CN103787878A - Method for preparing sec-butyl acetate from acetic acid and n-butene - Google Patents
Method for preparing sec-butyl acetate from acetic acid and n-butene Download PDFInfo
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- CN103787878A CN103787878A CN201210427678.9A CN201210427678A CN103787878A CN 103787878 A CN103787878 A CN 103787878A CN 201210427678 A CN201210427678 A CN 201210427678A CN 103787878 A CN103787878 A CN 103787878A
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- acetic acid
- reaction
- butene
- sulfone
- butyl acetate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
Abstract
The invention discloses a method for preparing sec-butyl acetate from acetic acid and n-butene. The method is as below: n-butene, a reaction solvent and acetic acid are subjected to an addition reaction by a fixed bed reactor equipped with a strong acidic cation exchange resin catalyst at the reaction temperature of 80-200 DEG C and reaction pressure of 1.0MPa-6.0MPa, with liquid hourly volume space velocity of acetic acid of 0.1-4 / h, and with the molar ratio of n-butene and acetic acid of 1.0:1-5.0:1; and the reaction solvent is one or more of sulfone compounds, and the addition of the sulfone compounds is 0.05-6 mass% of n-butene. The method uses the ion exchange resin catalyst, and the reaction solvent is added in the reaction raw materials to facilitate uniform mixing and fully contact of the reactants, thereby solving the problem of low reaction efficiency due to poor intersolubility of acetic acid and n-butene, and increasing the conversion rate of acetic acid under the same reaction conditions.
Description
Technical field
The present invention relates to a kind of method of being prepared 2-butyl acetate by acetic acid and n-butene, relating to specifically a kind of employing ion exchange resin is catalyzer, adds the method for the fixed bed continuous production 2-butyl acetate of reaction solvent in reaction raw materials n-butene and acetic acid.
Background technology
N-BUTYL ACETATE is a kind of good organic solvent, and it is widely used in nitrocotton, coating, leatheroid, medicine, ink and plastics industry.N-BUTYL ACETATE has four kinds of isomer: n-butyl acetate, 2-butyl acetate, isobutyl acetate and tert-butyl acetate.
In recent years, due to environmental requirement increasingly stringent, be restricted just gradually containing the use of the toxic substance solvents such as benzene, toluene, hydrochloric ether, the consumption of ester class environmentally friendly solvent sharply increases.At present, on market, N-BUTYL ACETATE series products is take n-butyl acetate as main, and n-butyl acetate oil carries out esterification preparation by propyl carbinol and acetic acid, and production cost is higher.Therefore, domestic and international many companies are developing one after another 2-butyl acetate and are substituting n-butyl acetate.
Character and the n-butyl acetate of 2-butyl acetate are close, are liquid colourless, inflammable, that have fruit fragrance, water insoluble, can be miscible with ethanol, ether.Can be widely used in paint, plastics, medicine and perfume industry, also can be used for doing the components such as extraction agent, dewatering agent and metal cleaner simultaneously.
2-butyl acetate preparation technology has two kinds: (1) acid alcohol esterification technique; (2) carboxylic acid/alkene esterification technique.
(1) acid alcohol esterification technique: take acetic acid and propyl carbinol or sec-butyl alcohol as raw material, prepare 2-butyl acetate using sulfuric acid or other strong acid as catalyzer.Belong to traditional technology, this explained hereafter 2-butyl acetate of industrial most employing;
(2) carboxylic acid/alkene esterification technique: adopting butylene (butene-1 and butene-2) and acetic acid is raw material, prepares 2-butyl acetate through addition reaction.A large amount of by-products of this process using refinery, cheap alkene are as raw material, the utilization ratio that improves Butene, reduces production costs greatly, significantly improves economic benefit, and in reaction process, a part acetic acid reacts generation a part 2-butyl acetate with a part butene-1 (or butene-2), do not have other unnecessary materials to produce, non-environmental-pollution, belongs to green chemical industry technique, reaction scheme is short, separate relatively easily, save energy, energy consumption is only 50% left and right of traditional technology.
Chinese patent CN1844076A, take sulfuric acid as catalyzer, produces N-BUTYL ACETATE with reaction rectification method, uses sulphur acid as catalyst, will inevitably cause corrosion to equipment, and discharges a large amount of acid-bearing wastewaters, and problem of environmental pollution is serious.
Chinese patent CN184187C discloses with super acids SO
4 2-/ Fe
2o
3-ZrO
2-SiO
2for catalyzer, prepared the method for 2-butyl acetate by acetic acid and butanols reaction.Acetic acid and butanols have water to generate in esterification, and water not only can cause the hydrolysis of ester, and super acidic catalyst is in reaction process, SO
4 2-easily run off, cause catalyst deactivation, and catalyzer after inactivation is difficult to regeneration.
