CN101735047A - Technology for continuously producing secbutyl acetate - Google Patents
Technology for continuously producing secbutyl acetate Download PDFInfo
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- CN101735047A CN101735047A CN200910232342A CN200910232342A CN101735047A CN 101735047 A CN101735047 A CN 101735047A CN 200910232342 A CN200910232342 A CN 200910232342A CN 200910232342 A CN200910232342 A CN 200910232342A CN 101735047 A CN101735047 A CN 101735047A
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- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000005516 engineering process Methods 0.000 title claims abstract description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 162
- 238000006243 chemical reaction Methods 0.000 claims abstract description 112
- 239000007788 liquid Substances 0.000 claims abstract description 63
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000000945 filler Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000002347 injection Methods 0.000 claims abstract description 11
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- 239000002994 raw material Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007921 spray Substances 0.000 claims description 49
- GQKZRWSUJHVIPE-UHFFFAOYSA-N sec-amyl acetate Natural products CCCC(C)OC(C)=O GQKZRWSUJHVIPE-UHFFFAOYSA-N 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000007791 liquid phase Substances 0.000 claims description 15
- 239000003377 acid catalyst Substances 0.000 claims description 12
- 238000010924 continuous production Methods 0.000 claims description 11
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- 241000282326 Felis catus Species 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000010533 azeotropic distillation Methods 0.000 claims description 4
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
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- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical group COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a technology for efficiently and continuously producing secbutyl acetate. In the technology, acetic acid and 1-butylene serve as raw materials, solid-liquid mixed acid serves as catalyst and an integrated system composed of an injection collision stream tower reactor, a rectification system, an oil-water separator and the like is adopted. Wherein the injection collision stream tower reactor is mainly composed of an injection-collision stream reaction section, a tower plate/filler tower-type reaction section, a forced circulation and control part and a catalyst replacing part, which greatly improves conversion rate of acetic acid and use ratio of butylene. The method for efficiently and continuously producing secbutyl acetate has the comprehensive advantages of compact structure, safety and reliability, high conversion rate, high material use ratio, low operation cost and the like.
Description
Technical field
The present invention relates to a kind of high-efficiency and continuous and produce the novel process of 2-butyl acetate.
Background technology
2-butyl acetate is a kind of colourless, inflammable, liquid with fruit fragrance, is widely used in paint, plastics, medicine and perfume industry, also can be used as extraction agent, dewatering agent and metal cleaner etc. simultaneously.The main synthetic method of 2-butyl acetate is two kinds of acid alcohol esterification process and alkene additive processes, and the former synthetic method is exactly acetic acid and sec-butyl alcohol esterification, but the speed of response of this method is slow, long reaction time, and product yield is low.The latter's alkene additive process is meant acetic acid and hybrid C 4 (or butylene) addition reaction under an acidic catalyst effect and direct acetic acid synthesized secondary butyl ester, this kind method has directly been utilized the alkene resource, need not alcohol and do intermediate, thereby reduced the production cost of 2-butyl acetate, have tangible economic advantages.In addition, along with the raising of China's ethylene production and crude capacity, the C4 that steam cracking device and catalytic cracking unit are a large amount of with by-product is effective way of C4 resource synergic and utilize the acetic acid synthesized secondary butyl ester of 1-butylene in the hybrid C 4.The synthetic tubular fixed-bed reactor or suspension stirred-tank reactors of adopting of 2-butyl acetate more, it is low that these old technologies exist transformation efficiency, and raw material availability is low, long reaction time, problems such as production cost height.
Summary of the invention
The objective of the invention is to solve the deficiency that exists in the above-mentioned background technology, proposing a kind of 2-butyl acetate synthetic novel process, is raw material with acetic acid and 1-butylene promptly, and solid-liquid mixing acid is catalyzer, adopt and spray collision stream tower reactor, the novel process of the acetic acid synthesized secondary butyl ester of high-efficiency and continuous.
