CN102584575A - Method for refining sec-butyl acetate coarse products through dual-reflux and preparation method of sec-butyl acetate - Google Patents
Method for refining sec-butyl acetate coarse products through dual-reflux and preparation method of sec-butyl acetate Download PDFInfo
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- CN102584575A CN102584575A CN2011100234852A CN201110023485A CN102584575A CN 102584575 A CN102584575 A CN 102584575A CN 2011100234852 A CN2011100234852 A CN 2011100234852A CN 201110023485 A CN201110023485 A CN 201110023485A CN 102584575 A CN102584575 A CN 102584575A
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Abstract
The invention provides a method for refining sec-butyl acetate coarse products through dual-reflux and a preparation method of sec-butyl acetate comprising the refining process. The refining method of the sec-butyl acetate coarse products comprises (1) enabling the sec-butyl acetate coarse products to feed in a rectifying tower through a first feed port, enabling the water to feed in the rectifying tower through a second feed port in a water vapor mode, conducting azeotropy rectification under operation conditions of the azeotropy rectification, and obtaining mixture mainly containing water and impurities from a tower top; and (2) cooling the mixture, conducting oil-water separation to obtain the water phase and the oil phase, enabling reflux maters at least containing partial oil phase to flow back the rectifying tower, enabling at least partial water phase to form the water vapor and returning the water vapor to return and add in the rectifying tower from a third feed port. The second feed port and the third feed port are same or different, and both located at the position of 1-10 tower boards or theoretical tower boards below the first feed port. The method can be used for preparing the sec-butyl acetate with high purity.
Description
Technical field
The present invention relates to a kind of method through the thick product of the secondary butyl ester of dual reflux purified acetic acid, and a kind of preparation method of sec-butyl acetate.
Background technology
Sec-butyl acetate is also referred to as acetate butyl ester, acetate second butyl ester in addition; Be one of four kinds of isomer of butylacetate; For liquid colourless, inflammable, that have the fruit flavor, in most of the cases all similar with the performance of other isomer, solubilized various kinds of resin and organism.Positive butyl ester and isobutylate that its boiling point is commonly used are low, and velocity of evaporation is very fast.Solvent, reaction medium, extraction agent component, metal cleaner, fruit flavors etc. can be widely used as, medicine industry can also be used for.Particularly in recent years, because the environmental requirement increasingly stringent, the use that contains noxious solvents such as benzene, toluene, hydrochloric ether is restricted, and the consumption of environmentally friendly solvents such as ester class sharply increases, and acetate product has become the market hot-sale products.
Butylacetate series products on the market is mainly n-butyl acetate now, because n-butyl acetate mainly is to be obtained by acetate and propyl carbinol reaction, and the propyl carbinol price is higher, causes the production cost of n-butyl acetate higher.And the technology of preparation sec-butyl acetate newly developed adopts refinery sub product C
4Alkene is raw material, prepares sec-butyl acetate with acetic acidreaction, and this raw materials technology source is wide and cheap, and therefore, its production cost is more much lower than n-butyl acetate.
Acetate and C
4After olefine reaction prepares sec-butyl acetate, contain a large amount of by products in the reaction product.Except sec-butyl acetate, also contain unreacted acetate and C in the reaction product
4Alkene, and C
4The superimposed C that waits reaction to form behind the olefin cracking
5Above hydrocarbon especially when having unusual active iso-butylene in the reaction product, also comprises C in the reaction product
8Above olefin polymer.Because exist a spot of moisture in the reaction product, therefore, also contain a certain amount of sec-butyl alcohol and butyl ether in the reaction product.In reaction product, because C
4Alkene and other component boiling point differ greatly, be easy to it separated through the method for conventional distillation, and acetate (boiling point is 118 ℃), sec-butyl acetate (boiling point is 113 ℃), C
8The boiling point of alkene (boiling point is 101-120 ℃) and sec-butyl alcohol (boiling point is 99.5 ℃) is very approaching, adopts conventional rectificating method to be difficult to realize the separation of these components.
Disclose a kind of method of from the reaction product of preparation sec-butyl acetate, isolating acetate and sec-butyl acetate among the CN101481307A, said reaction product contains sec-butyl acetate, acetate and C
8Alkene, this method comprises: under the operational condition of azeotropic distillation, water and said reaction product are got into carry out azeotropic distillation in first azeotrope column, take overhead azeotrope, at the bottom of tower, obtain acetate; The consumption of said water is at least and makes sec-butyl acetate and C
8Alkene is taken overhead with the form of azeotrope; The gained azeotrope is carried out oily water separation after condensation, obtain water-phase product and contain C
8The oil-phase product of alkene and sec-butyl acetate; Under the operational condition of azeotropic distillation, water and the above-mentioned oil-phase product that obtains are got into carry out azeotropic distillation in second azeotrope column, obtain azeotrope from cat head, at the bottom of tower, obtain sec-butyl acetate, the consumption of said water is at least and makes C
8Alkene is taken overhead with the form of azeotrope.
Disclose a kind of preparation method of sec-butyl acetate among the CN101486640A, this method comprises:
(1) in the presence of catalyzer and under the addition reaction condition, with C
4Alkene contacts, reacts with acetate several times;
(2) under the rectifying condition, step (1) gained reaction product is carried out rectifying separation in first azeotropy rectification column, from cat head extraction C
4Light constituent, extraction bottom product at the bottom of the tower, this bottom product contains sec-butyl acetate, C
8Alkene and unreacted acetate;
(3) under the azeotropic distillation condition, contain sec-butyl acetate, C with what step (2) obtained
8The bottom product of alkene and unreacted acetate and water get into and carry out azeotropic distillation in first azeotropy rectification column, and the consumption of water can make sec-butyl acetate and C
8Alkene with the form of azeotrope from the cat head extraction, acetate extraction at the bottom of the tower;
(4) azeotrope that step (3) is obtained carries out oily water separation after condensation, obtain water-phase product and contain C
8The oil-phase product of alkene and sec-butyl acetate;
(5) under the azeotropic distillation condition, oil-phase product that step (4) is obtained and water get into and carry out azeotropic distillation in second azeotropy rectification column, and the consumption of water can make C
8Alkene with the form of azeotrope from the cat head extraction, sec-butyl acetate extraction at the bottom of the tower.
The mode of all having mentioned the employing azeotropic distillation in the above patented claim is to sec-butyl acetate and C
8Alkene separates, and the entrainer of mentioning adding is water, though above separate mode has been realized sec-butyl acetate and C
8The separation of alkene.Yet in above-mentioned patented claim, entrainer (being water) is and contains C
8Alkene is added in the azeotropy rectification column with the oil-phase product of sec-butyl acetate, and it is insufficient that entrainer water and feed material are carried out exchange of substance like this, thereby makes sec-butyl acetate purity can not get guaranteeing.In addition, in above patented claim, water adds with liquid form, owing to undergo phase transition, needs the tower still that big calorimetric is provided, and misoperation is prone to take place to fall into water, and causes that water-content exceeds standard in the sec-butyl acetate product.
