CN101367723A - Process and apparatus for preparing n-butyl acetate - Google Patents
Process and apparatus for preparing n-butyl acetate Download PDFInfo
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- CN101367723A CN101367723A CNA2008101400557A CN200810140055A CN101367723A CN 101367723 A CN101367723 A CN 101367723A CN A2008101400557 A CNA2008101400557 A CN A2008101400557A CN 200810140055 A CN200810140055 A CN 200810140055A CN 101367723 A CN101367723 A CN 101367723A
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Abstract
The present invention relates to a method of producing n-butyl acetate with a reaction-rectification bulkhead column, and a device thereof. The device is characterized in that a separator extending from the middle to the middle-upper part of the column is arranged in the vertical direction in a conventional rectification column, and the right-side bottom of the separator is sealed, thereby dividing the internal space of the rectification column into five regions which have different functions, wherein, methyl acetate and n-butyl alcohol react in the reaction zone of the region (4) to produce n-butyl acetate and methanol, the products are separated in other regions to prepare the product n-butyl acetate with the purity more than 99.5 percent at the bottom of a stripping section in the region (5), and the byproduct methanol with the purity more than 98.5 percent is produced at the bottom of a side striping section in the region (3). The advantages of the reaction rectification and the bulkhead column are fully developed in the present invention, the transesterification and the separation purification of the products are realized in one column, the prior technical processes are simplified, and the energy consumption and equipment investment are greatly reduced.
Description
Technical field
The present invention relates to a kind of apparatus and method that prepare n-butyl acetate, specifically be meant and adopt reactive distillation and next door tower technology, prepare the apparatus and method of n-butyl acetate by methyl acetate and propyl carbinol transesterification reaction.
Background technology
N-butyl acetate is a kind of common chemical raw material, is widely used in industries such as chemical industry, pharmacy, process hides, plastics and spices.Organic solvent that Chang Zuowei is good and extraction agent are used in various refining of petroleum and the pharmacy procedure, also can be used as the composition of the composite and flavouring agent of spices.
The method of present industrial production n-butyl acetate mainly is to be catalyzer with the vitriol oil, is raw material with Glacial acetic acid and propyl carbinol, makes by rhythmic reaction.There is serious deficiency in this operation, mainly shows as: the catalyzer sulphuric acid catalysis also can make reactant and product that certain dehydration and oxidation take place simultaneously, brings difficulty for the recycling refining and raw material of product; Catalyzer can not directly separate with product, needs to remove catalyzer with operation in follow-up washing and the alkali, also can produce a large amount of waste water simultaneously; The vitriol oil is to the corrosion of equipment also especially severe, and periodical operation, and the throughput of equipment is low.Therefore alternative catalysts obtains broad research, Chinese patent CN1061901C provides a kind of load-type solid acid catalyst of producing n-butyl acetate, this catalyzer is with metal sulfate, and metal halide and metal oxide are as active ingredient, with silica gel, alumino silica gel, molecular sieve, kaolin, diatomite or acidic white earth are carrier, generate in the n-butyl acetate at acetic acid and propyl carbinol reaction, have very high selectivity and activity; Chinese patent CN1107136A provides a kind of continuous catalyzing rectifying to produce the method and apparatus of n-butyl acetate, equipment has comprised reaction fractionating tower, condenser, phase splitter, reboiler and other equipment, its processing method is acetate and propyl carbinol adverse current feeding, react at the reaction fractionating tower conversion zone, product stripping section at the bottom of tower is separated and is obtained purer n-butyl acetate product, unreacted reactant, water and a spot of n-butyl acetate enter phase splitter through the overhead condenser condensation, separate out to reenter reaction fractionating tower behind the moisture and recycle.