Technical scheme of the present invention is as follows:
A kind of technology of continuous production 2-butyl acetate, its flow process as shown in Figure 1, it mainly is made up of the following step:
Step 1. acetic acid raw material is entered by pipeline 1 and sprays in the collision stream tower reactor 3, and pressure is 0.2-1.5MPa (gauge pressure), and temperature of reaction is 60-150 ℃, preferred 70-130 ℃; Described catalyzer is a solid-liquid mixing acid, promptly form by Zeo-karb and liquid acid sulfuric acid, phosphoric acid or tosic acid, catalyst consumption is the 0.8%-10% (mass percent) of acetic acid, preferred 2%-5%, and liquid acid accounts for the 20-60% (H that liquid acid provides
+Amount account for whole H
+Amount per-cent, below identical), C4 gas mixture (or butylene) is then entered into through gas distributor 5 by pipeline 2 and sprays in the collision stream tower reactor 3 and acetic acid reacts;
The reaction mass that step 2. is sprayed in the collision stream tower reactor 3 filters through the strainer in the device 6, solid-phase catalyst in the reaction mass is trapped within and sprays in the collision stream tower reactor 3, liquid phase reacting material and partially liq acid catalyst enter impeller pump 8, again behind liquid meter 9 and interchanger 10, enter the injectors 4 that spray in the collision stream tower reactor 3 and gone into to spray collision stream tower reactor 3 by high-velocity jet and spray in the collision stream conversion zones; While Open valve 22, drawing one reaction solution of being carried by pump 8 upwards injects at a high speed and sprays collision stream tower reactor 3 and spray in the collision stream conversion zones by spraying bottom that collision stream tower reactor 3 sprays collision stream conversion zones through jet sparger 7, it forms collision stream with the logistics of spraying downwards, thereby form violent stirring within it, make the air pocket in the rising gaseous phase materials (butylene) be ground into various small bubbles, increased the mass transfer area of gas phase, strengthen between the reactant molecule and reactant molecule and catalyzer between effective the contact, improved the formation speed of product 2-butyl acetate effectively, reaction conversion ratio and selectivity
Because in spraying collision stream tower reactor 3, gas-liquid-solid three-phase is highly colliding under the stream effect, solid catalyst will keep suspending fully and high-speed motion state in reactor, so can avoid the part catalyzer at the deposition of reactor bottom and catalyzer skewness and influence reaction process in reactor.
Unreacted is gas completely, rises to the liquid level top of reactor, and the low pressure area of self-priming apparatus 13 in the nozzle place by injector entrainmented in the reactor by the fluid of high-speed motion and send into and continue reaction in the reactor body liquid phase.So circulation constantly can effectively improve the utilization ratio of butylene.
Step 3. was carried out 0.1-1.0 hour when reacting, preferred after 0.2-0.8 hour, Open valve 28, still the unreacted gas phase (being mainly C4) at reactor top is through gas distributor 21, enter the tower conversion zone 20 of column plate/filler, while Open valve 29, draw one liquid and enter tower conversion zone 20 from the top, with the further reaction again of unreacted butylene, transformation efficiency with further raising butylene, the unreacted C4 of last minute quantity and light constituent directly flow out from cat head, and the liquid phase part of the tower conversion zone of column plate/filler 20 bottoms is then entrainmented by the fluid of high-velocity jet by the low pressure area of self-priming apparatus 13 at the injector nozzle place by catch tray 37 and continues reaction in the reactor.The reaction here utilized in the liquid phase material liquid acid catalyst and owing to the broken solid powder th-1 catalyst that has passed strainer 6 of wearing and tearing, they still have stronger catalytic activity, owing to the reactivity of the tower conversion zone 20 of column plate/filler, make minimum being reduced to below 0.1% of content of butylene from the tail gas that top duct 12 is discharged.In addition, this tower reactive system can make the light constituent of C4 gas mixture be separated.Therefore the tower reactive system of this column plate/filler has not only effectively improved the utilization ratio of butylene, has increased the yield of total system, and has alleviated difficulty of post-processing, has simplified technology, has reduced energy consumption, also helps environment protection.