Summary of the invention
The objective of the invention is to overcome the above-mentioned defective that exists among the preparation method of existing sec-butyl acetate; Provide a kind of and can guarantee that the water-content in the sec-butyl acetate product is lower, and the method for the thick product of the secondary butyl ester of purified acetic acid of raising sec-butyl acetate product gas purity and the preparation method of sec-butyl acetate.
The invention provides a kind of method through the thick product of the secondary butyl ester of dual reflux purified acetic acid, the impurity in the thick product of this sec-butyl acetate contains C
5Above hydrocarbon, and optionally contain sec-butyl alcohol and butyl ether, this method may further comprise the steps:
(1) the thick product of said sec-butyl acetate is added in the rectifying tower through first opening for feed; The form of water with water vapor is added in the said rectifying tower through second opening for feed; Under the operational condition of azeotropic distillation, carry out azeotropic distillation; Obtain the mixture of main moisture and said impurity from cat head, at the bottom of the tower and/or tower bottom side line mainly contained the product of sec-butyl acetate;
(2) the said mixture that cat head is obtained is cooled to liquid phase; And carry out oily water separation and obtain water and oil phase; To contain at least that the material of the said oil phase of part is back in the said rectifying tower, and make to be back in the said rectifying tower through the 3rd opening for feed after the said water of part forms water vapor at least;
Wherein, said second opening for feed and said the 3rd opening for feed are identical or different, and all are positioned at the below 1-10 piece column plate of said first opening for feed or the position at theoretical tray place.
The present invention also provides a kind of preparation method of sec-butyl acetate, and this method may further comprise the steps:
(1) in the presence of catalyzer and under the addition reaction condition, makes C
4Alkene and acetate contact reacts;
(2) isolate unreacted C in the reaction product that from step (1), obtains
4Alkene obtains containing sec-butyl acetate, C
5The above hydrocarbon and the mixture of unreacted acetate;
(3) through azeotropic distillation from said sec-butyl acetate, the C of containing
5Isolate acetate in the above hydrocarbon and the mixture of unreacted acetate, obtain the thick product of sec-butyl acetate;
(4) according to aforesaid method by the thick product purification sec-butyl acetate of said sec-butyl acetate.
Said method through the thick product of the secondary butyl ester of dual reflux purified acetic acid provided by the invention has adopted the dual reflux technology of rectifying tower; Concrete; Through being added in the rectifying tower in position as the water vapor of entrainer; And will from overhead product, reflux from cat head by the isolated oil phase of part at least, and will from overhead product, be back in position in the rectifying tower by the isolated water of part at least, make that the entrainer in the azeotropic distillation process can contact with material fully; Make material transfer more abundant, thereby improved the sec-butyl acetate product gas purity.In addition, because the present invention adopts the form of steam to add entry as entrainer,, be not easy more water is fallen at the bottom of the tower, thereby can not cause the water-content of sec-butyl acetate product to exceed standard with the liquid water ratio of direct interpolation.
Description of drawings
Fig. 1 representes the said flow direction of material synoptic diagram that passes through the method for the thick product of the secondary butyl ester of dual reflux purified acetic acid provided by the invention.
Embodiment
According to an aspect of the present invention, as shown in Figure 1, the invention provides a kind of method through the thick product of the secondary butyl ester of dual reflux purified acetic acid, the impurity in the thick product of this sec-butyl acetate contains C
5Above hydrocarbon, and optionally contain sec-butyl alcohol and butyl ether, this method may further comprise the steps:
(1) the thick product 1 of said sec-butyl acetate is added in the rectifying tower 8 through first opening for feed; The form of water with water vapor is added in the said rectifying tower 8 through second opening for feed; Under the operational condition of azeotropic distillation, carry out azeotropic distillation; Obtain the mixture 2 of main moisture and said impurity from cat head, at the bottom of the tower and/or tower bottom side line mainly contained the product 7 of sec-butyl acetate;
(2) the said mixture that cat head is obtained is cooled to liquid phase 3; And carry out oily water separation and obtain water and oil phase; To contain at least that the material 4 of the said oil phase of part is back in the said rectifying tower 8, and make to be back in the said rectifying tower 8 through the 3rd opening for feed after the said water 5 of part forms water vapors at least;
Wherein, said second opening for feed and said the 3rd opening for feed are identical or different, and all are positioned at the below 1-10 piece column plate of said first opening for feed or the position at theoretical tray place.
According to said method provided by the invention; Stage number or theoretical plate number total in the said rectifying tower do not have special qualification, and under the preferable case, stage number that said rectifying tower is total or theoretical plate number are 1 2-200; More preferably 20-200 further is preferably 30-200.
A preferred embodiment of the invention, in said rectifying tower, said second opening for feed is identical with said the 3rd opening for feed, and is positioned at the below 1-5 piece column plate of said first opening for feed or the position at theoretical tray place.In this preferred implementation, at the bottom of the tower of said rectifying tower and/or the sec-butyl acetate product that obtains of tower bottom side line have higher purity, water cut is still less.In the present invention, said tower bottom side line be meant be positioned on the rectifying tower sidewall and opening for feed (comprising first opening for feed, second opening for feed and the 3rd opening for feed) below, have the discharge port or the pipeline that are communicated with said rectifying tower.In order to obtain more highly purified sec-butyl acetate product, said sec-butyl acetate product preferably obtains from the tower bottom side line of said rectifying tower.
According to said method provided by the invention, from said first opening for feed to tower at the bottom of stage number or the theoretical plate number 10-90% that preferably accounts for stage number or theoretical plate number total the said rectifying tower, more preferably 20-90% further is preferably 30-90%.
According to said method provided by the invention, in step (1), the amount that adds the water in the said rectifying tower can be confirmed according to the concentration of the sec-butyl acetate in the thick product of said sec-butyl acetate.When the concentration of said sec-butyl acetate higher (content that also is impurity is less), the add-on of water can be less relatively; Otherwise when the concentration of said sec-butyl acetate less (content that also is impurity is higher), the add-on of water can be higher relatively.In the present invention, the water and the weight ratio of the thick product of sec-butyl acetate that add in the rectifying tower can be 1-100 usually: 100, be preferably 10-80: and 100,20-40 more preferably: 100.In the present invention, the water that adds in the rectifying tower can disposablely add, and also can add several times.Under the preferable case, add water disposable the joining in the said rectifying tower when beginning to carry out azeotropic distillation in the rectifying tower, in rectifying tower, form after the water cycle, can stop to add water vapor.
