcohol refining tower for cyclic utilization, and obtaining a high-purity product, namely sec-butyl alcohol, at the tower bottom of the sec-butyl alcohol refining tower.
Analyzing the tower bottom material of the sec-butyl alcohol refining tower and the tower bottom material of the sec-butyl acetate refining tower, wherein the purity of a sec-butyl alcohol product of the tower bottom material of the sec-butyl alcohol refining tower is 99.78%, the purity of acetic acid of the tower bottom material of the sec-butyl acetate refining tower is 99.72%, and the one-way yield of the sec-butyl alcohol is 86.5% after calculation.
Example 3
Mixing sec-butyl acetate with water, and then sending the mixture into a hydrolysis reactor, wherein the hydrolysis conditions are as follows: the temperature is 75 ℃, the reaction pressure is 0.6MPa, the molar ratio of water to ester is 1.05:1, a mixture of sec-butyl alcohol, water, acetic acid and sec-butyl acetate is obtained through hydrolysis reaction, the mixture of sec-butyl alcohol, water, acetic acid and sec-butyl acetate obtained after the reaction is sent to a sec-butyl alcohol azeotropic rectifying tower for separation, and the operating conditions of the sec-butyl alcohol azeotropic rectifying tower are as follows: the number of theoretical plates of a sec-butyl alcohol azeotropic rectifying tower is 40, the pressure of the tower top is normal pressure, the temperature of the tower top is 80 ℃, a mixture of sec-butyl acetate, sec-butyl alcohol and water is evaporated from the tower top, the oil phase after condensation and delamination is refluxed, the oil phase obtained from the tower top is refluxed completely, the mixture of acetic acid and part of sec-butyl acetate falls into the tower bottom, the mixture of acetic acid and part of sec-butyl acetate at the tower bottom of the sec-butyl alcohol azeotropic rectifying tower is pumped out and sent into a sec-butyl acetate recovery tower, entrainer water is added for azeotropic rectification, the pressure of the tower top of the sec-butyl acetate recovery tower is normal pressure, the temperature of the tower top is 80 ℃, the temperature of the tower bottom is 116 ℃, the reflux ratio of the tower top is 1:1, the molar ratio of the sec-butyl acetate content to the water addition amount in the feed is 2:1, the mixture of sec-butyl acetate and water is obtained from the, obtaining high-purity acetic acid at the bottom of the tower, returning the high-purity acetic acid obtained at the bottom of the tower to an addition reactor of a sec-butyl acetate preparation device for recycling, pumping a mixed material containing sec-butyl alcohol, sec-butyl acetate and water from the upper side line of a sec-butyl alcohol azeotropic rectifying tower, feeding the mixed material into a ten-grade extraction tower, adding extractant chilled water, wherein the temperature of the chilled water is 1 ℃, and the operating conditions of the ten-grade extraction tower are as follows: the pressure of the top of the tower is normal pressure, the temperature is 30 ℃, the mass ratio of the addition amount of freezing water to a mixed material containing sec-butyl alcohol, sec-butyl acetate and water, which is extracted from the upper side line of the sec-butyl alcohol azeotropic distillation tower, is 5:1, the oil phase of the sec-butyl acetate is obtained at the top of a ten-stage extraction tower, the oil phase of the sec-butyl acetate obtained at the top of the ten-stage extraction tower returns to a hydrolysis reactor for reaction, the water phase containing the sec-butyl alcohol is obtained at the bottom of the tower, the water phase at the bottom of the tower is extracted and sent to a liquid separation tank, the temperature of the liquid separation tank is controlled to be 75 ℃, the oil phase of the sec-butyl alcohol is obtained at the upper layer of the liquid separation tank, the water phase containing a small amount of the sec-butyl alcohol is obtained at the lower layer of the liquid separation tank, the water phase containing a small amount of the sec-butyl alcohol is, the tower top temperature is 89 ℃, and the oil phase reflux ratio is 4:1, obtaining a mixture of sec-butyl acetate, sec-butyl alcohol and water at the tower top, condensing and layering, refluxing one part of an oil phase, returning the other part of the oil phase to a hydrolysis reactor for reaction, preferably returning the water phase to a sec-butyl alcohol refining tower for cyclic utilization, and obtaining a high-purity product, namely sec-butyl alcohol, at the tower bottom of the sec-butyl alcohol refining tower.