Step 4. reaction was carried out 0.2-2 hour, and is preferred after 0.5-1.5 hour, and liquid phase reacting material enters distillation system 31 and separates by valve 14 beginning dischargings.Acetic acid and 2-butyl acetate separate and can adopt the azeotropic distillation mode also can adopt the mode of conventional distillation.If adopt the azeotropic distillation mode, institute adds entrainer and can form the material of azeotrope with 2-butyl acetate for any one, and the boiling point of azeotropic point and acetic acid differs the material more than 10 ℃, also will the energy phase-splitting behind the azeotrope condensation liquefaction, and as water etc.Entrainer is from 32 addings, and azeotrope enters the water-and-oil separator 36 from cat head, and acetic acid at the bottom of rectifying tower 31 towers and liquid acid then turn back to sprays continuation reaction in the collision stream tower reactor 3.Water in the water-and-oil separator then continues to use as entrainer, the 2-butyl acetate crude product on upper strata then enters into rectifying tower 33 and makes with extra care, the by product of cat head turns back to and sprays the generation that suppresses side reaction in the collision stream tower reactor 3, and can to obtain purity be 2-butyl acetate more than 99.99% to discharge port 34 at the bottom of the tower.Simultaneously, the acetic acid raw material also begins from pipeline 1 toward spraying charging in the collision stream tower reactor 3, C4 gas mixture (or butylene) then enters from pipeline 2 continuously, and to guarantee the quality of material conservation of whole production system, whole thus technology enters into the production phase of steady and continuous.
The technology of above-mentioned continuous production 2-butyl acetate, after the operation regular hour, loss or active decline may appear in the solid-phase catalyst in the solid-liquid mixing acid, need add or change solid catalyst, and its step is as follows:
Step 1 '. open and spray collision stream tower reactor 3 bottoms and lead to valve 23 on catalyzer solid-liquid separation tank 15 pipelines and catalyzer solid-liquid separation tank 15 and lead to valve 24 on tundish 17 pipelines, be provided with high efficiency filter 16 in the catalyzer solid-liquid separation tank 15, solid catalyst particle is trapped in the filter screen upstream by filter screen in the feed liquid, the liquid phase feed liquid is then got back to tundish 17 by valve 24, turns back to through pump 18 then and sprays in the collision stream tower reactor 3;
After step 2 ' if. change solid catalyst, then treat step 1 ' is sprayed catalyzer in the collision stream tower reactor 3 and emptied, open the loam cake of catalyst feeding device 19, add live catalyst, close the catalyst feeding device loam cake then;
Step 3 '. open valve 26 and valve 27, valve-off 30, catalyzer will enter with acetic acid and spray in the collision stream tower reactor 3, and then open valve 30, valve-off 26,27;
Step 4 '. valve-off 23 and valve 24, open valve 26 and 27 then, valve-off 30 is removed the catalyzer that lost efficacy in catalyzer solid-liquid separation tank 15, and catalyzer replacing process is finished.
It is continuous that catalyzer is changed process, quick, do not have any gas, liquid leakage, do not influence normal running.
A kind of specific equipment of continuous production 2-butyl acetate technology according to claim 1 sprays collision stream tower reactor, as shown in drawings, it is made up of two portions, the bottom is divided into sprays collision stream conversion zone, top is divided into the tower conversion zone 20 of column plate/filler, in spraying collision stream conversion zone, injector 4 is arranged at the top, self-priming apparatus 13 is arranged on the top jet device 4, and acetic acid inlet tube 1 and catalyst feeding device 19, butylene inlet tube 2 is arranged at the bottom, butylene inlet tube 2 links to each other with the gas distributor that the injection collision is flowed in the conversion zone, the liquid that responds on lower sides outlet, before the reaction solution outlet, strainer 6 is arranged, reaction solution outlet passing through valve, impeller pump 8, under meter 9 links to each other with injector 4 with interchanger 10, spray collision stream conversion zone bottom ejector 7 and reaction solution outlet and control of export valve 23 are arranged, ejector 7 links to each other with impeller pump 8 outlets as bypass line with pipeline by valve 22, the gas distributors 21 that injection collision stream conversion zone top has pipeline process by-pass valve control 28 and injection to collide in the tower conversion zone 20 of column plate/filler on stream tower reactor top link to each other, catch tray 37 is arranged at the tower conversion zone of column plate/filler 20 bottoms, the top has pipeline to pass through interchanger 11 to link to each other with pneumatic outlet 12, the discharging reaction end gas.