Ester-interchange method also is a kind of production n-butyl acetate method with better prospect, and it utilizes by-product acetic acid methyl esters and propyl carbinol transesterification reaction in the polyvinyl alcohol production process to produce n-butyl acetate.And the transesterification reaction of methyl acetate and propyl carbinol is reversible reaction, and can form methyl alcohol-methyl acetate, two kinds of azeotropes of propyl carbinol-n-butyl acetate in reaction system, gives to produce with separating and brings great difficulty.Chinese patent CN101219950A provides a kind of methyl acetate and propyl carbinol of utilizing that the method that transesterification reaction is produced n-butyl acetate and methyl alcohol takes place in catalytic rectifying tower, macropore strong acid cation exchange resin or molecular sieve catalyst have been adopted, improved reaction conversion ratio, also overcome the equipment corrosion problem, but do not provide further product separation method, there is azeotrope in the product, unfavorable later separation.
Summary of the invention
The purpose of this invention is to provide a kind of processing method and reactive distillation next door tower apparatus that utilizes transesterification reaction to obtain the high purity n-butyl acetate.
Device of the present invention is a reactive distillation next door tower, a next door (6) that extends to the tower middle and upper part from the tower middle part promptly is set on the vertical direction in the popular response rectifying tower, right side, next door (6) closed bottom, space in the tower is divided into five parts: zone (1) is public rectifying section, and theoretical plate number is 5～15; Zone (2) is a rectifying section, and number of theoretical plate is 10～20; Zone (3) is the side line stripping section, and number of theoretical plate is 5～20; Zone (4) is a conversion zone, and theoretical plate number is 10～20; Zone (5) is a stripping section, and theoretical plate number is 5～15.The next door is that off-centre or center are provided with, and makes the rectifying section (2) and the cross-sectional area ratio of side line stripping section (3) be 1:1～20:1.Reactive distillation next door tower is tray column, packing tower or both arbitrary combination, and wherein filler is efficient wire packing, and as the BX-500 type, the CY-700 type can also be random packing, as the triangle helical packing.
Processing method of the present invention: fresh methyl acetate (8) through mixing tank (10) and the mixed logistics of return logistics (9) (11) by conversion zone (4) bottom feed, propyl carbinol (7) is by conversion zone (4) its top feed, carry out counter current contact at conversion zone (4) and generate n-butyl acetate and methyl alcohol, product separates through stripping section (5), obtains quality purity at stripping section (5) tower still and reaches n-butyl acetate (16) more than 99.5%.Product separates through rectifying section (2), the methyl acetate and the methanol azeotrope that form at public rectifying section (1) top are distillated by cat head, cool off through complete condenser (14), part is squeezed in the tower as backflow, the part with methyl acetate charging (8) after mixing tank (10) mixes, reenter conversion zone (4) bottom, recycle.The liquid phase at top, next door (6) enters rectifying section (2) and side line stripping section (3) respectively according to the mass distribution ratio of 1:1～20:1, obtains quality purity at side line stripping section (3) tower still and reaches methyl alcohol (15) more than 98.5%.
In the operating process of the present invention, the raw materials components mole ratio of propyl carbinol and methyl acetate is 1:1, and tower top temperature is 50～80 ℃, and conversion zone (4) temperature is 60～100 ℃, stripping section (5) tower still temperature is 110～140 ℃, and side line stripping section (3) bottom temp is 60～80 ℃.The working pressure of tower is 0.05～0.5MPa, and cat head adopts complete condenser (14) cooling, and reflux ratio is 1.0～5.0.It is 1:1～5:1 with the mass ratio that enters side line stripping section (3) that the liquid phase at top, next door (6) enters rectifying section (2).The reaction catalyzer that adopts is an acidic cation-exchange resin, as D001 type, NKC-9 type, Amberlyst15, or molecular sieve catalyst, as HZSM-5 type molecular sieve, the transformation efficiency of reaction reaches more than 99%.
Advantage of the present invention: the present invention has overcome not only in the traditional technology that equipment is perishable, the difficult separation of product and operate discontinuous drawback, also further simplified existing technical process, and transesterification reaction, product separation and purification be integrated in the same tower, when obtaining high purity product, facility investment and process cost have been significantly reduced.