According to said method provided by the invention, the composition of the thick product of said sec-butyl acetate can be following: the content of sec-butyl acetate is 50-99 weight %, C
5The content of above hydrocarbon is 0.1-30 weight %, and the content of butyl ether is 0-5 weight %, and the content of sec-butyl alcohol is 0-15 weight %; Under the preferable case, in the thick product of said sec-butyl acetate, the content of sec-butyl acetate is 80-98 weight %, C
5The content of above hydrocarbon is 1-19 weight %, and the content of butyl ether is 0.1-2 weight %, and the content of sec-butyl alcohol is 0.1-2 weight %.
In the present invention, said C
5Above hydrocarbon comprises C
5, C
6, C
7, C
8, C
9, C
10, C
11, C
12And C
12With first-class multiple hydrocarbons, be main mainly with alkene, wherein mainly contain C
8Alkene, C
8The content of alkene in the thick product of sec-butyl acetate can be 0.1-29.9 weight %, is preferably 0.1-18.5 weight %, C
5The mass content of alkene in the thick product of sec-butyl acetate can be 0-1%, C
6The mass content of alkene in the thick product of sec-butyl acetate can be 0-0.5%, C
7The mass content of alkene in the thick product of sec-butyl acetate can be 0-1%, C
9The mass content of alkene in the thick product of sec-butyl acetate can be 0-0.5%, C
10The mass content of alkene in the thick product of sec-butyl acetate can be 0-0.5%, C
11The mass content of alkene in the thick product of sec-butyl acetate can be 0-0.5%, C
12The mass content of alkene in the thick product of sec-butyl acetate can be 0-0.5%, C
12The above mass content of alkene in the thick product of sec-butyl acetate can be 0-0.5%.
In the present invention, the source of the thick product of said sec-butyl acetate does not have special qualification, and the thick rule of origin of various sec-butyl acetates with above-mentioned composition all can be used among the present invention.Under the preferable case, the thick product source of said sec-butyl acetate is in the technology of the preparation sec-butyl acetate of various routines; More preferably be derived from by C
4Alkene and acetate carry out addition reaction and prepare in the technology of sec-butyl acetate; Further under the preferable case, the thick product of said sec-butyl acetate is through making C
4Alkene and acetate carry out addition reaction, and the product that then this addition reaction is obtained carries out azeotropic distillation with water and obtains, and in this case; The thick product of the sec-butyl acetate that is obtained can also contain a spot of water and acetate, and is concrete, and the water-content in the thick product of this sec-butyl acetate can (be generally dissolving water for 0.01-2 weight %; The about 0.62 weight % of content); The content of acetate can be for 0-2 weight %, and according to the industry controlling index, acetic acid content is preferably below 0.01 weight %.In addition, because C
4Alkene has certain dissolubility in sec-butyl acetate, therefore, can also contain a spot of C in the thick product of said sec-butyl acetate
4Alkene, and C
4The content of alkene in the thick product of said sec-butyl acetate can be 0-1 weight %.
In said method provided by the invention, because C
4The boiling point of alkene is lower, in the process of azeotropic distillation, and C
4Alkene can steam in rectifying tower to cat head, is enriched in the return tank of top of the tower, and follows the cat head production to distillate; For other hydrocarbons, like C
5-C
9Hydrocarbons all can form azeotrope and steam, and C from cat head with water
10Above hydrocarbons belongs to high boiling material, and boiling point is usually about more than 170 ℃, and these hydrocarbons then can fall at the bottom of the tower, discharge at the bottom of tower with the form of deslagging at the bottom of the tower.
According to said method provided by the invention; As long as the operational condition of said azeotropic distillation can make impurity and the water in the thick product of sec-butyl acetate form azeotrope, concrete implementation condition can be confirmed according to composition of the impurity in the thick product of sec-butyl acetate and content.Under preferable case, the operational condition of said azeotropic distillation comprises: the temperature of cat head is 85-150 ℃, and the temperature at the bottom of the tower is 110-190 ℃, and gauge pressure is 0-0.5MPa; Further under the preferable case, the operational condition of said azeotropic distillation comprises: the temperature of cat head is 85-120 ℃, and the temperature at the bottom of the tower is 110-150 ℃, and gauge pressure is 0-0.15MPa; Under the preferred situation, the operational condition of said azeotropic distillation comprises: the temperature of cat head is 85-100 ℃, and the temperature at the bottom of the tower is 110-130 ℃, and gauge pressure is 0-0.1MPa.In the present invention, said azeotropic distillation process can be operated with the mode of total reflux, and the azeotrope that is promptly produced by the cat head of rectifying tower can all be back to oil phase that obtains and water in this rectifying tower after overcooling and oily water separation.Usually, the reflux ratio in the said azeotropic distillation process can be preferably more than 1 for more than 0.5, more preferably more than 5.In the present invention; Said reflux ratio is meant that the reflux and the overhead product that are back in the said rectifying tower (promptly discharge the overhead product of rectifying tower; The total amount that is back to reflux and overhead product in the said rectifying tower equals to obtain from cat head the amount of the mixture of main moisture and said impurity) weight ratio; Said reflux comprises the oil phase that is back to rectifying tower, also comprises the water that is back to rectifying tower.Generally, the pressure of rectifying tower is high more, and temperature is also just corresponding high more; And the temperature of cat head and the temperature at the bottom of the tower form a thermograde of successively decreasing gradually from top to bottom, therefore, and when tower top temperature is high; Corresponding column bottom temperature is also higher relatively; Otherwise when tower top temperature was hanged down, corresponding column bottom temperature was also relatively low.
According to said method provided by the invention; In step (2); The method that the azeotrope that cat head is obtained is cooled to liquid phase can adopt conventional heat exchange method to realize, for example can be through making the lower heat-eliminating medium of said azeotrope and temperature (for example, water) carry out heat exchange and realizing.
According to said method provided by the invention, in step (2), the method for said oily water separation can adopt conventional oily water separation mode to realize, for example can realize through in water-and-oil separator, leaving standstill.
According to said method provided by the invention, the material 4 of the said oil phase of part will be back to the operation in the said rectifying tower for containing at least, can adopt two kinds of embodiments to realize among the present invention.In first kind of embodiment, said oil phase and part water are mixed together the back and reflux from cat head, and remaining water is back to the rectifying tower from rectifying tower the 3rd opening for feed after being heated into water vapor; In second kind of embodiment, after said oil phase and water carried out oily water separation, oil phase was separately from trim the top of column, and water is back to the rectifying tower from rectifying tower the 3rd opening for feed after being heated into water vapor.In above-mentioned two kinds of embodiments, can also part oil phase and/or water be discharged from water-and-oil separator as cat head production 6; When if water is not enough, can from rectifying tower the 3rd opening for feed, add fresh water vapor in addition.The said oil phase of said part at least can account for the 50-100% of said oil phase gross weight, preferably accounts for 60-100%, further preferably accounts for 80-100%.
