CN101168506B - Preparation method for sec-butyl acetate with product separating technique - Google Patents
Preparation method for sec-butyl acetate with product separating technique Download PDFInfo
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Abstract
The invention relates to a process for preparing sec-butyl acetate, with product separation technology, which is characterized in that the reaction is processed in one catalysis distillation column composed of a column reactor, an exhausting section, a reaction section, a distillation section, and a column top reflux condenser, wherein the reaction section is filled with catalyst, acetic acid andmixture C4 or butene which are reversely contacted and reacted on the surface of catalyst, the non-reacted mixture C4 or butene is evaporated out from the top of the catalyst distillation column, theproduct mixture is fed into an azeotropic distillation column, added with an entrainer, the distillate at the top of the azeotropic distillation column can be laminated naturally, the entrainer or entrainer and part of sec-butyl acetate are refluxed into the top of the azeotropic distillation column, the azeotropic distillation column carrying little entrainer is fed into a treating column, to bedistilled to obtain sec-butyl acetate, and the bottom material of the azeotropic distillation column can be circulated and feedback to the reaction system. The invention has the advantages of high reaction conversion rate, simple separation process, low cost, low energy consumption, high material utilization and the like.
Description
Technical field
The present invention relates to a kind of preparation method of sec-butyl acetate, relate in particular to a kind of method for preparing sec-butyl acetate with product separating technique.
Background technology
At present, utilize acetate and mixed C
4(or butylene) is raw material, prepares the method for sec-butyl acetate, normally carries out esterification in calandria type fixed bed reactor and obtains.For traditional technology, with mixed C
4(or butylene) is raw material, and utilizing itself and acetic acidreaction to prepare sec-butyl acetate, to have raw material sources wide and cost is little, good in economic efficiency, advantages of environment protection.U.S. Pat 5457228 discloses a kind of method for preparing sec-butyl acetate, is with reaction mass acetate and mixed C
4(or butylene) feeds from calandria type fixed bed reactor top, comprises the unreacted mixed C
4The product mixtures of (or butylene), unreacted acetate and product sec-butyl acetate flows out from reactor bottom simultaneously.After product mixtures passed through recycle pump and interchanger successively, a part of product mixtures was sent to the separation circuit of back, and another part product mixtures is sent into reactor as recycle feed together with fresh feed.The deficiency of this method is: (1) adopts the calandria type fixed bed reactor of doing, and sending to isolating that part of product mixtures generally needs earlier through flashing tower, with the unreacted mixed C
4Therefore (or butylene) removed from product mixtures, strengthened the difficulty of subsequent products separating technology, and flashing tower temperature, pressure are all higher, and energy consumption is higher; (2) the reaction mass into reactor that circulates increases the olefinic polymerization tendency, influence the product purification; (3) use recycle pump and interchanger, increased energy consumption.
In addition, utilize acetate and mixed C
4The research report of the separation and purification technology of (or butylene) prepared in reaction sec-butyl acetate is less relatively.Though the US5457228 U.S. Patent Publication a kind of method of utilizing acetate and 1-butylene and 2-butylene reaction catalytic Synthesis of sec-Butyl Acetate, but separation for this reaction products therefrom mixture, only mention in this patent and utilize distillation just sec-butyl acetate can be separated from product mixtures, but do not announce concrete separation method, do not announce the purity that product reached after separating yet.Because the boiling point of sec-butyl acetate and acetate is very approaching, utilize simple distillating method to be difficult to sec-butyl acetate is fully separated with acetate.And in application number is the Chinese patent application of 200710200148X, disclose a kind of from acetate and mixed C
4The method of the secondary butyl ester of separating acetic acid in the post reaction mixture: (1) acetate and hybrid C 4 post reaction mixture enter flashing tower, by flash distillation from the unreacted mixed C of flash distillation removed overhead