Description of drawings
Fig. 1 reactive distillation next door tower schematic flow sheet.
Among the figure, 1 public rectifying section, 2 rectifying sections, 3 side line stripping sections, 4 conversion zones, 5 stripping sections, 6 next doors, 7 propyl carbinol chargings, 8 methyl acetate chargings, 9 return logistics, 10 liquid mixers, 11 mixture flow, 12,13 reboilers, 14 complete condensers, 15 methanol product, 16 n-butyl acetate products
Specific embodiments
The invention will be further described by means of embodiment below, but the present invention is not limited to embodiment.
Example 1: as shown in Figure 1, the tower diameter is 2800mm, tower height 27450mm.Rectifying section (2) is 17.8:1 with the ratio of the cross-sectional area of side line stripping section (3), whole each section of tower all adopts column plate, the actual plate number of each tower section is as shown in table 1, wherein the catalyzer that adopted of conversion zone (4) is Zeo-karb Amberlyst15, the raw materials components mole ratio of methyl acetate and propyl carbinol is 1:1, it is 2.46:1 with the mass ratio that enters side line stripping section (3) that the liquid phase at top, next door (6) enters conversion zone (4), and the trim the top of column ratio is 2.4.The flow and the massfraction of each logistics are as shown in table 1, and tower top temperature is 54.1 ℃, and conversion zone (4) temperature is 68.6～89.3 ℃, and stripping section (5) tower still temperature is 126.1 ℃, 64.5 ℃ of side line stripping section (3) bottom temps, and working pressure is 0.1MPa.
Each tower section actual plate number of table 1 and each logistics parameter
Example 2: as shown in Figure 1, the tower diameter is 2600mm, tower height 21350mm.Rectifying section (2) is 8.4:1 with the ratio of the cross-sectional area of side line stripping section (3).Conversion zone (4) adopts column plate, and the actual plate number is 18 plates, and other all tower sections all adopt BX500 type filler, and wherein public rectifying section (1) bed stuffing height is 3000mm; Rectifying section (2) bed stuffing height is 4000mm; Conversion zone (4) side line stripping section (3) bed stuffing height is 2500mm; Stripping section (5) bed stuffing height is 1750mm.The catalyzer that conversion zone (4) is adopted is Zeo-karb NKC-9, the raw materials components mole ratio of methyl acetate and propyl carbinol is 1:1, it is 1.47:1 with the liquid phase mass ratio that enters side line stripping section (3) that the liquid phase at top, next door (6) enters rectifying section (4), and the trim the top of column ratio is 2.7.The flow of each logistics and the massfraction of product are as shown in table 2, tower top temperature is 53.8 ℃, and conversion zone (4) temperature is 69.8～80.1 ℃, and stripping section (5) tower still temperature is 124.5 ℃, 62.8 ℃ of side line stripping section (3) tower still temperature, working pressure is 0.08MPa.
The flow of each logistics of table 2 and massfraction
| Charging/extraction | Mass rate (kg/h) | Propyl carbinol (%) | Methyl acetate (%) | Methyl alcohol (%) | N-butyl acetate (%) |
| Propyl carbinol charging (7) methyl acetate charging (8) n-butyl acetate product (16) methanol product (15) return logistics (9) | 7412.28 7407.94 11595.08 3225.24 17367.58 | 100.00 0.00 0.32 0.00 0.00 | 0.00 100.00 0.00 1.15 82.02 | 0.00 0.00 0.00 98.85 17.98 | 0.00 0.00 99.68 0.00 0.00 |
Example 3: as shown in Figure 1, the tower diameter is 1400mm, tower height 18500mm.Rectifying section (2) is 13.6:1 with the ratio of the cross-sectional area of side line stripping section (3), and whole each section of tower all adopts AX-250 type filler, the altitude distribution of each tower section: public rectifying section (1) bed stuffing height is 3000mm; Rectifying section (2) bed stuffing height is 4000mm; Side line stripping section (3) bed stuffing height is 2500mm; Conversion zone (4) bed stuffing height is 3750mm; Stripping section (5) bed stuffing height is 1750mm.The catalyzer that conversion zone (4) is adopted is a HZSM-5 type molecular sieve catalyst, the raw materials components mole ratio of methyl acetate and propyl carbinol is 1:1, it is 2.26:1 with the liquid phase mass ratio that enters side line stripping section (3) that the liquid phase at top, next door (6) enters conversion zone (4), and trim the top of column is than being 2.4:1.The flow of each logistics and the massfraction of product are as shown in table 3, tower top temperature is 55.8 ℃, and conversion zone (4) temperature is 81.0～87.4 ℃, and stripping section (5) tower still temperature is 129.1 ℃, 66.2 ℃ of side line stripping section (3) tower still temperature, working pressure is 0.2MPa.