Advantage of the present invention:
Compact construction of the present invention, safe and reliable, continuous operation, the acetic acid conversion height, the utilization ratio of C4 gas mixture (or butylene) can reach extreme value (almost all being reacted away), and production energy consumption and cost are low, are embodied in:
1) adopts novel injection collision stream tower reactor system; the liquid of high-velocity jet collision forms high turbulence; make the interior gas-liquid-solid three-phase of reactor be able to abundant contact; strengthened between the reactant molecule and reactant molecule and catalyzer between effective the contact; make catalyzer in reactor, be stirred more violently; it is more even to distribute, and the flexibility of this height cutout stirs had both protected catalyzer to avoid a large amount of breakages, had quickened the carrying out of reaction again.
2) spray collision stream tower reactor system and be provided with self-priming apparatus, utilize the negative pressure of the fluid formation of high-velocity jet that the still unreacted gas of reactor head is entrainmented in the reactor liquid phase, allow it enter the liquid phase reaction main body repeatedly, remedy very brief deficiency of the gas phase residence time in the gas-liquid reactor to greatest extent; Secondly, the fluid of high-velocity jet can be pulverized gas and be very little bubble, has increased the specific surface area of gas, has strengthened the effective contact between the gas-liquid-solid three-phase.Above-mentioned aggregate measures have improved formation speed, reaction conversion ratio and the selectivity of product 2-butyl acetate effectively
3) setting of the tower reactive system of column plate/filler can make unreacted C4 further be converted into product, and the light constituent among the C4 is separated.This system has not only improved yield, can also simplify aftertreatment work, cuts down the consumption of energy and cost, alleviates environmental pollution.
4) adopt the solid-liquid mixed-acid catalyst, promptly formed by Zeo-karb and liquid acid.Mixed-acid catalyst has same acid active centre, compares with single Zeo-karb, can reduce the consumption of resin, has reduced the volume of reactor, has reduced cost; Compare with single sulfuric acid liquid-phase catalyst, can effectively reduce the generation of by product, improve the selectivity of reaction.Small amount of liquid acid simultaneously is at the technological process reusable edible, the problem of environmental pollution of having avoided the discharging of a large amount of liquid acid to cause.In addition, ad hoc solid catalyst is added and the replacing system, and catalyzer is added and the continuous convenient and swift nothing leakage of replacing process, and the assurance production operation is carried out continuously.
5) solid-liquid filter of design and installation in the reactor can make solid catalyst particle and liquid phase separation in the reactor efficiently, thereby has guaranteed the continous-stable of operation.
6) material has a large amount of heat in the reactor, can directly be that rectifying tower is used, and it is integrated to carry out heat very easily, has reduced the energy consumption of separation system thus significantly.
7) turn back to the utilization of reactor internal recycle at the bottom of liquid acid and the tower of unreacted acetic acid, avoided discharging the problem of environmental pollution that causes, improved the utilization ratio of acetic acid simultaneously by liquid acid by rectifying tower 31.
8) the by product part separated of rectifying tower 32 cats head then turns back in the reactor, suppresses the generation of side reaction, improves the utilization ratio of acetic acid, reduces production costs.
In a word, this high-efficiency and continuous is produced the novel process of 2-butyl acetate, and speed of response is fast, the transformation efficiency height, and selectivity and yield height, energy consumption and cost are lower, and waste discharge is few, is an energy-saving and emission-reduction new technology efficiently.
Description of drawings
Accompanying drawing is a process flow sheet of the present invention, by specification sheets and embodiment shared, wherein:
1: acetic acid inlet tube, 2:C4 gas mixture (butylene+butane) inlet tube, 3: spray collision stream tower reactor, 4: injector, 5 and 21: gas distributor, 6: strainer, 7: ejector, 8 and 18: impeller pump, 9: under meter, 10 and 11: interchanger, 12: pneumatic outlet, 13: self-priming apparatus 14: reaction solution output tube valve, 15: liquid-solid separator tank, 16: high efficiency filter, 17: tundish, 19: catalyst feeding device, 20: the tower conversion zone of column plate/filler, 22-30: valve, 31 and 33: rectifying tower, 32: the entrainer inlet, 34: the 2-butyl acetate outlet, 35: impurity outlet, 36: water-and-oil separator, 37: catch tray.