4And light constituent; (2) the flashing tower bottom product enters azeotropy rectification column, adds entrainer A, by azeotropic distillation with sec-butyl acetate and separated from acetic acid; (3) azeotropic distillation cat head material enters treating tower, obtains sec-butyl acetate by rectifying; (4) amount that contains entrainer A when acetate from the extraction of azeotropy rectification column bottom to reaction impact or to catalyst activity with when impacting work-ing life, azeotropy rectification column bottom material enters sour upgrading tower, add entrainer B, through azeotropic distillation again, acetate is concentrated acetate recycle after concentrating; Or: the amount that contains entrainer A when the acetate from the extraction of azeotropy rectification column bottom can be to not impacting of reacting, and in the time of also can and not impacting work-ing life catalyst activity, azeotropy rectification column bottom material directly loops back reactive system and utilizes.The product that the disclosed separating technology of this Chinese patent application is only applicable to adopt calandria type fixed bed reactor to react separates, and the technology relative complex.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, and the method for preparing sec-butyl acetate of the band product separating technique that a kind of separation circuit is simplified, cost is little, energy consumption is low, raw material availability is high is provided.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is: a kind of method for preparing sec-butyl acetate with product separating technique, it is characterized in that being reflected in the catalytic distillation tower of forming by a tower still, stripping section, conversion zone, rectifying section and trim the top of column condenser and carry out, a kind of catalyzer of filling in the conversion zone, acetate enters in the tower mixed C from the upper rectifying section of catalytic distillation tower
4Or butylene enters in the tower from the bottom stripping section of catalytic distillation tower, and both are in the catalyst surface counter current contact and react unreacted mixed C
4Or butylene steams from the catalytic distillation column overhead, and reacted product mixtures goes out and sends into azeotropy rectification column from the catalytic distillation tower tower bottom flow; In azeotropy rectification column, add entrainer and carry out azeotropic distillation, azeotropy rectification column overhead product natural layering, entrainer or entrainer and part sec-butyl acetate pass back into the azeotropic distillation column overhead; The sec-butyl acetate that carries a small amount of entrainer enters treating tower after the azeotropic distillation column overhead distillates, obtain sec-butyl acetate in treating tower after the rectifying; Entrainer can form azeotrope with sec-butyl acetate for any one, and the boiling point of its azeotropic point and acetate differs the material more than 10 ℃.
Technique scheme adopts catalytic distillation tower to carry out acetate and mixed C
4The esterification of (or butylene).This catalytic distillation tower comprises a tower still, a stripping section, a conversion zone, a rectifying section and a trim the top of column condenser.The conversion zone of described catalytic distillation tower is meant the part that is filled with catalyzer, and catalyzer can be heteropolyacid or ion exchange resin; Rectifying section refers to be positioned at the part that conversion zone is above, the trim the top of column condenser is following; Stripping section refers to be positioned at the part that conversion zone is following, the tower still is above.
The operational condition of above-mentioned catalytic distillation tower is: tower top pressure is controlled at 0.30～1.20MPa, preferred 0.35～0.75MPa; Tower top temperature is controlled at 40～90 ℃, preferred 50～70 ℃; Conversion zone middle part temperature is 50～150 ℃, preferred 60～120 ℃; Tower still temperature is controlled at 140～220 ℃, preferred 160～190 ℃; Reflux ratio is 0.1～10; Acetate and butylene mol ratio are 0.7: 1～3.0: 1; The acetic acid feed air speed is 0.1～10.0hr
-1
Above-mentioned acetate and mixed C
4The mixed C that mainly contains sec-butyl acetate, acetate, trace in the reacted product mixtures
4And light constituent (indivedual situations under detect less than), mainly contain the butylene of sec-butyl acetate, acetate and trace in the product mixtures behind above-mentioned acetate and the butene reaction, the while also can produce a spot of hydrocarbon polymer and other materials in this two classes reaction process.Because above-mentioned acetate and mixed C
4What the reaction process of (or butylene) adopted is catalytic distillation technology, acetate and mixed C
4Esterification of (or butylene) and unreacted mixed C
4And the fractionation of light constituent (or butylene) can be carried out simultaneously.Unreacted mixed C
4And the direct catalytic distillation column overhead from reactor of light constituent (or butylene) steams.Therefore when carrying out follow-up product separation, can economize and remove mixed C
4And the operation of light constituent (or butylene), simplified production technique, reduced production cost, reduced energy consumption.