According to said method provided by the invention; Making at least, the method for the said water 5 formation water vapors of part can comprise: the said water of part carries out heat exchange, carries out heat exchange with superheated vapour again with the water of condensation that the azeotropic device comes out at the bottom of tower at least; Can utilize the waste heat of said water of condensation like this, thereby save energy consumption.In the present invention, after forming water vapor, return the 10-100 weight % that the said water that joins in the said rectifying tower can account for the water that obtains after the said oily water separation, be preferably 60-100 weight %, more preferably 80-100 weight %.
According to another aspect of the present invention, the present invention also provides a kind of preparation method of sec-butyl acetate, and this method may further comprise the steps:
(1) in the presence of catalyzer and under the addition reaction condition, makes C
4Alkene and acetate contact reacts;
(2) isolate unreacted C in the reaction product that from step (1), obtains
4Alkene obtains containing sec-butyl acetate, C
5The above hydrocarbon and the mixture of unreacted acetate;
(3) through azeotropic distillation from said sec-butyl acetate, the C of containing
5Isolate acetate in the above hydrocarbon and the mixture of unreacted acetate, obtain the thick product of sec-butyl acetate;
(4) according to said method through the secondary butyl ester of dual reflux purified acetic acid provided by the invention by the thick product purification sec-butyl acetate of said sec-butyl acetate.
The preparation method of sec-butyl acetate according to the present invention, said addition reaction condition can comprise: temperature of reaction is 30-300 ℃, the charging air speed is 0.2-20h
-1, reaction pressure is 0.1-10MPa.Under the preferable case, said addition reaction condition comprises: temperature of reaction is 50-200 ℃, and the charging air speed is 0.5-10h
-1, reaction pressure is 0.6-2MPa.Under the preferred situation, said addition reaction condition comprises: temperature of reaction is 60-150 ℃, and the charging air speed is 0.8-5h
-1, reaction pressure is 0.6-2MPa.Said reaction pressure is a gauge pressure.
The preparation method of sec-butyl acetate according to the present invention, the mol ratio of the consumption of the consumption of said acetate and said C4 alkene can be 0.5-10: 1, be preferably 0.8-5: 1, further be preferably 1-5: 1,1-3 more preferably: 1.
The preparation method of sec-butyl acetate according to the present invention, the said C4 alkene that is used as the addition reaction raw material can be 1-butylene, suitable-2-butylene, anti--2-butylene or their mixture, also can be the mixed C that contains above-mentioned alkene
4Adopt mixed C
4During for raw material, C
4In also possibly contain normal butane and Trimethylmethane, they do not participate in the reaction.
The preparation method of sec-butyl acetate according to the present invention, said catalyzer can comprise carried heteropoly acid or salt, non-loading type heteropolyacid or salt, strongly acidic cationic exchange resin, molecular sieve, SO
4 2-/ ZrO
2Type solid super-strong acid, or their mixture.Strongly acidic cationic exchange resin as catalyzer mainly is to obtain polystyrene resin by vinylbenzene-Vinylstyrene in the low suspension copolymerization that exists of pore-creating agent, and then with the vitriol oil, oleum or SO
3Carry out that sulfonation obtains.This resinoid can obtain according to the method that well known to a person skilled in the art is synthetic; Also can buy from market easily, be resins such as D72, D005, D006, D008, S54, Amberlyst 15, Amberlyst 35, Dowex50, K2611, K2431, Puolite 175, Puolite 275 like the trade mark.Selectable molecular sieve has Y series, ZSM is serial, MCM is serial, the serial equimolecular sieve of β.Selectable heteropolyacid comprises the heteropolyacid of Keggin structure, Dawson structure, Anderson structure, Silverton structure.Usually the heteropolyacid that uses the Keggin structure is like 12 phospho-wolframic acid (H
3PW
12O
40), 12 silicotungstic acid (H
4SiW
12O
40), 12 phosphomolybdate (H
3PMo
12O
40), 12 molybdovanaphosphoric acids and their hydrate be as catalyzer.For heteropolyacid, because its specific surface area is less and be difficult to independent moulding, therefore preferably it is loaded on the suitable carriers usually, form carried heteropoly acid catalyst.Available carrier comprises metal oxide carriers such as silicon-dioxide, aluminum oxide, large pore molecular sieve, gac, in the ion exchange resin of special processing (like charing) one or more.
The preparation method of sec-butyl acetate according to the present invention is because C
4The boiling point of other component in the reaction product that alkene and step (1) obtain differs bigger, therefore, isolates C in the reaction product that from step (1), obtains
4Alkene can adopt conventional method easily to realize, for example can the reaction product that obtain in the step (1) be added in the flashing tower, through the removed overhead C of flash distillation from flashing tower
4And other light constituent.Adopting mixed C
4As C
4Olefin feedstock prepares under the situation of sec-butyl acetate, is separating unreacted C in the step (2)
4In the time of alkene, also can isolate mixed C
4In other component that has neither part nor lot in reaction, for example, C
4Alkane (like normal butane, Trimethylmethane).
The preparation method of sec-butyl acetate according to the present invention is from said sec-butyl acetate, the C of containing
5The azeotropic distillation of isolating acetate in the above hydrocarbon and the mixture of unreacted acetate can be through with said sec-butyl acetate, the C of containing
5The above hydrocarbon and the mixture of unreacted acetate and water as entrainer are added to and carry out azeotropic distillation in the rectifying tower and realize; And the column bottom temperature of this rectifying tower can be 100-130 ℃; Be preferably 105-125 ℃, the tower top temperature of this rectifying tower can be 75-100 ℃, is preferably 78-90 ℃; Thereby can be at the bottom of the tower of this rectifying tower the unreacted acetate of extraction, obtain the thick product of sec-butyl acetate at the cat head of this rectifying tower.
Below through embodiment the present invention is described further.
Present embodiment is used to explain provided by the invention said through the method for the thick product of the secondary butyl ester of dual reflux purified acetic acid and the preparation method of sec-butyl acetate.