Analyzing the tower bottom material of the sec-butyl alcohol refining tower and the tower bottom material of the sec-butyl acetate refining tower, wherein the purity of a sec-butyl alcohol product of the tower bottom material of the sec-butyl alcohol refining tower is 99.72%, the purity of acetic acid of the tower bottom material of the sec-butyl acetate refining tower is 99.62%, and the once-through yield of the sec-butyl alcohol is 85.6% after calculation.
Example 4
Mixing sec-butyl acetate with water, and then sending the mixture into a hydrolysis reactor, wherein the hydrolysis conditions are as follows: the temperature is 85 ℃, the reaction pressure is 0.8MPa, the molar ratio of water to ester is 1.2:1, a mixture of sec-butyl alcohol, water, acetic acid and sec-butyl acetate is obtained through hydrolysis reaction, the mixture of sec-butyl alcohol, water, acetic acid and sec-butyl acetate obtained after the reaction is sent to a sec-butyl alcohol azeotropic rectifying tower for separation, and the operating conditions of the sec-butyl alcohol azeotropic rectifying tower are as follows: the number of theoretical plates of a sec-butyl alcohol azeotropic rectifying tower is 45, the pressure of the tower top is normal pressure, the temperature of the tower top is 82 ℃, a mixture of sec-butyl acetate, sec-butyl alcohol and water is evaporated from the tower top, the oil phase after condensation and delamination is refluxed, the oil phase obtained from the tower top is completely refluxed, the mixture of acetic acid and part of sec-butyl acetate falls into the tower bottom, the mixture of acetic acid and part of sec-butyl acetate at the tower bottom of the sec-butyl alcohol azeotropic rectifying tower is pumped out and sent into a sec-butyl acetate recovery tower, entrainer water is added for azeotropic rectification, the pressure of the tower top of the sec-butyl acetate recovery tower is normal pressure, the temperature of the tower top is 82 ℃, the temperature of the tower bottom is 117 ℃, the reflux ratio of the tower top is 1.2:1, the molar ratio of the sec-butyl acetate content to the added water amount in the feed is 7:1, the mixture of sec-butyl acetate and water is obtained from the tower, obtaining high-purity acetic acid at the bottom of the tower, returning the high-purity acetic acid obtained at the bottom of the tower to an addition reactor of a sec-butyl acetate preparation device for recycling, pumping a mixed material containing sec-butyl alcohol, sec-butyl acetate and water from the upper side line of a sec-butyl alcohol azeotropic rectifying tower, cooling to 9 ℃, sending the mixed material into a five-stage extraction tower, adding extractant chilled water, wherein the temperature of the chilled water is 5 ℃, and the operating conditions of the five-stage extraction tower are as follows: the pressure of the top of the rectifying tower is normal pressure, the temperature is 6 ℃, the mass ratio of the addition amount of the freezing water to the mixed material containing sec-butyl alcohol, sec-butyl acetate and water, which is extracted from the upper side line of the sec-butyl alcohol azeotropic rectifying tower, is 1.4:1, the oil phase of the sec-butyl acetate is obtained at the top of the five-stage extracting tower, the oil phase of the sec-butyl acetate obtained at the top of the five-stage extracting tower returns to the hydrolysis reactor for reaction, the water phase containing the sec-butyl alcohol is obtained at the bottom of the tower, the water phase at the bottom of the tower is extracted and then sent to the liquid separation tank, the temperature of the liquid separation tank is controlled to be 40 ℃, the oil phase of the sec-butyl alcohol is obtained at the upper layer of the liquid separation tank, the water phase containing a small amount of the sec-butyl alcohol is obtained at the lower layer of the liquid separation tank, the water phase containing a small amount of the sec-butyl, the tower top temperature is 88 ℃, and the oil phase reflux ratio is 1.2:1, obtaining a mixture of sec-butyl acetate, sec-butyl alcohol and water at the tower top, condensing and layering, refluxing one part of an oil phase, returning the other part of the oil phase to a hydrolysis reactor for reaction, preferably returning the water phase to a sec-butyl alcohol refining tower for cyclic utilization, and obtaining a high-purity product, namely sec-butyl alcohol, at the tower bottom of the sec-butyl alcohol refining tower.