Owing to from the reaction mixture that catalytic distillation tower comes out, also contain sec-butyl acetate and unreacted acetate, and the boiling point of sec-butyl acetate and acetate is very approaching, therefore can adopts the method for azeotropic distillation that sec-butyl acetate is effectively separated with acetate.Select a kind of entrainer in the azeotropic distillation process for use, described entrainer is that any one can form azeotrope with sec-butyl acetate, and the boiling point of its azeotropic point and acetate differs the material more than 10 ℃.According to known technology, after the substance classes that forms azeotrope was determined, its azeotropic consisted of fixed value, and promptly entrainer and sec-butyl acetate form the fixed value that consists of of azeotrope, add entrainer by this ratio of components.Preferably water of the present invention is as entrainer.Water is during as entrainer, and water is according to water: the ratio of sec-butyl acetate=1: 4 (mass ratio) is added.
In the above-mentioned azeotropic distillation process, the azeotropic distillation column bottom temperature is controlled at 100～130 ℃, preferred 105～125 ℃.Be higher than 130 ℃ as temperature, then acetate easily enters cat head; Be lower than 100 ℃ as temperature, the azeotrope of sec-butyl acetate and entrainer then can not effectively steam cat head.The azeotropy rectification column tower top temperature should be controlled at 75～100 ℃, preferred 78～90 ℃.After sec-butyl acetate and entrainer steam from the azeotropic distillation column overhead, through cooling, sec-butyl acetate and entrainer natural layering.Entrainer or entrainer and part sec-butyl acetate pass back into the azeotropic distillation column overhead, then enter treating tower after the sec-butyl acetate of carrying a small amount of entrainer secretly distillates from cat head.
The bottom temp of above-mentioned treating tower should be controlled at 110～135 ℃, preferred 112～125 ℃.Be higher than 135 ℃ as temperature, then have a large amount of sec-butyl acetates to steam cat head, output is reduced; Be lower than 110 ℃ as temperature, partial impurities can not be separated from product, has reduced the quality of product.Product purification top of tower temperature should be not less than 85 ℃, preferably is not less than 88 ℃.Rectifying by treating tower obtains highly purified sec-butyl acetate.
In the azeotropic distillation process, comprise acetate, a small amount of entrainer and/or sec-butyl acetate from azeotropy rectification column bottom extraction cut, the cut of bottom extraction can directly loop back reactive system and utilize, also can directly efflux recovery.
Compared with prior art, the invention has the advantages that: (1) adopts catalytic distillation technology to carry out acetate and mixed C
4The esterification of (or butylene) is not established and is used to remove the unreacted mixed C
4And the flashing tower of light constituent (or butylene), thereby product separating technique simplified, and production cost is reduced, and energy consumption reduces; (2) can be effectively with sec-butyl acetate from acetate and mixed C
4Separate in the post reaction mixture, the purity of the sec-butyl acetate that obtains is more than 98%, and quality of acetic acid content is less than 0.01%, and quality content is less than 0.05%; (3) the acetate reusable edible has improved utilization ratio of raw materials.
Description of drawings
Fig. 1 is the process flow sheet of each embodiment.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
In each of the embodiments described below, the reaction raw materials purity of preparation sec-butyl acetate is: acetate purity 〉=99.5%, butylene purity 〉=99.4%; Mixed C
4The quality percentage composition be: 1-butylene 4.72%, 2-butylene 49.22%, butane 46.01%, iso-butylene 0.05%.
Among the embodiment, acetate transformation efficiency, sec-butyl acetate selectivity calculate respectively according to the following equation:
Annotate: the percentage composition of each material all refers to the percentage composition in reaction product in the above-mentioned formula
Embodiment 1:
Adopt strong-acid ion exchange resin to make catalyzer, commercially available ZH-100 type.With total amount is the catalyzer of the 250Kg catalytic distillation tower conversion zone of packing into, and therefore obtains catalyst layer.
As shown in Figure 1, acetate 1, mixed C
42 enter in the tower from upper rectifying section A1, the bottom stripping section A3 of catalytic distillation tower A respectively, and both are in the catalyst surface counter current contact of conversion zone A2, acetate 1 and mixed C
42 reactions generate sec-butyl acetate, unreacted mixed C
43 steam from cat head, and product mixtures 4 goes out from tower bottom flow.