(1) preparation of the thick product of sec-butyl acetate
Strongly acidic ion-exchange resin catalyst (sulfonated phenylethylene-Vinylstyrene type resin, specific surface area 30m with 100 grams
2/ g, average particulate diameter are 1.0mm, pore volume 0.25mL/g) be loaded into fixed-bed reactor and (among the φ 32 * 4 * 1000mm), the speed of acetate with 1000 Grams Per Hours fed in the fixed-bed reactor, with C continuously
4Alkene mixture (quality group becomes: normal butane 36.2%, anti-butylene 39.5%, n-butene 4.2%, maleic 20.1%) adds in the fixed-bed reactor with the speed of 800 Grams Per Hours continuously.In reactor jacket, feeding temperature is 80 ℃ of recirculated water control reaction temperature, and the gauge pressure through the back pressure valve system is 1.5MPa.Then, in the product input flashing tower with the fixed-bed reactor outlet, the temperature at the bottom of the flash distillation Tata is controlled to be 188.5 ℃; The temperature of cat head is controlled to be 56 ℃, and the gauge pressure in the flashing tower is controlled to be 0.65MPa, and the product that obtains at the bottom of the tower of flashing tower is transported in first rectifying tower (stage number is 50); Add entrainer water, and the column bottom temperature of first rectifying tower is controlled to be 125 ℃, tower top temperature is controlled to be 87.5 ℃; Obtain the thick product of sec-butyl acetate from cat head; Adopt the 2ml microburette to carry out acid base titration and measure the acetic acid content in the sec-butyl acetate product, adopt micro-water analyzer to measure the water-content in the sec-butyl acetate product, adopt Agilent 6890 gas chromatograph analyses to learn other composition of the thick product of this sec-butyl acetate; The result as: sec-butyl acetate is 94.168 weight %; Acetate is 0.002 weight %, and water is 0.49 weight %, C
5Above hydrocarbon is 4.9 weight %, and sec-butyl alcohol is 0.26 weight %, and butyl ether is 0.18 weight %.
(2) the thick product of sec-butyl acetate is refining
Adopt technology shown in Figure 1 that the thick product of above-mentioned sec-butyl acetate is made with extra care.Concrete, thick product of sec-butyl acetate of preparation in above-mentioned (1) is added to second rectifying tower from first opening for feed, the stage number in this second rectifying tower is 50, and first opening for feed from the bottom of the tower to the position of the 25th block of column plate of cat head; Simultaneously water vapor is added to second rectifying tower from second opening for feed, the position at the 2nd piece column plate place of second opening for feed below said first opening for feed, and the weight ratio of water vapor and the thick product of sec-butyl acetate is 1: 5; The tower top temperature of second rectifying tower is controlled to be 95 ℃, column bottom temperature is controlled to be 125 ℃, the intravital gauge pressure of tower is controlled to be 0.035MPa, carry out total reflux, line obtains mainly to contain the product of sec-butyl acetate from the tower bottom side, obtains mainly moisture, C from cat head
5The mixture of above hydrocarbon, sec-butyl alcohol and butyl ether; This mixture is cooled to liquid phase, and carries out oily water separation, obtain oil phase and water, with said oil phase from trim the top of column to second rectifying tower, said water be heated into behind the water vapor to return from above-mentioned second opening for feed join second rectifying tower.
After above-mentioned azeotropic distillation process circulation was carried out 5 hours; Adopt the 2ml microburette to carry out acid base titration and measure the acetic acid content in the sec-butyl acetate product; Adopt micro-water analyzer to measure the water-content in the sec-butyl acetate product; Adopt Agilent 6890 gas chromatographs that other composition of the sec-butyl acetate product of tower bottom side line acquisition is analyzed, its result is as shown in table 1 below.
Comparative Examples 1
(1) preparation of the thick product of sec-butyl acetate
According to preparing the thick product of sec-butyl acetate with embodiment 1 identical method.
(2) the thick product of sec-butyl acetate is refining
Method according to embodiment 1 is made with extra care the thick product of sec-butyl acetate; Different is; The position at the 12nd piece column plate place of second opening for feed below said first opening for feed, the water vapor that also promptly is added in second rectifying tower is added in second rectifying tower with the position of the water that returns the formation water vapor that joins in second rectifying tower from the 12nd block of column plate of the below of said first opening for feed.
After above-mentioned azeotropic distillation process circulation was carried out 5 hours; Adopt the 2ml microburette to carry out acid base titration and measure the acetic acid content in the sec-butyl acetate product; Adopt micro-water analyzer to measure the water-content in the sec-butyl acetate product; Adopt Agilent 6890 gas chromatographs that other composition of the sec-butyl acetate product of tower bottom side line acquisition is analyzed, its result is as shown in table 1 below.
Comparative Examples 2
(1) preparation of the thick product of sec-butyl acetate
According to preparing the thick product of sec-butyl acetate with embodiment 1 identical method.
(2) the thick product of sec-butyl acetate is refining
Method according to embodiment 1 is made with extra care the thick product of sec-butyl acetate; Different is; First opening for feed is identical with the position of second opening for feed; All from the bottom of the tower to the position of the 25th block of column plate of cat head, the water vapor that also promptly is added in second rectifying tower is added to second rectifying tower from identical opening for feed with the water that returns the formation water vapor that joins in second rectifying tower.
After above-mentioned azeotropic distillation process circulation was carried out 5 hours; Adopt the 2ml microburette to carry out acid base titration and measure the acetic acid content in the sec-butyl acetate product; Adopt micro-water analyzer to measure the water-content in the sec-butyl acetate product; Adopt Agilent 6890 gas chromatographs that other composition of the sec-butyl acetate product of tower bottom side line acquisition is analyzed, its result is as shown in table 1 below.
Comparative Examples 3
(1) preparation of the thick product of sec-butyl acetate
According to preparing the thick product of sec-butyl acetate with embodiment 1 identical method.
(2) the thick product of sec-butyl acetate is refining
Method according to embodiment 1 is made with extra care the thick product of sec-butyl acetate; Different is; The position at the 1st piece column plate place of second opening for feed above said first opening for feed, the water vapor that also promptly is added in second rectifying tower is added in second rectifying tower with the position of the water that returns the formation water vapor that joins in second rectifying tower from the 1st block of column plate of the top of said first opening for feed.
After above-mentioned azeotropic distillation process circulation was carried out 5 hours; Adopt the 2ml microburette to carry out acid base titration and measure the acetic acid content in the sec-butyl acetate product; Adopt micro-water analyzer to measure the water-content in the sec-butyl acetate product; Adopt Agilent 6890 gas chromatographs that other composition of the sec-butyl acetate product of tower bottom side line acquisition is analyzed, its result is as shown in table 1 below.
Embodiment 2
Present embodiment is used to explain provided by the invention said through the method for the thick product of the secondary butyl ester of dual reflux purified acetic acid and the preparation method of sec-butyl acetate.