Analyzing the tower bottom material of the sec-butyl alcohol refining tower and the tower bottom material of the sec-butyl acetate refining tower, wherein the purity of a sec-butyl alcohol product of the tower bottom material of the sec-butyl alcohol refining tower is 99.85%, the purity of acetic acid of the tower bottom material of the sec-butyl acetate refining tower is 99.73%, and the one-way yield of the sec-butyl alcohol is 88.2% after calculation.
Example 5
Mixing sec-butyl acetate with water, and then sending the mixture into a hydrolysis reactor, wherein the hydrolysis conditions are as follows: the temperature is 90 ℃, the reaction pressure is 1.2MPa, the molar ratio of water to ester is 3:1, a mixture of sec-butyl alcohol, water, acetic acid and sec-butyl acetate is obtained through hydrolysis reaction, the mixture of sec-butyl alcohol, water, acetic acid and sec-butyl acetate obtained after the reaction is sent to a sec-butyl alcohol azeotropic rectifying tower for separation, and the operating conditions of the sec-butyl alcohol azeotropic rectifying tower are as follows: the number of theoretical plates of a sec-butyl alcohol azeotropic rectifying tower is 55, the pressure of the tower top is normal pressure, the temperature of the tower top is 88 ℃, a mixture of sec-butyl acetate, sec-butyl alcohol and water is evaporated from the tower top, the oil phase after condensation and delamination is refluxed, the oil phase obtained from the tower top is totally refluxed, the mixture of acetic acid and part of sec-butyl acetate falls into the tower bottom, the mixture of acetic acid and part of sec-butyl acetate at the tower bottom of the sec-butyl alcohol azeotropic rectifying tower is pumped out and sent into a sec-butyl acetate recovery tower, entrainer water is added for azeotropic rectification, the pressure of the tower top of the sec-butyl acetate recovery tower is normal pressure, the temperature of the tower top is 85 ℃, the temperature of the tower bottom is 117.5 ℃, the reflux ratio of the tower top is 1.3:1, the molar ratio of the content of sec-butyl acetate to the added water amount in the feed is 3:1, the mixture of sec-butyl acetate and water is obtained from the, obtaining high-purity acetic acid at the bottom of the tower, returning the high-purity acetic acid obtained at the bottom of the tower to an addition reactor of a sec-butyl acetate preparation device for recycling, pumping a mixed material containing sec-butyl alcohol, sec-butyl acetate and water from the upper side line of a sec-butyl alcohol azeotropic rectifying tower, cooling to 8 ℃, sending the mixed material into a third-stage extraction tower, adding extractant chilled water, wherein the temperature of the chilled water is 4 ℃, and the operating conditions of the third-stage extraction tower are as follows: the pressure of the top of the rectification tower is normal pressure, the temperature is 5 ℃, the mass ratio of the addition amount of the freezing water to the mixed material containing sec-butyl alcohol, sec-butyl acetate and water, which is extracted from the upper side line of the sec-butyl alcohol azeotropic rectification tower, is 1.2:1, the oil phase of the sec-butyl acetate is obtained at the top of the three-stage extraction tower, the oil phase of the sec-butyl acetate obtained at the top of the three-stage extraction tower returns to the hydrolysis reactor for reaction, the water phase containing the sec-butyl alcohol is obtained at the bottom of the rectification tower, the water phase at the bottom of the rectification tower is extracted and then sent to the liquid separation tank, the temperature of the liquid separation tank is controlled at 50 ℃, the oil phase of the sec-butyl alcohol is obtained at the upper layer of the liquid separation tank, the water phase containing a small amount of the sec-butyl alcohol is obtained at the lower layer of the liquid separation tank, the water phase containing a small amount of, the tower top temperature is 80 ℃, the oil phase reflux ratio is 10: 1, obtaining a mixture of sec-butyl acetate, sec-butyl alcohol and water at the tower top, condensing and layering, refluxing one part of an oil phase, returning the other part of the oil phase to a hydrolysis reactor for reaction, preferably returning the water phase to a sec-butyl alcohol refining tower for cyclic utilization, and obtaining a high-purity product, namely sec-butyl alcohol, at the tower bottom of the sec-butyl alcohol refining tower.
