CN102911044B - Method for preparing sec-butyl acetate via n-butene addition - Google Patents
Method for preparing sec-butyl acetate via n-butene addition Download PDFInfo
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- CN102911044B CN102911044B CN201110217520.4A CN201110217520A CN102911044B CN 102911044 B CN102911044 B CN 102911044B CN 201110217520 A CN201110217520 A CN 201110217520A CN 102911044 B CN102911044 B CN 102911044B
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- butylene
- butyl acetate
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Abstract
The present invention discloses a method for preparing sec-butyl acetate via n-butene addition. Addition reactions of n-butene, a reaction solvent and acetic acid are performed through a fixed bed reactor equipped with a strongly acidic cation-exchange resin catalyst, wherein the LHSV (liquid hourly space velocity) of the acetic acid is between 0.1h<-1> an 2h<-1>; the molar ratio of n-butene and acetic acid is between 1:1 and 5:1; the reaction temperature is from 60 DEGC to 160 DEG C; the reaction pressure is between 1.5MPa and 6.0MPa; the reaction solvent is one or more selected from C2 - C6 ester compounds; and the addition amount of the reaction solvent is 0.05% to 5% of butene by mass. Compared with the prior art, problems of low acetic acid conversion rate and low sec-butyl selectivity, which exist in the existing technology, are overcome according to the method, so that power consumption and production costs can be drastically reduced.
Description
Technical field
The invention discloses a kind of butylene addition and prepare the method for 2-butyl acetate, particularly, under storng-acid cation exchange resin exists, prepared the method for 2-butyl acetate by butylene addition.
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.2-butyl acetate is one of four kinds of isomer of N-BUTYL ACETATE, and it is the liquid that a class is colourless, inflammable, 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.
The operational path of current industrial production 2-butyl acetate is: acetic acid and sec-butyl alcohol be raw material, with sulfuric acid or other an acidic catalyst direct esterification system.The waste water that this explained hereafter cost is high, equipment corrosion is serious, side reaction is many, product separation is difficult, produce can cause environmental pollution.
US6018076A and US5994578 have reported that what generate with acidic ion exchange resin catalysis acetic acid and iso-butylene that the method RU2176239 of N-BUTYL ACETATE also uses is that acidic ion exchange resin is as catalyzer.CN101121656A discloses a kind of method with acetic acid and the acetic acid synthesized secondary butyl ester of linear butylene, adopt fixed-bed reactor, use solid catalyst, at butylene pressure is 90 ℃～160 ℃ of 0.2MPa～1.5MPa, temperature of reaction, make acetic acid under the condition of gas-liquid-solid phase reaction, react acetic acid synthesized secondary butyl ester with butylene: wherein acetic acid is with butylene than being 1:1.15～1.8, and acetic acid charging air speed is 1.0h
-1～1.8h
-1, drop to 56% through the transformation efficiency of 1000 hours running acetic acid by 70%.
" chemical engineer " the 3rd phase in 2007 has been reported and has used SnCl
4nature-changed cation resin catalyst, take butylene and acetic acid as the acetic acid synthesized secondary butyl ester of raw material, the transformation efficiency of acetic acid is brought up to 70% after modification by 35% before unmodified." 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%.
From above-mentioned patent and document, be not difficult to find, although people have taked various ways and measure, the transformation efficiency of acetic acid is lower all the time.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method that butylene and acetic acid are the acetic acid synthesized secondary butyl ester of raw material.In reaction system, add C
2～C
6one or more of ester compound, can improve the selectivity of transformation efficiency and the 2-butyl acetate of acetic acid.
The present invention comprises take butylene and acetic acid as the method for the acetic acid synthesized secondary butyl ester of raw material: n-butene (1-butylene and/or 2-butylene), reaction solvent and acetic acid carry out addition reaction by the fixed-bed reactor that strong acid cation exchange resin catalyst is housed, and when the liquid of acetic acid, volume space velocity is 0.1h
-1～2h
-1, the mol ratio of n-butene and acetic acid is 1:1～5:1, and temperature of reaction is 60 ℃～160 ℃, and reaction pressure is 1.5MPa～6.0MPa, and reaction solvent is C
2～C
6one or more of ester compound, reaction solvent add-on is 0.05%～5% of n-butene quality.