(1) preparation of the thick product of sec-butyl acetate
Strongly acidic ion-exchange resin catalyst (sulfonated phenylethylene-Vinylstyrene type resin, specific surface area 30m with 100 grams
2/ g, average particulate diameter are 1.0mm, pore volume 0.25mL/g) be loaded into fixed-bed reactor and (among the φ 32 * 4 * 1000mm), the speed of acetate with 900 Grams Per Hours fed in the fixed-bed reactor, with C continuously
4Alkene mixture (quality group becomes: Trimethylmethane 39.0%, normal butane 9.7%, anti-butylene 20.1%, n-butene 17.5%, maleic 13.7%) adds in the fixed-bed reactor with the speed of 800 Grams Per Hours continuously.In reactor jacket, feeding temperature is 80 ℃ of recirculated water control reaction temperature, and the gauge pressure through the back pressure valve system is 1.5MPa.Then, in the product input flashing tower with the fixed-bed reactor outlet, the temperature at the bottom of the flash distillation Tata is controlled to be 165 ℃; The temperature of cat head is controlled to be 48 ℃, and the gauge pressure in the flashing tower is controlled to be 0.38MPa, and the product that obtains at the bottom of the tower of flashing tower is transported to first rectifying tower (stage number is 50); Add entrainer water, and the column bottom temperature of first rectifying tower is controlled to be 115 ℃, tower top temperature is controlled to be 85 ℃; Obtain the thick product of sec-butyl acetate from cat head; Adopt the 2ml microburette to carry out acid base titration and measure the acetic acid content in the sec-butyl acetate product, adopt micro-water analyzer to measure the water-content in the sec-butyl acetate product, adopt Agilent 6890 gas chromatograph analyses to learn other composition of the thick product of this sec-butyl acetate; The result as: sec-butyl acetate is 83.234 weight %; Acetate is 0.006 weight %, and water is 1.8 weight %, C
5Above hydrocarbon is 13.91 weight %, and sec-butyl alcohol is 0.6 weight %, and butyl ether is 0.45 weight %.
(2) the thick product of sec-butyl acetate is refining
Adopt technology shown in Figure 1 that the thick product of above-mentioned sec-butyl acetate is made with extra care.Concrete, thick product of sec-butyl acetate of preparation in above-mentioned (1) is added to second rectifying tower from first opening for feed, the stage number in this second rectifying tower is 90, and first opening for feed from the bottom of the tower to the position of the 40th block of column plate of cat head; Simultaneously water vapor is added to second rectifying tower from second opening for feed, the position at the 8th piece column plate place of second opening for feed below said first opening for feed, and the weight ratio of water vapor and the thick product of sec-butyl acetate is 2: 5; The tower top temperature of second rectifying tower is controlled to be 98 ℃, column bottom temperature is controlled to be 127 ℃, the intravital gauge pressure of tower is controlled to be 0.05MPa, control of reflux ratio is 19: 1, and line obtains mainly to contain the product of sec-butyl acetate from the tower bottom side, obtains mainly moisture, C from cat head
5The mixture of above hydrocarbon, sec-butyl alcohol and butyl ether; This mixture is cooled to liquid phase; And carry out oily water separation; Obtain oil phase and water; With the said oil phase of 90 weight % and the said water of 10 weight % from trim the top of column to second rectifying tower, remaining water be heated into behind the water vapor to return from above-mentioned second opening for feed join second rectifying tower.
After above-mentioned azeotropic distillation process circulation was carried out 5 hours; Adopt the 2ml microburette to carry out acid base titration and measure the acetic acid content in the sec-butyl acetate product; Adopt micro-water analyzer to measure the water-content in the sec-butyl acetate product; Adopt Agilent 6890 gas chromatographs that other composition of the sec-butyl acetate product of tower bottom side line acquisition is analyzed, its result is as shown in table 1 below.
Embodiment 3
Present embodiment is used to explain provided by the invention said through the method for the thick product of the secondary butyl ester of dual reflux purified acetic acid and the preparation method of sec-butyl acetate.
(1) preparation of the thick product of sec-butyl acetate
Strongly acidic ion-exchange resin catalyst (sulfonated phenylethylene-Vinylstyrene type resin, specific surface area 30m with 100 grams
2/ g, average particulate diameter are 1.0mm, pore volume 0.25mL/g) be loaded into fixed-bed reactor and (among the φ 32 * 4 * 1000mm), the speed of acetate with 900 Grams Per Hours fed in the fixed-bed reactor, with C continuously
4Alkene mixture (quality group becomes: Trimethylmethane 39.0%, normal butane 9.7%, anti-butylene 20.1%, n-butene 17.5%, maleic 13.7%) adds in the fixed-bed reactor with the speed of 1000 Grams Per Hours continuously.In reactor jacket, feeding temperature is 100 ℃ of recirculated water control reaction temperature, and the gauge pressure through the back pressure valve system is 2MPa.Then, in the product input flashing tower with the fixed-bed reactor outlet, the temperature at the bottom of the flash distillation Tata is controlled to be 180 ℃; The temperature of cat head is controlled to be 52 ℃, and the gauge pressure in the flashing tower is controlled to be 0.56MPa, and the product that obtains at the bottom of the tower of flashing tower is transported in first rectifying tower (stage number is 50); Add entrainer water, and the column bottom temperature of first rectifying tower is controlled to be 121 ℃, tower top temperature is controlled to be 82.5 ℃; Through azeotropic distillation, obtain the thick product of sec-butyl acetate from cat head, adopt the 2ml microburette to carry out acid base titration and measure the acetic acid content in the sec-butyl acetate product; Adopt micro-water analyzer to measure the water-content in the sec-butyl acetate product; Adopt Agilent 6890 gas chromatograph analyses to learn other composition of the thick product of this sec-butyl acetate, the result as: sec-butyl acetate is 88.295 weight %, and acetate is 0.005 weight %; Water is 0.5 weight %, C
5Above hydrocarbon is 11.03 weight %, and sec-butyl alcohol is 0.06 weight %, and butyl ether is 0.11 weight %.
(2) the thick product of sec-butyl acetate is refining
Adopt technology shown in Figure 1 that the thick product of above-mentioned sec-butyl acetate is made with extra care.Concrete, thick product of sec-butyl acetate of preparation in above-mentioned (1) is added to second rectifying tower from first opening for feed, the stage number in this second rectifying tower is 40, and first opening for feed from the bottom of the tower to the position of the 25th block of column plate of cat head; Simultaneously water vapor is added to second rectifying tower from second opening for feed, the position at the 6th piece column plate place of second opening for feed below said first opening for feed, and the weight ratio of water vapor and the thick product of sec-butyl acetate is 3: 10; The tower top temperature of second rectifying tower is controlled to be 93 ℃; Column bottom temperature is controlled to be 120 ℃, the intravital gauge pressure of tower is controlled to be 0.025MPa, control of reflux ratio is 9: 1; Line obtains mainly to contain the product of sec-butyl acetate from the tower bottom side, obtains mainly moisture, C from cat head
5The mixture of above hydrocarbon, sec-butyl alcohol and butyl ether; This mixture is cooled to liquid phase, and carries out oily water separation, obtain oil phase and water, with said oil phase from trim the top of column to second rectifying tower, the said water of 80 weight % be heated into behind the water vapor to return from above-mentioned second opening for feed join the rectifying tower.