Analyzing the tower bottom material of the sec-butyl alcohol refining tower and the tower bottom material of the sec-butyl acetate refining tower, wherein the purity of a sec-butyl alcohol product of the tower bottom material of the sec-butyl alcohol refining tower is 99.59%, the purity of acetic acid of the tower bottom material of the sec-butyl acetate refining tower is 99.64%, and the one-way yield of the sec-butyl alcohol is 86.7% after calculation.
Example 6
Mixing sec-butyl acetate with water, and then sending the mixture into a hydrolysis reactor, wherein the hydrolysis conditions are as follows: the temperature is 110 ℃, the reaction pressure is 1.25MPa, the molar ratio of water to ester is 4:1, a mixture of sec-butyl alcohol, water, acetic acid and sec-butyl acetate is obtained through hydrolysis reaction, the mixture of sec-butyl alcohol, water, acetic acid and sec-butyl acetate obtained after the reaction is sent to a sec-butyl alcohol azeotropic rectifying tower for separation, and the operating conditions of the sec-butyl alcohol azeotropic rectifying tower are as follows: the number of theoretical plates of a sec-butyl alcohol azeotropic rectifying tower is 46, the pressure of the tower top is normal pressure, the temperature of the tower top is 90 ℃, a mixture of sec-butyl acetate, sec-butyl alcohol and water is evaporated from the tower top, the oil phase after condensation and delamination is refluxed, the oil phase obtained from the tower top is completely refluxed, the mixture of acetic acid and part of sec-butyl acetate falls into the tower bottom, the mixture of acetic acid and part of sec-butyl acetate at the tower bottom of the sec-butyl alcohol azeotropic rectifying tower is pumped out and sent into a sec-butyl acetate recovery tower, entrainer water is added for azeotropic rectification, the pressure of the tower top of the sec-butyl acetate recovery tower is normal pressure, the temperature of the tower top is 88 ℃, the temperature of the tower bottom is 118 ℃, the reflux ratio of the tower top is 1.7:1, the molar ratio of the sec-butyl acetate content to the added water amount in the feed is 6:1, the mixture of sec-butyl acetate and water is obtained from the tower, obtaining high-purity acetic acid at the bottom of the tower, returning the high-purity acetic acid obtained at the bottom of the tower to an addition reactor of a sec-butyl acetate preparation device for recycling, pumping a mixed material containing sec-butyl alcohol, sec-butyl acetate and water from the upper side line of a sec-butyl alcohol azeotropic rectifying tower, cooling to 7 ℃, sending the mixed material into a six-stage extraction tower, adding extractant chilled water, wherein the temperature of the chilled water is 3 ℃, and the operating conditions of the six-stage extraction tower are as follows: the pressure of the tower top is normal pressure, the temperature is 5 ℃, the mass ratio of the addition amount of freezing water to a mixed material containing sec-butyl alcohol, sec-butyl acetate and water, which is extracted from the upper side line of the sec-butyl alcohol azeotropic distillation tower, is 1:1, the oil phase of the sec-butyl acetate is obtained at the tower top of the six-stage extraction tower, the oil phase of the sec-butyl acetate obtained at the tower top of the six-stage extraction tower returns to the hydrolysis reactor for reaction, the water phase containing the sec-butyl alcohol is obtained at the tower bottom, the water phase at the tower bottom is extracted and sent to the liquid separation tank, the temperature of the liquid separation tank is controlled to be 60 ℃, the oil phase of the sec-butyl alcohol is obtained at the upper layer of the liquid separation tank, the water phase containing a small amount of the sec-butyl alcohol is obtained at the lower layer of the liquid separation tank, the water phase containing a small amount of the sec-butyl alcohol is returned to the six-, the tower top temperature is 82 ℃, the oil phase reflux ratio is 2:1, obtaining a mixture of sec-butyl acetate, sec-butyl alcohol and water at the tower top, condensing and layering, refluxing one part of an oil phase, returning the other part of the oil phase to a hydrolysis reactor for reaction, preferably returning the water phase to a sec-butyl alcohol refining tower for cyclic utilization, and obtaining a high-purity product, namely sec-butyl alcohol, at the tower bottom of the sec-butyl alcohol refining tower.
Analyzing the tower bottom material of the sec-butyl alcohol refining tower and the tower bottom material of the sec-butyl acetate refining tower, wherein the purity of a sec-butyl alcohol product of the tower bottom material of the sec-butyl alcohol refining tower is 99.68%, the purity of acetic acid of the tower bottom material of the sec-butyl acetate refining tower is 99.56%, and the one-way yield of the sec-butyl alcohol is 87.5% after calculation.