The operational condition of catalytic distillation tower A is: tower top pressure 0.65MPa, and 50 ℃ of tower top temperatures, 100 ℃ of conversion zone A2 middle part temperature, 180 ℃ of tower still temperature, reflux ratio are 5, acetate 1 and mixed C
4The mol ratio of butylene in 2 (sour alkene ratio) is 1.3, and acetate 1 charging air speed is 1.1hr
-1
Every 4hr sampling analysis reaction product is formed, and analyzes and adopts vapor-phase chromatography, records the acetate transformation efficiency more than 65%, and the sec-butyl acetate selectivity reaches more than 99%, mixed C in the catalytic distillation tower bottoms material
4Content is less than 0.1%.Move 1 month, catalyst activity is stable, and considerable change does not appear in acetate transformation efficiency and sec-butyl acetate selectivity.
The quality group that above-mentioned reaction is obtained becomes the product mixtures 4 of sec-butyl acetate 63.94%, acetate 32.24%, hydro carbons and other material 3.82% and sends into azeotropy rectification column B, and simultaneously in sec-butyl acetate: the ratio of water=4: 1 (mass ratio) adds entrainer water 5 in azeotropy rectification column B.
Azeotropy rectification column B bottom temp is 125 ℃, and tower top temperature is 87.5 ℃, the overhead product 6 that obtains, and its quality group becomes: sec-butyl acetate 94.16%, acetate 0.01%, water 1.0%, hydro carbons and other material 4.83%.Azeotropy rectification column overhead product 6 removes product purification tower C.121 ℃ of product purification column bottom temperature, 107 ℃ of head temperature obtain the overhead product 9 for the treatment of tower bottom after product is refining, and its quality group becomes: sec-butyl acetate 99.103%, acetate 0.007%, water 0.04%, hydro carbons and other material 0.85%.The secondary butyl ester 8 of impurity and small amount of acetic acid is discharged through treating tower C cat head.
Azeotropy rectification column bottom extraction cut 7, it consists of: sec-butyl acetate 6.39%, acetate 89.68%, water 0.69%, hydro carbons and other material 3.24%.Bottom extraction cut 7 directly loops back reactive system.
Embodiment 2:
As shown in Figure 1, adopt strong-acid ion exchange resin to make catalyzer, commercially available ZH-100 type.With total amount is the catalyzer of the 250Kg catalytic distillation tower conversion zone of packing into, and therefore obtains catalyst layer.
Acetate 1, mixed C
42 enter in the tower from upper rectifying section A1, the bottom stripping section A3 of catalytic distillation tower respectively, and both are in the catalyst surface counter current contact of conversion zone A2, acetate 1 and mixed C
42 reactions generate sec-butyl acetate, unreacted mixed C
43 steam from cat head, and product mixtures 4 goes out from tower bottom flow.
The operational condition of catalytic distillation tower A is: tower top pressure 0.5MPa, and 55 ℃ of tower top temperatures, 60 ℃ of conversion zone A2 middle part temperature, 160 ℃ of tower still temperature, reflux ratio are 0.5, acetate 1 and mixed C
4The mol ratio of butylene in 2 (sour alkene ratio) is 3.0, and acetate 1 charging air speed is 0.2hr
-1
Every 4hr sampling analysis reaction product is formed, and analyzes and adopts vapor-phase chromatography, records the acetate transformation efficiency more than 65%, and the sec-butyl acetate selectivity reaches more than 99.5%, mixed C in the catalytic distillation tower bottoms material
4Content is less than 0.05%.
The quality group that above-mentioned reaction is obtained becomes the product mixtures 4 of sec-butyl acetate 63.15%, acetate 33.19%, hydro carbons and other material 3.66% and sends into azeotropy rectification column B, and simultaneously in sec-butyl acetate: the ratio of water=4: 1 (mass ratio) adds entrainer water 5 in azeotropy rectification column B.
The azeotropic distillation column bottom temperature is 115 ℃, and tower top temperature is 78.1 ℃, the overhead product 6 that obtains, its quality group becomes: sec-butyl acetate 96.23%,, acetate 0.05%, water 1.0%, hydro carbons and other material 2.72%.Azeotropy rectification column overhead product 6 removes product purification tower C.112 ℃ of product purification column bottom temperature, 88 ℃ of head temperature obtain treating tower bottom overhead product 9 after product is refining, and its quality group becomes: sec-butyl acetate 98.805%, acetate 0.005%, water 0.04%, hydro carbons and other material 1.15%.The secondary butyl ester 8 of impurity and small amount of acetic acid is discharged through the treating tower cat head.