After above-mentioned azeotropic distillation process circulation was carried out 3 hours; Adopt the 2ml microburette to carry out acid base titration and measure the acetic acid content in the sec-butyl acetate product; Adopt micro-water analyzer to measure the water-content in the sec-butyl acetate product; Adopt Agilent 6890 gas chromatographs that other composition of the sec-butyl acetate product of tower bottom side line acquisition is analyzed, its result is as shown in table 1 below.
Embodiment 4
Present embodiment is used to explain provided by the invention said through the method for the thick product of the secondary butyl ester of dual reflux purified acetic acid and the preparation method of sec-butyl acetate.
(1) preparation of the thick product of sec-butyl acetate
The thick product of sec-butyl acetate as follows is formed in method preparation according to embodiment 1:
Sec-butyl acetate is 92.976 weight %, and acetate is 0.004 weight %, and water is 0.2 weight %, C
5Above hydrocarbon is 5.89 weight %, and sec-butyl alcohol is 0.39 weight %, and butyl ether is 0.54 weight %.
(2) the thick product of sec-butyl acetate is refining
Method according to embodiment 1 is made with extra care the thick product of sec-butyl acetate; Different is; The position at the 4th piece column plate place of said second opening for feed below said first opening for feed, and the water vapor and the weight ratio of the thick product of sec-butyl acetate that add in second rectifying tower are 2: 5.
After above-mentioned azeotropic distillation process circulation was carried out 3 hours; Adopt the 2ml microburette to carry out acid base titration and measure the acetic acid content in the sec-butyl acetate product; Adopt micro-water analyzer to measure the water-content in the sec-butyl acetate product; Adopt Agilent 6890 gas chromatographs that other composition of the sec-butyl acetate product of tower bottom side line acquisition is analyzed, its result is as shown in table 1 below.
Present embodiment is used to explain provided by the invention said through the method for the thick product of the secondary butyl ester of dual reflux purified acetic acid and the preparation method of sec-butyl acetate.
(1) preparation of the thick product of sec-butyl acetate
The thick product of sec-butyl acetate as follows is formed in method preparation according to embodiment 1:
Sec-butyl acetate is 97.598 weight %, and acetate is 0.002 weight %, and water is 0.4 weight %, C
5Above hydrocarbon is 1.69 weight %, and sec-butyl alcohol is 0.06 weight %, and butyl ether is 0.25 weight %.
(2) the thick product of sec-butyl acetate is refining
Method according to embodiment 1 is made with extra care the thick product of sec-butyl acetate; Different is; The position at the 1st piece column plate place of said second opening for feed below said first opening for feed, and the water vapor and the weight ratio of the thick product of sec-butyl acetate that add in second rectifying tower are 1: 10.
After above-mentioned azeotropic distillation process circulation was carried out 2 hours; Adopt the 2ml microburette to carry out acid base titration and measure the acetic acid content in the sec-butyl acetate product; Adopt micro-water analyzer to measure the water-content in the sec-butyl acetate product; Adopt Agilent 6890 gas chromatographs that other composition of the sec-butyl acetate product of tower bottom side line acquisition is analyzed, its result is as shown in table 1 below.
Embodiment 6
Present embodiment is used to explain provided by the invention said through the method for the thick product of the secondary butyl ester of dual reflux purified acetic acid and the preparation method of sec-butyl acetate.
(1) preparation of the thick product of sec-butyl acetate
The thick product of sec-butyl acetate as follows is formed in method preparation according to embodiment 1:
Sec-butyl acetate is 98.698 weight %, and acetate is 0.002 weight %, and water is 0.04 weight %, C
5Above hydrocarbon is 1.01 weight %, and sec-butyl alcohol is 0.05 weight %, and butyl ether is 0.2 weight %.
(2) the thick product of sec-butyl acetate is refining
Method according to embodiment 1 is made with extra care the thick product of sec-butyl acetate; Different is; The position at the 1st piece column plate place of said second opening for feed below said first opening for feed, and the water vapor and the weight ratio of the thick product of sec-butyl acetate that add in second rectifying tower are 1: 20.
After above-mentioned azeotropic distillation process circulation was carried out 2 hours; Adopt the 2ml microburette to carry out acid base titration and measure the acetic acid content in the sec-butyl acetate product; Adopt micro-water analyzer to measure the water-content in the sec-butyl acetate product; Adopt Agilent 6890 gas chromatographs that other composition of the sec-butyl acetate product of tower bottom side line acquisition is analyzed, its result is as shown in table 1 below.
Present embodiment is used to explain provided by the invention said through the method for the thick product of the secondary butyl ester of dual reflux purified acetic acid and the preparation method of sec-butyl acetate.
(1) preparation of the thick product of sec-butyl acetate
The thick product of sec-butyl acetate as follows is formed in method preparation according to embodiment 1:
Sec-butyl acetate is 59.924 weight %, and acetate is 0.006 weight %, and water is 1.2 weight %, C
5Above hydrocarbon is 25.73 weight %, and sec-butyl alcohol is 11.89 weight %, and butyl ether is 1.25 weight %.
(2) the thick product of sec-butyl acetate is refining
Method according to embodiment 1 is made with extra care the thick product of sec-butyl acetate; Different is; The position at the 10th piece column plate place of said second opening for feed below said first opening for feed, and the water vapor and the weight ratio of the thick product of sec-butyl acetate that add in second rectifying tower are 1: 1.
After above-mentioned azeotropic distillation process circulation was carried out 3 hours; Adopt the 2ml microburette to carry out acid base titration and measure the acetic acid content in the sec-butyl acetate product; Adopt micro-water analyzer to measure the water-content in the sec-butyl acetate product; Adopt Agilent 6890 gas chromatographs that other composition of the sec-butyl acetate product of tower bottom side line acquisition is analyzed, its result is as shown in table 1 below.
Table 1
Can find out from above-mentioned table 1, adopt method of the present invention can prepare highly purified sec-butyl acetate.And through embodiment 1 is compared and can find out with the data of documents 1, the sec-butyl acetate for preparing according to said method provided by the invention has higher purity, and water-content is obviously less; Through embodiment 1 is compared and can find out with the data of Comparative Examples 2 and 3, though the water-content in the sec-butyl acetate product of preparation is also very little in Comparative Examples 2 and 3, the sec-butyl acetate product of preparation has obvious higher purity among the embodiment 1.