Example 7
Mixing sec-butyl acetate with water, and then sending the mixture into a hydrolysis reactor, wherein the hydrolysis conditions are as follows: the temperature is 120 ℃, the reaction pressure is 1.3MPa, the molar ratio of water to ester is 6:1, a mixture of sec-butyl alcohol, water, acetic acid and sec-butyl acetate is obtained through hydrolysis reaction, the mixture of sec-butyl alcohol, water, acetic acid and sec-butyl acetate obtained after the reaction is sent to a sec-butyl alcohol azeotropic rectifying tower for separation, and the operating conditions of the sec-butyl alcohol azeotropic rectifying tower are as follows: the number of theoretical plates of a sec-butyl alcohol azeotropic rectifying tower is 48, the pressure of the tower top is normal pressure, the temperature of the tower top is 89 ℃, a mixture of sec-butyl acetate, sec-butyl alcohol and water is evaporated from the tower top, the oil phase after condensation and delamination is refluxed, the oil phase obtained from the tower top is refluxed completely, the mixture of acetic acid and part of sec-butyl acetate falls into the tower bottom, the mixture of acetic acid and the sec-butyl acetate at the tower bottom of the sec-butyl alcohol azeotropic rectifying tower is pumped out and sent into a sec-butyl acetate recovery tower, entrainer water is added for azeotropic rectification, the pressure of the tower top of the sec-butyl acetate recovery tower is normal pressure, the temperature of the tower top is 92 ℃, the temperature of the tower bottom is 119 ℃, the reflux ratio of the tower top is 1.5:1, the molar ratio of the sec-butyl acetate content to the water addition amount in the feed is 5:1, the mixture of the sec-butyl acetate and the water is obtained from the, obtaining high-purity acetic acid at the bottom of the tower, returning the high-purity acetic acid obtained at the bottom of the tower to an addition reactor of a sec-butyl acetate preparation device for recycling, extracting a mixed material containing sec-butyl alcohol, sec-butyl acetate and water from the upper side line of a sec-butyl alcohol azeotropic rectifying tower, feeding the mixed material into a seven-stage extraction tower, adding extractant chilled water, wherein the temperature of the chilled water is 3 ℃, and the operating conditions of the seven-stage extraction tower are as follows: the pressure of the tower top is normal pressure, the temperature is 10 ℃, the mass ratio of the addition amount of freezing water to a mixed material containing sec-butyl alcohol, sec-butyl acetate and water, which is extracted from the upper side line of a sec-butyl alcohol azeotropic distillation tower, is 1.6:1, the oil phase of the sec-butyl acetate is obtained at the tower top of a seven-stage extraction tower, the oil phase of the sec-butyl acetate obtained at the tower top of the seven-stage extraction tower returns to a hydrolysis reactor for reaction, the water phase containing the sec-butyl alcohol is obtained at the tower bottom, the water phase at the tower bottom is extracted and sent to a liquid separation tank, the temperature of the liquid separation tank is controlled to be 90 ℃, the oil phase of the sec-butyl alcohol is obtained at the upper layer of the liquid separation tank, the water phase containing a small amount of the sec-butyl alcohol is obtained at the lower layer of the liquid separation tank, the water phase containing a small amount of the sec-butyl alcohol is returned to the seven-, the tower top temperature is 85 ℃, the oil phase reflux ratio is 1:1, obtaining a mixture of sec-butyl acetate, sec-butyl alcohol and water at the tower top, condensing and layering, refluxing one part of an oil phase, returning the other part of the oil phase to a hydrolysis reactor for reaction, preferably returning the water phase to a sec-butyl alcohol refining tower for cyclic utilization, and obtaining a high-purity product, namely sec-butyl alcohol, at the tower bottom of the sec-butyl alcohol refining tower.
Analyzing the tower bottom material of the sec-butyl alcohol refining tower and the tower bottom material of the sec-butyl acetate refining tower, wherein the purity of a sec-butyl alcohol product of the tower bottom material of the sec-butyl alcohol refining tower is 99.65%, the purity of acetic acid of the tower bottom material of the sec-butyl acetate refining tower is 99.68%, and the one-way yield of the sec-butyl alcohol is 88.6% after calculation.