In above-mentioned reaction process, reaction conditions is preferably: when the liquid of acetic acid, volume space velocity is preferably 0.5h
-1～1.5h
-1, the mol ratio of n-butene and acetic acid is 1.5:1～3:1, and reaction solvent add-on is preferably 0.05%～2% of n-butene quality, and temperature of reaction is preferably 60 ℃～150 ℃, and reaction pressure is preferably 2.0MPa～5.0MPa.And the reaction conditions that override is selected is: when the liquid of acetic acid, volume space velocity is 0.5h
-1～1.0h
-1; The mol ratio of n-butene and acetic acid is 2.0:1～2.5:1, and reaction solvent add-on is 0.1%～1.0% of n-butene quality, 65 ℃～120 ℃ of temperature of reaction, reaction pressure 2.0MPa～3.0MPa.
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.
Reaction solvent is selected C
2～C
6one or more of ester compound, preferably acetic acid and C
2～C
4the acetic ester that forms of alcohol, specifically, as one or more in vinyl acetic monomer, propyl acetate, n-butyl acetate, 2-butyl acetate, Iso Butyl Acetate, tert-butyl acetate etc., be preferably 2-butyl acetate, add-on is 0.1%～0.5% of n-butene quality.
Compared with prior art, the present invention has added C in reactive system
2～C
6one or more of ester compound, under the reaction conditions of acetic acid and n-butene, due to the existence of a small amount of acetic acid esterified compound, 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, increase the formation of carbonium ion, improve the speed of addition reaction, thereby improve the speed of response of acetic acid and n-butene, can reach under the same conditions higher acetic acid transformation efficiency.
Embodiment
Below by specific embodiment, the present invention will be further described.Acetic acid transformation efficiency and 2-butyl acetate selectivity in embodiment and comparative example are calculated by following formula.
If * add 2-butyl acetate in reaction mass, need to deduct the amount of the 2-butyl acetate adding.
Embodiment 1-5
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 C
2～C
6ester compound, sends into preheater with volume pump according to the ratio of defined, and material is preheating to 70 ℃～170 ℃.Material after preheating enters fixed-bed reactor and carries out addition reaction, and controlling temperature of reaction is 60 ℃～160 ℃, and reaction pressure is 1.5MPa～6.0MPa.Unreacted n-butene recycles.
Embodiment 6-10
According to the method for embodiment 1, adopt the DA-330 type heatproof resin catalyst through ordinary method modification.
Embodiment 11-15
According to the method for embodiment 1, adopt the D-005 resin catalyst of commercial goods.
Embodiment 16-20
According to the method for embodiment 1, adopt commercially available D-72 resin catalyst.
Comparative example 1～4
According to the method for embodiment 1, in charging, do not add any reaction solvent.
Above used DA-330 type heatproof resin catalyst physico-chemical property is in table 1, and commercially available D-005 resin catalyst physical property is in table 2, and commercially available D-72 resin catalyst physical property is in table 3.
The reaction conditions of embodiment 1～20 and comparative example is in table 4, and reaction result is shown in 5.
Table 1 has been listed test DA-330 type heatproof resin catalyst physical property used.
| Sequence number | Index name | Technical indicator |
| 1 | Rate of small round spheres/% after mill | 95.57 |
| 2 | Exchange capacity/molL -1 | 1.48 |
| 3 | Water content/quality % | 52.51 |
| 4 | Wet volume density/gmL -1 | 0.81 |
| 5 | Wet true density/gmL -1 | 1.21 |
Table 2 has been listed test D-005 heatproof resin catalyst physical property used.
| Sequence number | Index name | Technical indicator |
| 1 | Mass exchange capacity, mmol/g[H +] | 5.34 |
| 2 | Wet true density, g/mL | 1.25 |
| 3 | Wet volume density, g/mL | 0.81 |
| 4 | Water content, % | 55.25 |
Table 3 has been listed test D-72 resin catalyst physical property used.
| Sequence number | Physical property | Technical indicator |
| 1 | Mass exchange capacity, mmol/g [H +] | 4.50 |
| 2 | Water content, % | 53.50 |
| 3 | Wet volume density, g/mL | 0.75 |
| 4 | Wet true density, g/mL | 1.25 |
The reaction conditions (1) of table 4-1 embodiment 1～20 and comparative example.