The flow of each logistics of table 3 and massfraction
| Charging/extraction | Mass rate (kg/h) | Propyl carbinol (%) | Methyl acetate (%) | Methyl alcohol (%) | N-butyl acetate (%) |
| Propyl carbinol charging (7) methyl acetate charging (8) n-butyl acetate product (16) methanol product (15) return logistics (9) | 1482.46 1481.59 2318.98 645.07 2844.68 | 100.00 0.00 0.32 0.00 0.00 | 0.00 100.00 0.00 1.15 72.33 | 0.00 0.00 0.00 98.85 27.67 | 0.00 0.00 99.68 0.00 0.00 |
Claims (8)
1. a n-butyl acetate synthetic device comprises reactive distillation next door tower (17), complete condenser (14), reboiler (12,13), mixing tank (10) and other utility appliance.Reactive distillation next door tower (17) inside is provided with a vertical next door (6), and next door (6) extend to the middle and upper part of tower from the middle part of tower, right side, next door (6) closed bottom.The space is divided into five zones in the Tata of reactive distillation next door: zone (1) is public rectifying section, and zone (2) is a rectifying section, and zone (3) is the side line stripping section, and zone (4) is a conversion zone, and zone (5) is a stripping section.
2. device described in claim 1 is characterized in that next door (6) is provided with for the center or eccentric the setting, and the cross-sectional area that makes rectifying section (2) and side line stripping section (3) is than being 1:1～20:1.
3. device as claimed in claim 1 is characterized in that reactive distillation next door tower (17) can be tray column, packing tower or both arbitrary combination.
4. n-butyl acetate synthetic processing method is characterized in that in the reactive distillation next door tower (17) described in claim 1 synthesizing n-butyl acetate and carries out Separation ﹠ Purification, and the concrete steps of process are as follows:
A) raw acetic acid methyl esters (8) mixes with return logistics (9) through mixing tank (10), mixture flow (11) is entered in the tower by conversion zone (4) bottom, raw material propyl carbinol (7) is entered in the tower by conversion zone (4) top, carry out transesterification reaction in conversion zone (4) counter current contact, generate n-butyl acetate and methyl alcohol.
B) part of reaction product methyl alcohol is separated through rectifying section (2) with unreacted methyl acetate, forms azeotrope at public rectifying section (1), cools off through complete condenser (14), part is squeezed in the tower as backflow, part is extracted out, and mixes at mixing tank (10) with the charging methyl acetate, recycles.
C) another part of reaction product methyl alcohol and unreacted completely methyl acetate enter side line stripping section (3) by public rectifying section (1) and separate, methyl acetate returns public rectifying section (1) to be separated again, and obtains methanol product (15) in side line stripping section (3) bottom.
D) reaction product n-butyl acetate and unreacted completely propyl carbinol separate through stripping section (5), unreacted propyl carbinol reenters conversion zone (4) and participates in reaction, and obtains n-butyl acetate product (16) in stripping section (5) bottom.
5. processing method as claimed in claim 4, charging propyl carbinol and methyl acetate mol ratio are 1:1.