Claims (10)

1. The preparation method of sec-butyl alcohol comprises (1) mixing sec-butyl acetate with water, feeding into a hydrolysis reactor, and carrying out hydrolysis reaction under hydrolysis conditions to obtain a mixture of sec-butyl alcohol, water, acetic acid and sec-butyl acetate;
(2) sending a mixture of sec-butyl alcohol, water, acetic acid and sec-butyl acetate obtained after reaction into a sec-butyl alcohol azeotropic rectifying tower for separation, evaporating the mixture of sec-butyl acetate, sec-butyl alcohol and water from the tower top, refluxing an oil phase obtained after condensation and delamination, preferably, fully refluxing the oil phase obtained from the tower top, more preferably discharging irregular impurities, and enabling the mixture of acetic acid and part of sec-butyl acetate to fall into the tower bottom;
(3) extracting a mixture of acetic acid and part of sec-butyl acetate at the bottom of a sec-butyl alcohol azeotropic distillation tower, feeding the mixture into a sec-butyl acetate recovery tower, adding entrainer water for azeotropic distillation, obtaining a mixture of sec-butyl acetate and water at the top of the tower, preferably returning the mixture of the sec-butyl acetate and the water obtained at the top of the tower to a hydrolysis reactor for reaction, obtaining high-purity acetic acid at the bottom of the tower, and preferably returning the high-purity acetic acid obtained at the bottom of the tower to an addition reactor of a sec-butyl acetate preparation device for recycling;
(4) extracting a mixed material containing sec-butyl alcohol, sec-butyl acetate and water from the upper side line of a sec-butyl alcohol azeotropic rectifying tower, feeding the mixed material into a multistage extraction tower, adding extractant chilled water, obtaining an oil phase of the sec-butyl acetate at the top of the multistage extraction tower, preferably returning the oil phase of the sec-butyl acetate obtained at the top of the multistage extraction tower to a hydrolysis reactor for reaction, obtaining a water phase containing the sec-butyl alcohol at the bottom of the multistage extraction tower, extracting the water phase at the bottom of the multistage extraction tower, feeding the water phase into a liquid separation tank, obtaining the oil phase of the sec-butyl alcohol at the upper layer of the liquid separation tank, obtaining the water phase containing a small amount of the sec-butyl alcohol at the lower layer of the liquid;
(5) and (3) sending the oil phase of the sec-butyl alcohol obtained from the upper layer of the liquid separation tank into a sec-butyl alcohol refining tower for refining, adding entrainer water, obtaining a mixture of sec-butyl acetate, sec-butyl alcohol and water at the tower top, refluxing one part of the oil phase after condensation and delamination, preferably returning the other part of the oil phase to the hydrolysis reactor for reaction, preferably returning the water phase to the sec-butyl alcohol refining tower for recycling, and obtaining the high-purity product sec-butyl alcohol at the tower bottom of the sec-butyl alcohol refining tower.
2. The method as claimed in claim 1, wherein the mixed material containing sec-butyl alcohol, sec-butyl acetate and water is extracted from the upper side line of the sec-butyl alcohol azeotropic distillation tower, cooled to 5-10 ℃ and then sent to a multistage extraction tower.
3. The method according to claim 1 or 2, characterized in that the temperature of the extracting agent frozen water is 1-5 ℃, and the mass ratio of the frozen water to the mixed material containing sec-butyl alcohol, sec-butyl acetate and water extracted from the upper side line of the sec-butyl alcohol azeotropic distillation tower is 1.0-5.0:1, preferably 1.0-4.0:1, more preferably 1.0-3.0:1, more preferably 1.0-2.0:1, more preferably 1.2-1.8:1, and more preferably 1.4-1.6: 1.
4. The method according to claim 1 or 2, wherein the multistage extraction column is a countercurrent extraction column, and the number of extraction stages of the extraction column is 3 to 10, preferably 3 to 9, preferably 3 to 8, more preferably 4 to 7, and further preferably 4 to 6.
5. The process according to claim 1 or 2, characterized in that the number of theoretical plates of the sec-butanol azeotropic distillation tower is set to 40 to 60 blocks, preferably 40 to 55 blocks, more preferably 40 to 50 blocks, and further preferably 45 to 50 blocks.