Specific embodiments
Embodiment 1
Technical process as shown in Figure 1, the volume that wherein sprays the conversion zone of collision stream tower reactor 3 is 6m
3, diameter is 1.6m, highly is 3.2m; The diameter of the tower conversion zone 20 of column plate/filler is 1.0m, highly is 6m, and injector is provided by two grand engineering development company limited.
Acetic acid and butylene are 1: 1.1 by the ratio of amount of substance, spray in the collision stream tower reactor 3 with joining after solid-liquid mixed-acid catalyst (catalytic amount account for acetic acid quality 10%) mixes through pipeline 1 and in catalyst feeding device 19, butylene is entered into through gas distributor 5 by pipeline 2 and sprays in the collision stream tower reactor 3,110 ℃ of temperature of reaction, pressure is 0.8MPa (gauge pressure), wherein solid catalyst is Amberlyst 15 (production of U.S. Rhom and Hass), liquid catalyst is a sulfuric acid, wherein liquid acid accounts for 20% (amount of the H+ that liquid acid provides accounts for the amount per-cent of whole H+, below identical).The material that sprays in the collision stream tower reactor 3 enters impeller pump 8 through filter 6, through liquid meter 9 and interchanger 10, spurt in the injection collision stream tower reactor 3 by injector 4, Open valve 22 simultaneously draws one liquid ejector 7 of flowing through and enters and spray in collision stream tower reactor 3 conversion zones.The gas that sprays collision stream tower reactor 3 conversion zones top is then entrainmented in the reaction solution by self-priming apparatus 13, after reaction is carried out 0.2 hour, open valve 28, unreacted gas completely enters into the tower conversion zone 20 of column plate/filler through gas distributor 21, and while Open valve 29 draws one liquid and enters the tower conversion zone 20 of column plate/filler from the top.After reaction is carried out 0.5 hour, reaction solution begins to enter into rectifying tower 31 from pipeline 14 with entrainer 32 to be separated, azeotrope advances rectifying tower 33 from cat head through water-and-oil separator 36 and makes with extra care, be that acetic acid and sulfuric acid mixture then turn back to spray in collision stream tower reactor 3 conversion zones and continue reaction at the bottom of the tower, begin simultaneously to replenish acetic acid and butylene, guarantee the quality of material conservation of whole technology toward spraying in the collision stream tower reactor 3.This process acetic acid conversion is 93%, and the content of butylene is 0.09% in the gas of reaction back, and production capacity is 1000kg/h.
Embodiment 2
Adopt conversion unit similarly to Example 1, similar with embodiment 1 working method, the mol ratio of acetic acid and butylene is 1: 1.2,120 ℃ of temperature of reaction, the pressure that sprays collision stream tower reactor 5 is 1.2MPa (gauge pressure), and the catalyzer that is adopted is solid-liquid mixed-acid catalyst (catalytic amount account for acetic acid quality 7%), and wherein solid phase is strong-acid ion exchange resin Amberlyst 36 (production of U.S. Rhom and Hass), liquid catalyst is a tosic acid, accounts for 50%.This process acetic acid conversion is 94.5%, and the content of butylene is 1.2% in the gas of reaction back, and production capacity is 1020kg/h.
Embodiment 3
Adopt conversion unit similarly to Example 1, similar with embodiment 1 working method, the mol ratio of acetic acid and butylene is 1: 0.8,130 ℃ of temperature of reaction, the pressure that sprays collision stream tower reactor 5 is 1.4MPa (gauge pressure), and the catalyzer that is adopted is solid-liquid mixed-acid catalyst (catalytic amount account for acetic acid quality 5%), and wherein solid phase is strong-acid ion exchange resin Amberlyst 35 (production of U.S. Rhom and Hass), liquid catalyst is a phosphoric acid, and phosphoric acid accounts for 40%.This process acetic acid conversion is 91%, and the content of butylene is 0.04% in the gas of reaction back, and production capacity is 970kg/h.