Above-mentioned patent adopts acid alcohol esterification technique, and the waste water that its production cost is high, equipment corrosion is serious, side reaction is many, product separation is difficult, produce causes environmental pollution, and wastewater treatment is loaded down with trivial details.
The research of 2-butyl acetate mainly concentrates on carboxylic acid/alkene esterification technique (acetic acid and butylene direct esterification technique) at present.This process using heteropolyacid, as catalyzer, has higher activity, and is difficult for inactivation, in the direct esterification reaction of acetic acid and butylene, obtain application, but due to the generation along with ester in reaction process, heteropolyacid is separated out gradually from solution, causes the Efficiency Decreasing of catalyzer.This process using Zeo-karb and modified cation-exchange resin are as follows as the bibliographical information of catalyzer.
US5457228 disclose a kind of take acidic cation-exchange resin as catalyzer, butylene and acetic acid carries out the technique of circulating reaction in fixed-bed reactor.Be 70 ℃～120 ℃ in temperature of reaction, reaction pressure is 25 kg/cm～50kg/cm
2, the mol ratio of acetic acid and butylene is 1.0:1～2.0:1, air speed (LHSV) is 0.1 h
-1～10.0h
-1under condition, butene conversion is more than 68.6%, and the selectivity of 2-butyl acetate reaches more than 89.5%.In this method, product mixtures is successively after recycle pump and interchanger, and a part of product mixtures is sent to separation circuit below, and another part product mixtures is sent into reactor as recycle feed together with fresh feed.Reaction mass circulates into reactor, and olefinic polymerization tendency is increased, and affects product and purifies, and use recycle pump and interchanger, increases energy consumption.U.S. Pat 6018076A, US5994578 and Russ P RU2176239 have reported the method that generates N-BUTYL ACETATE with acidic ion exchange resin catalysis acetic acid and iso-butylene.
CN101121656A discloses a kind of method by acetic acid and the acetic acid synthesized secondary butyl ester of linear butylene, and the method adopts fixed-bed reactor, uses solid catalyst, acetic acid is reacted under the condition of gas-liquid-solid phase reaction to acetic acid synthesized secondary butyl ester with butylene.Adopt composite resin catalyzer, at 90 ℃～160 ℃ of temperature of reaction, pressure 2kg/cm
2～15kg/cm
2, acetic acid air speed 1.0h
-1～1.8h
-1, the mol ratio of acetic acid and butylene is that under 1:1.15～1:1.80 condition, the transformation efficiency of acetic acid can remain on more than 60%.This characteristic feature of an invention is to adopt fixed-bed process and solid catalyst, can overcome the existing equipment corrosion of traditional technology, side reaction and the reluctant problem of waste reaction solution at all.
CN101168505A has proposed a kind of method of preparing 2-butyl acetate, adopt strong-acid ion exchange resin to make catalyzer, in catalytic distillation tower, react, tower top pressure is controlled at 0.30 MPa～1.20MPa, 40 ℃～90 ℃ of tower top temperatures, temperature 50 C～150 ℃, conversion zone middle part, 140 ℃～220 ℃ of tower reactor temperature, reflux ratio is 0.1～10, and the mol ratio of acetic acid and butylene is 0.7:1～3.0:1, and acetic acid charging air speed is 0.1 h
-1～10.0h
-1, acetic acid transformation efficiency is more than 60%.The advantage of this invention is to adopt catalytic distillation technology to carry out acetic acid and mixed C
4esterification, product separating technique simplify, acetic acid recycling capable of circulation.
Chinese patent CN 101402566A provides a kind of method of preparing high-purity low-class fat vinegar, adopt appropriate water or C1～C6 alcohol as reaction control agent, C2～C6 alkene and the organic shuttle acid of C1～C5 are passed in the reactive system that strongly acidic catalyst is housed and carries out addition reaction, generate low-grade fatty acid ester.
Chemical engineer has reported and has used SnCl the 3rd phase in 2007
4nature-changed cation resin catalyst, to solve the inactivation problem of catalyzer, but its transformation efficiency has only reached 70%, and catalyzer cost is higher.
Fine chemistry industry the 5th phase in 2000 has been reported 2-butyl acetate synthesis technique, adopting Zeo-karb is the experiment that catalyzer has synthesized 2-butyl acetate in stirring tank, 100 ℃～200 ℃ of temperature of reaction, reaction pressure 1.5MPa～2.5 MPa, n-butene content is 80%, olefin(e) acid mass ratio is under the condition of 1.3:1, and the transformation efficiency of acetic acid is 50%～80%.