6. The method according to claim 1 or 2, characterized in that the temperature of the liquid separation tank is controlled to be 40 ℃ to 90 ℃, preferably 50 ℃ to 90 ℃, more preferably 60 ℃ to 90 ℃, and further preferably 70 ℃ to 90 ℃.
7. A process according to claim 1 or 2, characterized in that the temperature of the hydrolysis reactor is 75-150 ℃, preferably 80-130 ℃, more preferably 85-125 ℃, even more preferably 90-120 ℃; the reaction pressure is 0.6 to 1.5MPa, preferably 0.8 to 1.3MPa, more preferably 0.8 to 1.25MPa, still more preferably 0.8 to 1.2MPa, and the molar ratio of water to ester is 1.05 to 8:1, preferably 1.2 to 4:1, still more preferably 1.2 to 2: 1.
8. The method according to claim 1 or 2, characterized in that the overhead pressure of the sec-butyl alcohol azeotropic distillation tower is normal pressure, the overhead temperature is 80-100 ℃, preferably 82-98 ℃, and further preferably 85-92 ℃; the top pressure of the sec-butyl alcohol refining tower is normal pressure, the top temperature is 80-100 ℃, the preferred temperature is 82-95 ℃, the further preferred temperature is 85-90 ℃, and the oil phase reflux ratio is 0.5-10: 1, preferably 1 to 4:1, more preferably 1.2 to 2: 1; the overhead pressure of the sec-butyl acetate recovery tower is normal pressure, the overhead temperature is 80-95 ℃, preferably 82-95 ℃, more preferably 82-90 ℃, the bottom temperature is 115-120 ℃, preferably 116-119 ℃, more preferably 117-118 ℃, the overhead reflux ratio is 1-2:1, 1.3-1.7:1, more preferably 1.5:1, and the molar ratio of the sec-butyl acetate content to the water addition amount in the feed is 2-8:1, preferably 3-5:1, more preferably 4: 1.
9. The method according to claim 1 or 2, wherein the operating pressure of the multi-stage extraction tower is normal pressure, and the operating temperature is 1-30 ℃, preferably 1-20 ℃, more preferably 1-10 ℃, and further preferably 5-10 ℃.
10. A system for producing sec-butanol, the system comprising: the hydrolysis reactor is provided with sec-butyl acetate and water feeding pipelines, the outlet of the reactor is connected with the feeding hole of the sec-butyl acetate azeotropic rectifying tower through a pipeline, the tower top of the sec-butyl alcohol azeotropic rectifying tower is connected with a discharging pipeline of a mixture of sec-butyl acetate, sec-butyl alcohol and water, the outlet at the tower bottom is connected with the feeding hole of the sec-butyl acetate recovering tower through a pipeline, the tower top of the sec-butyl acetate recovering tower is connected with a discharging pipeline of a mixture of sec-butyl acetate and water, the tower bottom is connected with a discharging pipeline of acetic acid, the upper part of the sec-butyl alcohol azeotropic rectifying tower is provided with a side draw outlet, the side draw outlet at the upper part is connected with the lower feeding hole of the multistage extraction tower through a pipeline, the upper part of the multistage extraction tower is connected with a chilled water feeding pipeline, and the top is connected with a discharging pipeline of a sec-butyl acetate oil phase, the outlet at the bottom is connected with the feed inlet of the liquid separating tank through a pipeline, the upper part of the liquid separating tank is provided with a discharge pipeline of a sec-butyl alcohol oil phase, the discharge pipeline is connected with the feed inlet of the sec-butyl alcohol refining tower through a pipeline, the top of the sec-butyl alcohol refining tower is provided with a water feeding pipeline, the top of the sec-butyl alcohol refining tower is provided with a discharge pipeline of a mixture of sec-butyl acetate, sec-butyl alcohol and water, and the bottom of the tower is provided.
The sec-butyl alcohol azeotropic rectifying tower, the sec-butyl acetate recovery tower and the sec-butyl alcohol refining tower respectively comprise a tower top condenser, a reflux tank and a tower bottom reboiler, and the sec-butyl acetate recovery tower and the multistage extraction tower are provided with water feeding pipelines.
CN201811606166.2A 2018-12-27 2018-12-27 Preparation method and system of sec-butyl alcohol Pending CN111377802A (en)

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