Embodiment 4
Adopt conversion unit similarly to Example 1, similar with embodiment 1 working method, the mol ratio of acetic acid and butylene is 1: 1.5,100 ℃ of temperature of reaction, the pressure that sprays collision stream tower reactor 5 is 0.7MPa (gauge pressure), and the catalyzer that is adopted is solid-liquid mixed-acid catalyst (catalytic amount account for acetic acid quality 0.8%), and wherein solid phase is strong-acid ion exchange resin D72 (Chemical Plant of Nankai Univ.'s production), liquid catalyst is a sulfuric acid, accounts for 60%.This process acetic acid conversion is 96%, and the content of butylene is 2.3% in the gas of reaction back, and production capacity is 1030kg/h.
Embodiment 5
Adopt conversion unit similarly to Example 1, similar with embodiment 1 working method, the mol ratio of acetic acid and butylene is 1: 0.5,80 ℃ of temperature of reaction, the pressure that sprays collision stream tower reactor 5 is 0.3MPa (gauge pressure), and the catalyzer that is adopted is solid-liquid mixed-acid catalyst (catalytic amount account for acetic acid quality 2%), and wherein solid phase is strong-acid ion exchange resin D61 (Chemical Plant of Nankai Univ.'s production), liquid catalyst is a tosic acid, accounts for 50%.This process acetic acid conversion is 57%, and the content of butylene is 0.02% in the gas of reaction back, and production capacity is 620kg/h.
Embodiment 6
Adopt conversion unit similarly to Example 1, similar with embodiment 1 working method, the mol ratio of acetic acid and butylene is 1: 2,60 ℃ of temperature of reaction, the pressure that sprays collision stream tower reactor 5 is 0.1MPa (gauge pressure), and the catalyzer that is adopted is solid-liquid mixed-acid catalyst (catalytic amount account for acetic acid quality 2.6%), and wherein solid phase is strong-acid ion exchange resin strong-acid ion exchange resin D005 or NKC-9 (Chemical Plant of Nankai Univ.'s production), liquid catalyst is a sulfuric acid, accounts for 30%.This process acetic acid conversion is 97%, and the content of butylene is 7.6% in the gas of reaction back, and production capacity is 1050kg/h.
Embodiment 7
Adopt conversion unit similarly to Example 1, similar with embodiment 1 working method, the mol ratio of acetic acid and butylene is 1: 1.8,80 ℃ of temperature of reaction, the pressure that sprays collision stream tower reactor 5 is 0.45MPa (gauge pressure), and the catalyzer that is adopted is solid-liquid mixed-acid catalyst (catalytic amount account for acetic acid quality 2.6%), and wherein solid phase is strong-acid ion exchange resin D005 or NKC-9 (Chemical Plant of Nankai Univ.'s production), liquid catalyst is a sulfuric acid, accounts for 60%.This process acetic acid conversion is 97%, and the content of butylene is 5.6% in the gas of reaction back, and production capacity is 1050kg/h.