Above-mentioned patent and bibliographical information, unmodified Zeo-karb thermostability is poor, and in the time that temperature of reaction raises, its active ingredient (sulfonic acid group) easily runs off, and causes catalyst deactivation, and the non-renewable life-span of catalyzer is shorter; And nature-changed cation resin catalyst, catalyzer cost is higher; Add the 3rd component as conditioning agent, reaction conversion ratio is still lower.
In a word, from above-mentioned patent and bibliographical information, prepare 2-butyl acetate reaction by acetic acid and n-butene addition and still exist the problem that reaction conversion ratio is lower at present.
Summary of the invention
For the problem of the acetic acid low conversion rate existing in prior art, the invention provides a kind of method of being prepared 2-butyl acetate by acetic acid and butylene.Adopt ion-exchange resin catalyst, by add reaction solvent in reaction raw materials, reactant is mixed, contact more fully, solved acetic acid and n-butene mutual solubility is poor, cause the problem that reaction efficiency is low, under identical reaction conditions, improve acetic acid transformation efficiency.
A kind of method of being prepared 2-butyl acetate by acetic acid and n-butene, comprise following content: n-butene, reaction solvent and acetic acid carry out addition reaction by the fixed-bed reactor that strong acid cation exchange resin catalyst is housed, described reaction solvent is one or more in sulfone compound, the add-on of sulfone compound is 0.05%～6.0% of n-butene quality, is preferably 0.5%～1.5%.
In the inventive method, temperature of reaction is 80 ℃～200 ℃, and reaction pressure is 1.0MPa～6.0MPa.When the liquid of acetic acid, volume space velocity is 0.1h
-1～4h
-1, the mol ratio of n-butene and acetic acid is 1.0:1～5.0:1.
In the inventive method, temperature of reaction is preferably 100 ℃～160 ℃, and reaction pressure is preferably 2.5MPa～5.0MPa.When the liquid of acetic acid, volume space velocity is preferably 0.5h
-1～2.0h
-1, the mol ratio of n-butene and acetic acid is preferably 2.0:1～4.0:1.
In the inventive method, sulfone compound is one or more in tetramethylene sulfone, 2-methyl sulfolane, 3-methyl sulfolane, 3-propyl group tetramethylene sulfone, 3-butyl tetramethylene sulfone, dimethyl sulfone, ethyl sulfone, the first and second sulfones, dipropyl sulfone, wherein preferred tetramethylene sulfone, dimethyl sulfone.
In the inventive method, catalyzer is storng-acid cation exchange resin, can use commercial goods, also can be by existing method preparation, the DA-330 type high-temperature cation-exchange resin catalyzer of specifically producing as Dandong Mingzhu Special Type Resin Co., Ltd..Preferably select the storng-acid cation exchange resin that uses ordinary method modification.
Find through research, prepare 2-butyl acetate reaction mechanism by acetic acid and n-butene addition as follows: under an acidic catalyst effect, reaction raw materials acetic acid is preferentially adsorbed on catalyst surface, and form one deck acetic acid molecule liquid film at catalyst surface.When n-butene molecular diffusion is behind liquid film surface, must penetrate this layer of liquid film and be adsorbed on catalyst surface with chemical adsorption states form, regeneration carbonium ion and acetic acid generation electrophilic addition reaction.React from prepared 2-butyl acetate by acetic acid and n-butene addition the raw material physical property adopting, acetic acid and n-butene mutual solubility are poor, no matter reaction process adopts gas and liquid phase reaction or liquid-liquid phase reaction, exist gas phase and could contact with catalyzer and react or two kinds of raw materials of acetic acid and n-butene contact inadequate problem by liquid film, cause that speed of reaction is lower and acetic acid transformation efficiency is lower.
The present invention has added one or more in sulfone class reaction solvent in reaction process.Under suitable reaction conditions, in the time having a small amount of sulfone class reaction solvent to exist, improve the mutual solubility of n-butene and acetic acid, make catalyst surface seldom form acetic acid molecule liquid film or make the acetic acid thinning of liquid film forming, thereby reduce the resistance of n-butene to catalyst surface diffusion, increased the formation of carbonium ion, improved the addition reaction speed of acetic acid and n-butene, thus improved under the same conditions acetic acid transformation efficiency and.
Embodiment
Below by embodiment, the present invention is described further.