| Project | Temperature of reaction/℃ | Reaction pressure/MPa | Butylene/acetic acid/moL | Acetic acid air speed/h -1 |
| Embodiment 1 | 70 | 1.5 | 1:1 | 0.1 |
| Embodiment 2 | 85 | 2.5 | 2:1 | 0.5 |
| Embodiment 3 | 100 | 3.5 | 3:1 | 1.0 |
| Embodiment 4 | 110 | 4.5 | 4:1 | 1.5 |
| Embodiment 5 | 120 | 5.0 | 5:1 | 2.0 |
| Embodiment 6 | 60 | 2.0 | 1:1 | 0.3 |
| Embodiment 7 | 80 | 3.0 | 2:1 | 0.5 |
| Embodiment 8 | 100 | 4.0 | 3:1 | 1.0 |
| Embodiment 9 | 120 | 5.0 | 4:1 | 1.5 |
| Embodiment 10 | 140 | 6.0 | 5:1 | 2.0 |
| Embodiment 11 | 65 | 1.5 | 1:1 | 0.2 |
| Embodiment 12 | 85 | 3.5 | 2:1 | 0.5 |
| Embodiment 13 | 105 | 4.5 | 3:1 | 1.0 |
| Embodiment 14 | 125 | 5.5 | 4:1 | 1.5 |
| Embodiment 15 | 145 | 6.0 | 5:1 | 2.0 |
| Embodiment 16 | 80 | 2.0 | 1:1 | 0.2 |
| Embodiment 17 | 115 | 3.0 | 2:1 | 0.5 |
| Embodiment 18 | 140 | 1.5 | 3:1 | 1.0 |
| Embodiment 19 | 150 | 5.0 | 4:1 | 1.5 |
| Embodiment 20 | 160 | 6.0 | 5:1 | 2.0 |
| Comparative example 1 | 90 | 0.2 | 3:1 | 1.0 |
| Comparative example 2 | 110 | 0.5 | 3:1 | 1.0 |
| Comparative example 3 | 130 | 1.0 | 3:1 | 1.0 |
| Comparative example 4 | 150 | 1.5 | 3:1 | 1.0 |
The reaction conditions (2) of table 4-2 embodiment 1～20 and comparative example.
| Project | Reaction solvent kind (mass ratio) | Reaction solvent add-on, % |
| Embodiment 1 | Vinyl acetic monomer | 0.05 |
| Embodiment 2 | Propyl acetate | 0.1 |
| Embodiment 3 | Propyl acetate+N-BUTYL ACETATE (1:1) | 0.5 |
| Embodiment 4 | 2-butyl acetate | 1.0 |
| Embodiment 5 | N-butyl acetate | 3.0 |
| Embodiment 6 | Propyl acetate | 0.2 |
| Embodiment 7 | Vinyl acetic monomer | 0.3 |
| Embodiment 8 | N-butyl acetate | 0.4 |
| Embodiment 9 | 2-butyl acetate+n-butyl acetate (2:1) | 0.6 |
| Embodiment 10 | Iso Butyl Acetate | 0.8 |
| Embodiment 11 | N-butyl acetate | 0.5 |
| Embodiment 12 | Tert-butyl acetate | 1.0 |
| Embodiment 13 | 2-butyl acetate+vinyl acetic monomer (2:1) | 2.0 |
| Embodiment 14 | Vinyl acetic monomer | 3.0 |
| Embodiment 15 | Tert-butyl acetate | 5.0 |
| Embodiment 16 | N-butyl acetate+Iso Butyl Acetate (1:1) | 0.3 |
| Embodiment 17 | 2-butyl acetate | 0.6 |
| Embodiment 18 | Propyl acetate | 1.5 |
| Embodiment 19 | Vinyl acetic monomer | 2.5 |
| Embodiment 20 | Tert-butyl acetate | 4.5 |
| Comparative example 1 | - | - |
| Comparative example 2 | - | - |
| Comparative example 3 | - | - |
| Comparative example 4 | - | - |
The reaction result of the each embodiment of table 5 and comparative example.