Azeotropy rectification column bottom extraction cut 7, its quality group becomes: sec-butyl acetate 7.49%, acetate 85.24%, water 0.55%, hydro carbons and other material 6.72%.Bottom extraction cut 7 directly loops back reactive system.
Embodiment 3:
As shown in Figure 1, adopt strong-acid ion exchange resin to make catalyzer, commercially available ZH-100 type.With total amount is the catalyzer of the 250Kg catalytic distillation tower conversion zone of packing into, and therefore obtains catalyst layer.
Acetate 1, mixed C
42 enter in the tower from upper rectifying section A1 and the bottom stripping section A3 of catalytic distillation tower A respectively, and both are in the catalyst surface counter current contact of conversion zone A2, acetate 1 and mixed C
42 reactions generate sec-butyl acetate, unreacted mixed C
43 steam from cat head, and product mixtures 4 goes out from tower bottom flow.
The operational condition of catalytic distillation tower A is: tower top pressure 0.35MPa, and 65 ℃ of tower top temperatures, 110 ℃ of conversion zone A2 middle part temperature, 185 ℃ of tower still temperature, reflux ratio are 10, acetate 1 and mixed C
4The mol ratio of butylene in 2 (sour alkene ratio) is 1.15, and acetate 1 charging air speed is 0.5hr
-1
Every 4hr sampling analysis reaction product is formed, and analyzes and adopts vapor-phase chromatography, records the acetate transformation efficiency more than 80%, and the sec-butyl acetate selectivity reaches more than 99.5%, does not detect mixed C in the catalytic distillation tower bottoms material
4
The quality group that above-mentioned reaction is obtained becomes the product mixtures 4 of sec-butyl acetate 80.33%, acetate 16.34%, hydro carbons and other material 3.33% and sends into azeotropy rectification column B, and simultaneously in sec-butyl acetate: the ratio of water=4: 1 (mass ratio) adds entrainer water 5 in azeotropy rectification column B.
The azeotropic distillation column bottom temperature is 122 ℃, and tower top temperature is 87 ℃, the overhead product 6 that obtains, and its quality group becomes: sec-butyl acetate 95.00%, acetate 0.06%, water 1.0%, hydro carbons and other material 2.94%.Azeotropy rectification column overhead product 6 removes product purification tower C.122 ℃ of product purification column bottom temperature, 105 ℃ of head temperature obtain the overhead product 9 for the treatment of tower bottom after product is refining, and its quality group becomes: sec-butyl acetate 99.105%, acetate 0.005%, water 0.04%, hydro carbons and other material 0.85%.The secondary butyl ester 8 of impurity and small amount of acetic acid is discharged through the treating tower cat head.
Azeotropy rectification column bottom extraction cut 7, its quality group becomes: sec-butyl acetate 10.66%, acetate 80.75%, water 0.54%, hydro carbons and other material 8.05%.Bottom extraction cut 7 directly loops back reactive system.
Embodiment 4:
As shown in Figure 1, adopt strong-acid ion exchange resin to make catalyzer, commercially available ZH-100 type.With total amount is the catalyzer of the 250Kg catalytic distillation tower conversion zone of packing into, and therefore obtains catalyst layer.
Acetate 1, mixed C
42 enter in the tower from upper rectifying section A1, the bottom stripping section A3 of catalytic distillation tower A respectively, and both are in the catalyst surface counter current contact of conversion zone A2, acetate 1 and mixed C
42 reactions generate sec-butyl acetate, unreacted mixed C
43 steam from cat head, and product mixtures 4 goes out from tower bottom flow.