Embodiment 1 ~ 20
The acetic acid synthesized secondary butyl ester of n-butene and acetic acid reaction is to carry out in the stainless steel fixed-bed reactor of Φ 18mm × 1200mm, in reactor, pack the DA-330 type heatproof resin catalyst that 30ml Dandong Mingzhu Special Type Resin Co., Ltd. produces into, reactor head and bottom, be respectively charged into the quartz sand that diameter is Φ 0.5mm～1.2mm, after reactor installs, with nitrogen replacement three times, and tightness test is qualified, by n-butene, acetic acid and sulfone compound, send into preheater with volume pump according to the ratio of defined, material is preheating to 70 ℃～170 ℃.Material after preheating enters fixed-bed reactor and carries out addition reaction, and temperature of reaction is controlled at 100 ℃～200 ℃, and reaction pressure is controlled at 1.0MPa～5.0MPa, recycles unreacted material.The reaction conditions of embodiment 1～20 is in table 1, and reaction result is shown in 2.
Table 1 embodiment 1 ~ 20 reaction conditions
Table 2 embodiment 1 ~ 20 reaction result
| Sequence number | Acetic acid transformation efficiency/% | 2-butyl acetate selectivity/% |
| Embodiment 1 | 84.3 | 96.3 |
| Embodiment 2 | 86.7 | 98.4 |
| Embodiment 3 | 91.1 | 97.1 |
| Embodiment 4 | 93.8 | 98.8 |
| Embodiment 5 | 90.2 | 98.1 |
| Embodiment 6 | 88.1 | 97.2 |
| Embodiment 7 | 89.2 | 97.8 |
| Embodiment 8 | 91.4 | 98.1 |
| Embodiment 9 | 90.1 | 89.2 |
| Embodiment 10 | 85.2 | 97.6 |
| Embodiment 11 | 94.2 | 98.4 |
| Embodiment 12 | 87.8 | 88.1 |
| Embodiment 13 | 92.8 | 97.5 |
| Embodiment 14 | 90.2 | 96.8 |
| Embodiment 15 | 91.6 | 97.1 |
| Embodiment 16 | 86.6 | 97.9 |
| Embodiment 17 | 90.1 | 97.2 |
| Embodiment 18 | 89.0 | 97.4 |
| Embodiment 19 | 89.1 | 98.1 |
| Embodiment 20 | 91.5 | 96.5 |
Embodiment 21
N-butene, acetic acid and reaction solvent tetramethylene sulfone are sent into preheater by volume pump ratio as requested, and the reaction mass after preheating enters above-mentioned fixed-bed reactor and carries out addition reaction.Be 110 ℃ in temperature of reaction, reaction pressure is 3.0MPa, and when the liquid of acetic acid, volume space velocity is 2.0h
-1, the mol ratio of n-butene and acetic acid is 3.0:1, reaction solvent tetramethylene sulfone add-on is acetic acid synthesized secondary butyl ester under 1.0% condition of butylene quality, continuous operation 1000 hours.
Operation result shows, reacts initial, and the transformation efficiency of acetic acid is 93.1%, and the selectivity of 2-butyl acetate is 98.4%; Turn round after 1000 hours, the transformation efficiency of acetic acid is 92.0%, and the selectivity of 2-butyl acetate is 98.0%.
Embodiment 22
Reaction solvent dimethyl sulfone add-on is 0.5% of butylene quality, and temperature of reaction is 120 ℃, and reaction pressure is 4.0MPa, and when the liquid of acetic acid, volume space velocity is 3.0h
-1, the mol ratio of n-butene and acetic acid is 2.0:1, acetic acid synthesized secondary butyl ester under condition, continuous operation 1000 hours.
Operation result shows, the transformation efficiency reaction of acetic acid is initially 94.0%, turns round and still keeps more than 92.0% after 1000 hours, and the selectivity of 2-butyl acetate remains on more than 98.0%.
Comparative example 1
In reaction raw materials, add water as reaction solvent, it is acetic acid synthesized that n-butene and acetic acid carry out addition reaction
Secondary butyl ester, all the other conditions are with embodiment 22.
Operation result shows, water is during as reaction solvent, and the initial transformation efficiency of n-butene is 81.6%, turns round after 1000 hours, and n-butene transformation efficiency drops to below 74.5%, and 2-butyl acetate selectivity drops to below 90.0%.
Comparative example 2
In reaction raw materials, add ethanol as reaction solvent, n-butene and acetic acid carry out the acetic acid synthesized secondary butyl ester of addition reaction, and all the other conditions are with embodiment 22.