6. it is 1:1～5:1 with the mass ratio that enters side line stripping section (3) that processing method as claimed in claim 4, the liquid phase that it is characterized in that top, next door (6) enter rectifying section (2).
7. processing method as claimed in claim 4 is characterized in that the catalyzer that conversion zone (4) adopts is acidic cation-exchange resin or molecular sieve catalyst.
8. processing method as claimed in claim 4, tower top temperature are 50～80 ℃, and conversion zone (4) temperature is 60～100 ℃, and stripping section (5) tower still temperature is 110～140 ℃, and side line stripping section (3) bottom temp is 60～80 ℃.The working pressure of reactive distillation next door tower (17) is 0.05～0.5MPa, and the trim the top of column ratio is 1.0～5.0.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008101400557A CN101367723A (en) | 2008-09-18 | 2008-09-18 | Process and apparatus for preparing n-butyl acetate |
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| CNA2008101400557A CN101367723A (en) | 2008-09-18 | 2008-09-18 | Process and apparatus for preparing n-butyl acetate |
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| CN101367723A true CN101367723A (en) | 2009-02-18 |
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| CNA2008101400557A Pending CN101367723A (en) | 2008-09-18 | 2008-09-18 | Process and apparatus for preparing n-butyl acetate |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265429A (en) * | 2013-05-24 | 2013-08-28 | 青岛理工大学 | Technical method for synthesizing methyl acetate |
| CN108503547A (en) * | 2018-04-09 | 2018-09-07 | 沈阳化工大学 | A method of by transesterification path synthesizing n-butyl acetate |
| CN108530294A (en) * | 2018-04-10 | 2018-09-14 | 沈阳化工大学 | A method of by transesterification path synthesis of acetic acid ester |
| CN108658760A (en) * | 2018-04-09 | 2018-10-16 | 沈阳化工大学 | A kind of process by transesterification path synthesizing n-butyl acetate |
| CN114349663A (en) * | 2021-12-27 | 2022-04-15 | 天津均凯农业科技有限公司 | Preparation method of 2-methoxyethyl-2- (4-tert-butylphenyl) cyanate |
| CN116271905A (en) * | 2023-03-02 | 2023-06-23 | 珠海谦信新材料有限公司 | System for high-efficient production methyl acetate |
| CN114349663B (en) * | 2021-12-27 | 2024-05-28 | 天津均凯农业科技有限公司 | Preparation method of 2-methoxyethyl-2- (4-tert-butylphenyl) cyanate |
-
2008
- 2008-09-18 CN CNA2008101400557A patent/CN101367723A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265429A (en) * | 2013-05-24 | 2013-08-28 | 青岛理工大学 | Technical method for synthesizing methyl acetate |
| CN108503547A (en) * | 2018-04-09 | 2018-09-07 | 沈阳化工大学 | A method of by transesterification path synthesizing n-butyl acetate |
| CN108658760A (en) * | 2018-04-09 | 2018-10-16 | 沈阳化工大学 | A kind of process by transesterification path synthesizing n-butyl acetate |
| CN108530294A (en) * | 2018-04-10 | 2018-09-14 | 沈阳化工大学 | A method of by transesterification path synthesis of acetic acid ester |
| CN114349663A (en) * | 2021-12-27 | 2022-04-15 | 天津均凯农业科技有限公司 | Preparation method of 2-methoxyethyl-2- (4-tert-butylphenyl) cyanate |
| CN114349663B (en) * | 2021-12-27 | 2024-05-28 | 天津均凯农业科技有限公司 | Preparation method of 2-methoxyethyl-2- (4-tert-butylphenyl) cyanate |
| CN116271905A (en) * | 2023-03-02 | 2023-06-23 | 珠海谦信新材料有限公司 | System for high-efficient production methyl acetate |
| CN116271905B (en) * | 2023-03-02 | 2023-10-20 | 珠海谦信新材料有限公司 | System for high-efficient production methyl acetate |
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Open date: 20090218 |