Above embodiment only is used to describe preferred implementation of the present invention; But; The present invention is not limited to the detail in the above-mentioned embodiment; In technical conceive scope of the present invention, can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Need to prove that in addition each the concrete technical characterictic described in above-mentioned embodiment under reconcilable situation, can make up through any suitable manner.For fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between the various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be regarded as the disclosed content of the present invention equally.
Claims (13)
1. method through the thick product of the secondary butyl ester of dual reflux purified acetic acid, the impurity in the thick product of this sec-butyl acetate contains C
5Above hydrocarbon, and optionally contain sec-butyl alcohol and butyl ether, it is characterized in that this method may further comprise the steps:
(1) the thick product of said sec-butyl acetate is added in the rectifying tower through first opening for feed; The form of water with water vapor is added in the said rectifying tower through second opening for feed; Under the operational condition of azeotropic distillation, carry out azeotropic distillation; Obtain the mixture of main moisture and said impurity from cat head, at the bottom of the tower and/or tower bottom side line mainly contained the product of sec-butyl acetate;
(2) the said mixture that cat head is obtained is cooled to liquid phase; And carry out oily water separation and obtain water and oil phase; To contain at least that the material of the said oil phase of part is back in the said rectifying tower, and make to be back in the said rectifying tower through the 3rd opening for feed after the said water of part forms water vapor at least;
Wherein, said second opening for feed and said the 3rd opening for feed are identical or different, and all are positioned at the below 1-10 piece column plate of said first opening for feed or the position at theoretical tray place.
2. method according to claim 1, wherein, stage number that said rectifying tower is total or theoretical plate number are 12-200.
3. method according to claim 1 and 2, wherein, said second opening for feed is identical with said the 3rd opening for feed, and is positioned at the below 1-5 piece column plate of said first opening for feed or the position at theoretical tray place.
4. method according to claim 1 and 2, wherein, from said first opening for feed to tower at the bottom of stage number or the theoretical plate number 10-90% that accounts for stage number or theoretical plate number total the said rectifying tower.
5. method according to claim 1 and 2, wherein, from said first opening for feed to tower at the bottom of stage number or the theoretical plate number 30-90% that accounts for stage number or theoretical plate number total the said rectifying tower.
6. method according to claim 1, wherein, in step (1), the water in the adding rectifying tower and the weight ratio of the thick product of sec-butyl acetate are 1-100: 100.
7. method according to claim 1, wherein, in step (1), the water in the adding rectifying tower and the weight ratio of the thick product of sec-butyl acetate are 10-80: 100.
8. method according to claim 1, wherein, in the thick product of said sec-butyl acetate, the content of sec-butyl acetate is 50-99 weight %, C
5The content of above hydrocarbon is 0.1-30 weight %, and the content of butyl ether is 0-5 weight %, and the content of sec-butyl alcohol is 0-15 weight %.
9. method according to claim 1, wherein, in the thick product of said sec-butyl acetate, the content of sec-butyl acetate is 80-98 weight %, C
5The content of above hydrocarbon is 1-19 weight %, and the content of butyl ether is 0.1-2 weight %, and the content of sec-butyl alcohol is 0.1-2 weight %.
10. method according to claim 1, wherein, the operational condition of said azeotropic distillation comprises: the temperature of cat head is 85-150 ℃, and the temperature at the bottom of the tower is 110-190 ℃, and gauge pressure is 0-0.5MPa.
11. method according to claim 1, wherein, the operational condition of said azeotropic distillation comprises: the temperature of cat head is 85-120 ℃, and the temperature at the bottom of the tower is 110-150 ℃, and gauge pressure is 0-0.15MPa.
12. the preparation method of a sec-butyl acetate, this method may further comprise the steps:
(1) in the presence of catalyzer and under the addition reaction condition, makes C
4Alkene and acetate contact reacts;
(2) isolate unreacted C in the reaction product that from step (1), obtains
4Alkene obtains containing sec-butyl acetate, C
5The above hydrocarbon and the mixture of unreacted acetate;
(3) through azeotropic distillation from said sec-butyl acetate, the C of containing
5Isolate acetate in the above hydrocarbon and the mixture of unreacted acetate, obtain the thick product of sec-butyl acetate;
(4) according to any described method among the claim 1-11 by the thick product purification sec-butyl acetate of said sec-butyl acetate.
13. method according to claim 12, wherein, said addition reaction condition comprises: temperature of reaction is 30-300 ℃, and the charging air speed is 0.2-20h
-1, reaction pressure is 0.1-10MPa, acetate and C
4The mol ratio of alkene is 0.5-10: 1; Said catalyzer is carried heteropoly acid or salt, non-loading type heteropolyacid or salt, strongly acidic cationic exchange resin, molecular sieve, SO
4 2-/ ZrO
2Type solid super-strong acid, or their mixture; Said C
4Alkene is one or more in 1-butylene, suitable-2-butylene and the anti--2-butylene.
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| CN103980115A (en) * | 2014-06-03 | 2014-08-13 | 湖南瑞源石化股份有限公司 | Method for recycling acetic acid sec-butyl ester from reaction product during preparation of acetic acid sec-butyl ester with high efficiency |
| CN107226771A (en) * | 2016-03-24 | 2017-10-03 | 中国石油化工股份有限公司 | The separation method of logistics containing hexamethylene and acetic acid and the production method of cyclohexyl acetate and the method for coproduction cyclohexanol and ethanol |
| CN113717051A (en) * | 2021-09-16 | 2021-11-30 | 泰兴金江化学工业有限公司 | Preparation method of butyl acetate |
| CN113880712A (en) * | 2021-09-16 | 2022-01-04 | 泰兴金江化学工业有限公司 | Preparation method of ethyl acetate |
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| CN103980115A (en) * | 2014-06-03 | 2014-08-13 | 湖南瑞源石化股份有限公司 | Method for recycling acetic acid sec-butyl ester from reaction product during preparation of acetic acid sec-butyl ester with high efficiency |
| CN107226771A (en) * | 2016-03-24 | 2017-10-03 | 中国石油化工股份有限公司 | The separation method of logistics containing hexamethylene and acetic acid and the production method of cyclohexyl acetate and the method for coproduction cyclohexanol and ethanol |
| CN107226771B (en) * | 2016-03-24 | 2020-08-18 | 中国石油化工股份有限公司 | Method for separating stream containing cyclohexane and acetic acid, method for producing cyclohexyl acetate and method for co-producing cyclohexanol and ethanol |
| CN113717051A (en) * | 2021-09-16 | 2021-11-30 | 泰兴金江化学工业有限公司 | Preparation method of butyl acetate |
| CN113880712A (en) * | 2021-09-16 | 2022-01-04 | 泰兴金江化学工业有限公司 | Preparation method of ethyl acetate |
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| CN113880712B (en) * | 2021-09-16 | 2023-08-04 | 泰兴金江化学工业有限公司 | Preparation method of ethyl acetate |
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