The operational condition of catalytic distillation tower A is: tower top pressure 0.35MPa, and 65 ℃ of tower top temperatures, 110 ℃ of conversion zone A2 middle part temperature, 185 ℃ of tower still temperature, reflux ratio are 10, acetate 1 and mixed C
4The mol ratio of butylene in 2 (sour alkene ratio) is 1.15, and acetate 1 charging air speed is 0.5hr
-1
Every 4hr sampling analysis reaction product is formed, and analyzes and adopts vapor-phase chromatography, records the acetate transformation efficiency more than 80%, and the sec-butyl acetate selectivity reaches more than 99.5%, does not detect mixed C in the catalytic distillation tower bottoms material
4
The quality group that above-mentioned reaction is obtained becomes the product mixtures 4 of sec-butyl acetate 80.33%, acetate 16.34%, hydro carbons and other material 3.33% and sends into azeotropy rectification column B, and simultaneously in sec-butyl acetate: the ratio of water=4: 1 (mass ratio) adds entrainer water 5 in azeotropy rectification column B.
The azeotropic distillation column bottom temperature is 122 ℃, and tower top temperature is 87 ℃, the overhead product 6 that obtains, and its quality group becomes: sec-butyl acetate 95.00%, acetate 0.06%, water 1.0%, hydro carbons and other material 2.54%.Azeotropy rectification column overhead product 6 removes product purification tower C.116 ℃ of product purification column bottom temperature, 95 ℃ of head temperature obtain the overhead product 9 for the treatment of tower bottom after product is refining, and its quality group becomes: sec-butyl acetate 99.105%, acetate 0.005%, water 0.04%, hydro carbons and other material 0.85%.The secondary butyl ester 8 of impurity and small amount of acetic acid is discharged through the treating tower cat head.
Azeotropy rectification column bottom extraction cut 7, its quality group becomes: sec-butyl acetate 10.66%, acetate 80.75%, water 0.54%, hydro carbons and other material 8.05%.Bottom extraction cut 7 directly loops back reactive system.
Embodiment 5:
As shown in Figure 1, select for use heteropolyacid as catalyzer.With total amount is the catalyzer of the 10L catalytic distillation tower conversion zone of packing into, and therefore obtains catalyst layer.
Acetate 1, butylene 2 enter in the tower from upper rectifying section A1, the bottom stripping section A3 of catalytic distillation tower A respectively, both are in the catalyst surface counter current contact of conversion zone A2,2 reactions of acetate 1 and butylene generate sec-butyl acetates, and unreacted butylene 3 steams from cat head, and product mixtures 4 goes out from tower bottom flow.
The operational condition of catalytic distillation tower A is: tower top pressure 0.5MPa, and 60 ℃ of tower top temperatures, 80 ℃ of conversion zone A2 middle part temperature, 175 ℃ of tower still temperature, reflux ratio are 5, and acetate 1 is 1.5 with the mol ratio (sour alkene ratio) of butylene 2, and acetate 1 charging air speed is 1.0hr
-1
Every 4hr sampling analysis reaction product is formed, and analyzes and adopts vapor-phase chromatography, records the acetate transformation efficiency more than 70%, and the sec-butyl acetate selectivity reaches more than 99.5%, and butene content is less than 0.1% in the catalytic distillation tower bottoms material.Move 500hr under test conditions, catalyst activity is stable, and considerable change does not appear in reaction conversion ratio and selectivity.
The product mixtures 4 that the quality group of above-mentioned reaction gained is become sec-butyl acetate 68.29%, acetate 28.16%, hydro carbons and other material 3.55% is sent into azeotropy rectification column B, and simultaneously in sec-butyl acetate: the ratio of water=4: 1 (mass ratio) adds entrainer water 5 in azeotropy rectification column B.
The azeotropic distillation column bottom temperature is 121 ℃, and tower top temperature is 86.5 ℃.The overhead product 6 that obtains, its quality group becomes: sec-butyl acetate 94.84%, acetate 0.07%, water 1.0%, hydro carbons and other material 4.09%.Azeotropy rectification column overhead product 6 removes product purification tower C.125 ℃ of product purification tower C bottom temps, 107 ℃ of head temperature obtain treating tower bottom overhead product 9 after product is refining, and its quality group becomes: sec-butyl acetate 98.154%, acetate 0.006%, water 0.04%, hydro carbons and other material 1.80%.The secondary butyl ester 8 of impurity and small amount of acetic acid is discharged through the treating tower cat head.
Azeotropy rectification column bottom extraction cut 7, its quality group becomes: sec-butyl acetate 5.48%, acetate 90.61%, water 0.73%, hydro carbons and other material 3.18%.Bottom extraction cut 7 directly loops back reactive system.