Claims (7)
1. the technology of a continuous production 2-butyl acetate is characterized in that it mainly is made up of the following step:
Step 1. acetic acid raw material is entered by pipeline (1) and sprays in the collision stream tower reactor (3), gauge pressure pressure is 0.2-1.5MPa, temperature of reaction is 60-150 ℃, described catalyzer is a solid-liquid mixing acid, promptly form by Zeo-karb and liquid acid sulfuric acid, phosphoric acid or tosic acid, catalyst consumption is the 0.8%-10% of acetic acid mass percent, liquid acid accounts for 20-60%, and C4 gas mixture or butylene are then entered into to spray in the collision stream tower reactor (3) through gas distributor (5) by pipeline (2) and react with acetic acid;
The reaction mass that step 2. is sprayed in the collision stream tower reactor (3) filters through the strainer (6) in the device, solid-phase catalyst in the reaction mass is trapped within and sprays in the collision stream tower reactor (3), Partial Liquid Phase reaction mass and partially liq acid catalyst enter impeller pump (8), again behind liquid meter (9) and interchanger (10), enter the injector (4) that sprays in the collision stream tower reactor (3) and gone into to spray collision stream tower reactor (3) by high-velocity jet and spray in the collision stream conversion zone; While Open valve (22) draws one reaction solution of being carried by pump (8) and is upwards injected at a high speed in the injection collision stream conversion zone by the bottom of spraying collision stream tower reactor (3) injection collision stream conversion zone through jet sparger (7);
Step 3. is after reaction is carried out 0.1-1.0 hour, Open valve (28), spray collision stream tower reactor (3) and spray the still unreacted gas phase at collision stream conversion zone top through gas distributor (21), enter the tower conversion zone of column plate/filler (20), while Open valve (29), draw one liquid and enter tower conversion zone (20) from the tower conversion zone of column plate/filler (20) top, with the further reaction again of unreacted butylene, transformation efficiency with further raising butylene, the unreacted C4 of last minute quantity and light constituent are directly discharged from cat head pipeline (12), and the liquid phase part of the tower conversion zone of column plate/filler (20) bottom is then entrainmented by the fluid of high-velocity jet by the low pressure area of self-priming apparatus (13) at the injector nozzle place by catch tray (37) and continues reaction in the reactor;
After step 4. reaction is carried out 0.2-2 hour, liquid phase reacting material is by valve (14) beginning discharging, entering distillation system (31) separates, acetic acid and 2-butyl acetate separate the mode that adopts azeotropic distillation mode or conventional distillation, if adopt the azeotropic distillation mode, entrainer adds from entrainer inlet (32), azeotrope enters the water-and-oil separator (36) from cat head, acetic acid at the bottom of rectifying tower (31) tower and liquid acid then turn back to spray and continue reaction in the collision stream tower reactor (3), water in the water-and-oil separator then continues to use as entrainer, the 2-butyl acetate crude product on upper strata then enters into rectifying tower (33) and makes with extra care, the by product of rectifying tower (33) cat head turns back to and sprays the generation that suppresses side reaction in the collision stream tower reactor (3), it is 2-butyl acetate more than 99.99% that discharge port at the bottom of the tower (34) obtains purity, simultaneously, the acetic acid raw material also begins from pipeline (1) toward spraying the interior charging of collision stream tower reactor (3), C4 gas mixture or butylene then enter from pipeline (2) continuously, to guarantee the quality of material conservation of whole production system, whole thus technology enters into the production phase of steady and continuous.
2. the technology of continuous production 2-butyl acetate according to claim 1 is characterized in that: the described temperature of reaction of step 1 is 70-130 ℃.
3. the technology of continuous production 2-butyl acetate according to claim 1 is characterized in that: the described catalyst consumption of step 1 is the 2%-5% of acetic acid mass percent.
4. the technology of continuous production 2-butyl acetate according to claim 1 is characterized in that: step 3 is described after reaction is carried out 0.2-0.8 hour, Open valve (28).
5. the technology of continuous production 2-butyl acetate according to claim 1 is characterized in that: step 4 is described after reaction is carried out 0.5-1.5 hour, and liquid phase reacting material is by valve (14) beginning discharging.