Operation result shows, ethanol is during as reaction solvent, and the initial transformation efficiency of n-butene is 82.5%, turns round after 1000 hours, and n-butene transformation efficiency drops to 76.1%, and 2-butyl acetate selectivity drops to below 92.0%.
Comparative example 3 ~ 7
In reaction raw materials, do not add any reaction solvent, n-butene and acetic acid carry out the acetic acid synthesized secondary butyl ester of addition reaction, and the reaction conditions of comparative example 3～7 is in table 3, and reaction result is shown in 4.
Table 3 comparative example 3 ~ 7 reaction conditionss
| Sequence number | Temperature of reaction/℃ | Reaction pressure/MPa | Acetic acid air speed/h -1 | Butylene/acetic acid/mol |
| Comparative example 3 | 100 | 4.0 | 1.0 | 2:1 |
| Comparative example 4 | 180 | 6.0 | 4.0 | 4:1 |
| Comparative example 5 | 80 | 1.5 | 0.2 | 1:1 |
| Comparative example 6 | 120 | 5.0 | 2.5 | 3:1 |
| Comparative example 7 | 160 | 3.5 | 1.5 | 5:1 |
Table 4 comparative example 3 ~ 7 reaction results
| Sequence number | Acetic acid transformation efficiency/% | 2-butyl acetate selectivity/% |
| Comparative example 3 | 65.1 | 87.1 |
| Comparative example 4 | 68.2 | 88.2 |
| Comparative example 5 | 72.1 | 84.5 |
| Comparative example 6 | 74.3 | 86.8 |
| Comparative example 7 | 66.9 | 84.3 |
Comparative example 8
In reaction raw materials, do not add any reaction solvent, temperature of reaction is 120 ℃, and reaction pressure is 5.0MPa, and when the liquid of acetic acid, volume space velocity is 2.5h
-1, the mol ratio of n-butene and acetic acid is under 3.0:1 condition, n-butene and acetic acid carry out the acetic acid synthesized secondary butyl ester of addition reaction, continuous operation 1000 hours.
Operation result shows, the initial conversion of acetic acid is 74.3%, and the selectivity of 2-butyl acetate remains on 86.8%; Turn round 1000 hours, the transformation efficiency of acetic acid drops to 40.6%, and the selectivity of 2-butyl acetate is 83.2%.
Claims (10)
1. prepared the method for 2-butyl acetate by acetic acid and n-butene for one kind, comprise following content: n-butene, reaction solvent and acetic acid carry out addition reaction by the fixed-bed reactor that strong acid cation exchange resin catalyst is housed, it is characterized in that: described reaction solvent is one or more in sulfone compound, the add-on of sulfone compound is 0.05%～6.0% of n-butene quality.
2. method according to claim 1, is characterized in that: the add-on of described sulfone compound is 0.5%～1.5% of n-butene quality.
3. method according to claim 1, is characterized in that: temperature of reaction is 80 ℃～200 ℃, and reaction pressure is 1.0MPa～6.0MPa.
4. method according to claim 3, is characterized in that: temperature of reaction is 100 ℃～160 ℃, and reaction pressure is 2.5MPa～5.0MPa.
5. method according to claim 1, is characterized in that: when the liquid of acetic acid, volume space velocity is 0.1h
-1～4h
-1, the mol ratio of n-butene and acetic acid is 1.0:1～5.0:1.
6. method according to claim 6, is characterized in that: when the liquid of acetic acid, volume space velocity is 0.5h
-1～2.0h
-1, the mol ratio of n-butene and acetic acid is 2.0:1～4.0:1.
7. method according to claim 1, is characterized in that: described sulfone compound is one or more in tetramethylene sulfone, 2-methyl sulfolane, 3-methyl sulfolane, 3-propyl group tetramethylene sulfone, 3-butyl tetramethylene sulfone, dimethyl sulfone, ethyl sulfone, the first and second sulfones, dipropyl sulfone.
8. method according to claim 7, is characterized in that: described sulfone compound is tetramethylene sulfone, dimethyl sulfone.
9. method according to claim 1, is characterized in that: strong acid cation exchange resin catalyst uses commercial goods or prepares by existing method.
10. according to the method described in claim 1 or 9, it is characterized in that: the storng-acid cation exchange resin that uses ordinary method modification is selected in storng-acid cation exchange resin catalysis.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100425A (en) * | 2007-06-26 | 2008-01-09 | 王伟 | Process for synthesizing acetic ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100425A (en) * | 2007-06-26 | 2008-01-09 | 王伟 | Process for synthesizing acetic ester |
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Application publication date: 20140514 |