The preparation method of heteropolyacid catalyst is in the present embodiment:
With SiO
2Content is that the water glass of 250g/l and the dilute sulphuric acid of 10% concentration are mixed into glue, and is aging after 4 hours, filtration washing, and drying, roasting 4 hours under 600 ℃ of conditions then obtains SiO
2Sample.With the SiO that makes
2Sample 50g and 60g mass concentration are that the potassium salt soln of 5% phospho-wolframic acid mixes, dynamically flood 4 hours after, under 120 ℃ of conditions, dry 2h, roasting 5 hours under 550 ℃ of conditions then obtains heteropolyacid catalyst.
Claims (8)
1. method for preparing sec-butyl acetate with product separating technique, it is characterized in that: be reflected in the catalytic distillation tower of forming by a tower still, stripping section, conversion zone, rectifying section and trim the top of column condenser and carry out, a kind of catalyzer of filling in the conversion zone, acetate enters in the tower mixed C from the upper rectifying section of catalytic distillation tower
4Or butylene enters in the tower from the bottom stripping section of catalytic distillation tower, and both are in the catalyst surface counter current contact and react unreacted mixed C
4Or butylene steams from the catalytic distillation column overhead, and reacted product mixtures goes out and sends into azeotropy rectification column from the catalytic distillation tower tower bottom flow; In azeotropy rectification column, add entrainer, azeotropy rectification column overhead product natural layering, entrainer or entrainer and part sec-butyl acetate pass back into the azeotropic distillation column overhead; The sec-butyl acetate that carries a small amount of entrainer enters treating tower, obtains sec-butyl acetate in treating tower after the rectifying;
Described catalyzer is heteropolyacid or ion exchange resin; Described entrainer is a water.
2. according to the described method of claim 1, the operational condition that it is characterized in that described catalytic distillation tower is: tower top pressure is controlled at 0.30～1.20MPa, tower top temperature is controlled at 40～90 ℃, conversion zone middle part temperature is controlled at 50～150 ℃, tower still temperature is controlled at 140～220 ℃, reflux ratio is 0.1～10, and acetate and butylene mol ratio are 0.7: 1～3.0: 1, and the acetic acid feed air speed is 0.1～10.0hr
-1
3. according to the described method of claim 2, the operational condition that it is characterized in that described catalytic distillation tower is: tower top pressure is controlled at 0.35～0.75MPa, tower top temperature is controlled at 50～70 ℃, and conversion zone middle part temperature is controlled at 60～120 ℃, and tower still temperature is controlled at 160～190 ℃.
4. according to each described method in the claim 1～3, it is characterized in that described azeotropic distillation column bottom temperature is controlled at 100～130 ℃, the azeotropy rectification column tower top temperature is controlled at 75～100 ℃; Described treating tower bottom temp is controlled at 110～135 ℃, and the treating tower head temperature is not less than 85 ℃.
5. according to the described method of claim 4, it is characterized in that described azeotropic distillation column bottom temperature is controlled at 105～125 ℃, the azeotropy rectification column tower top temperature is controlled at 78～90 ℃; Described treating tower bottom temp is controlled at 112～125 ℃, and the treating tower head temperature is not less than 88 ℃.
6. according to each described method in the claim 1～3, it is characterized in that described azeotropic distillation column bottom temperature is controlled at 105～125 ℃, the azeotropy rectification column tower top temperature is controlled at 78～90 ℃; Described treating tower bottom temp is controlled at 112～125 ℃, and the treating tower head temperature is not less than 88 ℃.
7. according to the described method of claim 5, it is characterized in that described azeotropy rectification column bottom extraction cut, directly loop back reactive system and utilize again.
8. according to each described method in the claim 1～3, it is characterized in that described azeotropy rectification column bottom extraction cut, directly loop back reactive system and utilize again.
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| CN102452934B (en) * | 2010-10-22 | 2014-08-06 | 中国石油化工股份有限公司 | Preparation method of sec-butyl acetate |
| CN104649902B (en) * | 2013-11-19 | 2016-05-11 | 中国石油天然气股份有限公司 | A kind of production method of sec-butyl acetate |
| CN104311390A (en) * | 2014-10-17 | 2015-01-28 | 深圳市飞扬实业有限公司 | Method for synthesizing sec-butyl alcohol |
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