6. the technology of continuous production 2-butyl acetate according to claim 1 is characterized in that: after the operation regular hour, loss or active decline have appearred in the solid-phase catalyst in the solid-liquid mixing acid, need add or change solid catalyst, and its step is as follows:
Step 1 '. open and spray collision stream tower reactor (3) bottom and lead to valve (23) on catalyzer solid-liquid separation tank (15) pipeline and catalyzer solid-liquid separation tank (15) and lead to valve (24) on tundish (17) pipeline, be provided with high efficiency filter (16) in the catalyzer solid-liquid separation tank (15), solid catalyst particle is trapped in the filter screen upstream by filter screen in the feed liquid, the liquid phase feed liquid is then got back to tundish (17) by valve (24), turns back to through pump (18) then and sprays in the collision stream tower reactor (3);
After step 2 ' if. change solid catalyst, then treat step 1 ' is sprayed catalyzer in the collision stream tower reactor (3) and emptied, open the loam cake of catalyst feeding device (19), add live catalyst, close the catalyst feeding device loam cake then;
Step 3 '. open valve (26) and valve (27), valve-off (30), catalyzer will enter with acetic acid and spray in the collision stream tower reactor (3), and then open valve (30), valve-off (26) and valve (27);
Step 4 '. valve-off (23) and valve (24), open valve 26 and 27 then, valve-off 30 is removed the catalyzer that lost efficacy in catalyzer solid-liquid separation tank (15), and catalyzer replacing process is finished.、
7. the specific equipment of a continuous production 2-butyl acetate technology according to claim 1 sprays collision stream tower reactor (3), it is characterized in that: it is made up of two portions, the bottom is divided into sprays collision stream conversion zone, top is divided into the tower conversion zone of column plate/filler (20), in spraying collision stream conversion zone, injector (4) is arranged at the top, self-priming apparatus (13) is arranged on the top jet device (4), and acetic acid inlet tube (1) and catalyst feeding device (19), C4 or butylene inlet tube (2) are arranged at the bottom, C4 or butylene inlet tube (2) gas distributor (5) interior with spraying collision stream conversion zone links to each other, the liquid that responds on lower sides outlet, before the reaction solution outlet, strainer (6) is arranged, reaction solution outlet passing through valve, impeller pump (8), under meter (9) links to each other with injector (4) with interchanger (10), spray collision stream conversion zone bottom ejector (7) and reaction solution outlet and control of export valve (23) are arranged, ejector (7) links to each other with impeller pump (8) outlet as bypass line with pipeline by valve (22), the gas distributor (21) that injection collision stream conversion zone top has pipeline process by-pass valve control (28) and injection to collide in the tower conversion zone of column plate/filler (20) on stream tower reactor top links to each other, catch tray (37) is arranged at the tower conversion zone of column plate/filler (20) bottom, the top has pipeline to pass through interchanger (11) to link to each other with pneumatic outlet (12), the discharging reaction end gas.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102344364A (en) * | 2011-11-24 | 2012-02-08 | 长春工业大学 | Method for producing sec-butyl acetate by synthesizing acetic acid and mixed C4 |
| CN103058860A (en) * | 2013-01-04 | 2013-04-24 | 宜兴市恒兴精细化工有限公司 | System for producing ethyl butyrate continuously |
| CN103506151A (en) * | 2012-06-15 | 2014-01-15 | 中国石油化工股份有限公司 | Catalyst for preparation of sec-butyl acetate from C4 olefins |
| CN103755950A (en) * | 2014-01-16 | 2014-04-30 | 南京红宝丽股份有限公司 | Continuous preparation method of flame retardant polyether polyol |
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| CN101100425A (en) * | 2007-06-26 | 2008-01-09 | 王伟 | Process for synthesizing acetic ester |
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| CN102344364A (en) * | 2011-11-24 | 2012-02-08 | 长春工业大学 | Method for producing sec-butyl acetate by synthesizing acetic acid and mixed C4 |
| CN103506151A (en) * | 2012-06-15 | 2014-01-15 | 中国石油化工股份有限公司 | Catalyst for preparation of sec-butyl acetate from C4 olefins |
| CN103506151B (en) * | 2012-06-15 | 2016-02-24 | 中国石油化工股份有限公司 | C 4 olefin prepares 2-butyl acetate catalyst |
| CN103058860A (en) * | 2013-01-04 | 2013-04-24 | 宜兴市恒兴精细化工有限公司 | System for producing ethyl butyrate continuously |
| CN103755950A (en) * | 2014-01-16 | 2014-04-30 | 南京红宝丽股份有限公司 | Continuous preparation method of flame retardant polyether polyol |
| CN106552668A (en) * | 2015-09-25 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of method of modifying of cation exchange resin catalyst and its application |
| CN106554275A (en) * | 2015-09-25 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of method comprehensively utilized by C-4-fraction after ether |
| CN106552668B (en) * | 2015-09-25 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of method of modifying of cation exchange resin catalyst and its application |
| CN105348090A (en) * | 2015-11-27 | 2016-02-24 | 江门谦信化工发展有限公司 | Green circulation production process for acetate |
| CN107434767A (en) * | 2016-05-27 | 2017-12-05 | 中国石油化工股份有限公司 | A kind of method that cyclohexanol and cyclohexyl acetate are prepared using cyclohexene and acetic acid |
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