| Project | Acetic acid transformation efficiency, % | 2-butyl acetate selectivity, % |
| Embodiment 1 | 85.5 | 92.3 |
| Embodiment 2 | 87.5 | 92.6 |
| Embodiment 3 | 90.6 | 90.3 |
| Embodiment 4 | 91.3 | 91.5 |
| Embodiment 5 | 93.4 | 90.2 |
| Embodiment 6 | 89.5 | 93.5 |
| Embodiment 7 | 90.5 | 91.7 |
| Embodiment 8 | 92.4 | 90.6 |
| Embodiment 9 | 94.5 | 90.5 |
| Embodiment 10 | 95.8 | 89.8 |
| Embodiment 11 | 86.5 | 89.5 |
| Embodiment 12 | 88.3 | 88.7 |
| Embodiment 13 | 93.2 | 92.3 |
| Embodiment 14 | 91.8 | 88.5 |
| Embodiment 15 | 92.3 | 89.8 |
| Embodiment 16 | 87.5 | 90.8 |
| Embodiment 17 | 90.9 | 90.5 |
| Embodiment 18 | 89.8 | 89.7 |
| Embodiment 18 | 90.6 | 88.4 |
| Embodiment 20 | 94.5 | 89.5 |
| Comparative example 1 | 68.3 | 88.5 |
| Comparative example 2 | 70.6 | 89.1 |
| Comparative example 3 | 74.5 | 85.1 |
| Comparative example 4 | 76.7 | 78.4 |
Can find out from above embodiment and comparative example data, the inventive method, owing to having added ester compound in reaction system, has increased the mutual solubility of butylene and acetic acid, and compared with the existing technique that does not use reaction solvent, transformation efficiency and selectivity obviously improve.
Claims (5)
1. the method for 2-butyl acetate is prepared in a butylene addition, butylene is 1-butylene and/or 2-butylene, it is characterized in that: butylene, reaction solvent and acetic acid carry out addition reaction by the fixed-bed reactor that strong acid cation exchange resin catalyst is housed, when the liquid of acetic acid, volume space velocity is 0.1h
-1～2h
-1, the mol ratio of butylene and acetic acid is 1:1～5:1, and temperature of reaction is 60 ℃～160 ℃, and reaction pressure is 1.5MPa～6.0MPa, and reaction solvent is selected acetic acid and C
2～C
4alcohol form acetic ester, reaction solvent add-on is 0.05%～5% of butylene quality.
2. it is characterized in that in accordance with the method for claim 1: when the liquid of acetic acid, volume space velocity is 0.5h
-1～1.5h
-1, the mol ratio of butylene and acetic acid is 1.5:1～3:1, and reaction solvent add-on is 0.05%～2% of butylene quality, and temperature of reaction is 60 ℃～150 ℃, and reaction pressure is 2.0MPa～5.0MPa.
3. it is characterized in that in accordance with the method for claim 1: when the liquid of acetic acid, volume space velocity is 0.5h
-1～1.0h
-1; The mol ratio of butylene and acetic acid is 2.0:1～2.5:1, and reaction solvent add-on is 0.1%～1.0% of butylene quality, 65 ℃～120 ℃ of temperature of reaction, reaction pressure 2.0MPa～3.0MPa.
4. it is characterized in that in accordance with the method for claim 1: reaction solvent is one or more in vinyl acetic monomer, propyl acetate, n-butyl acetate, 2-butyl acetate, Iso Butyl Acetate, tert-butyl acetate.
5. it is characterized in that in accordance with the method for claim 1: reaction solvent add-on is 0.1%～0.5% of butylene quality.
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|---|---|---|---|
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|---|---|---|---|
| CN201110217520.4A CN102911044B (en) | 2011-08-01 | 2011-08-01 | Method for preparing sec-butyl acetate via n-butene addition |
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| CN102911044B true CN102911044B (en) | 2014-06-25 |
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| CN104557523B (en) * | 2014-08-28 | 2016-11-23 | 丹东明珠特种树脂有限公司 | A kind of Catalyst packing method synthesizing sec-Butyl Acetate |
| CN110105208A (en) * | 2019-06-11 | 2019-08-09 | 中触媒新材料股份有限公司 | A method of preparing cyclohexyl acetate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5866714A (en) * | 1997-09-30 | 1999-02-02 | Arco Chemical Technology, L.P. | Ester preparation |
| WO1999054276A1 (en) * | 1998-04-16 | 1999-10-28 | Arco Chemical Technology, L.P. | Tertiary alkyl ester preparation |
| EP1050526A1 (en) * | 1999-05-07 | 2000-11-08 | SUMIKA FINE CHEMICALS Co., Ltd. | Process for preparing tert-alkyl ester from carboxylic acid |
| CN101007759A (en) * | 2007-02-02 | 2007-08-01 | 胡先念 | Preparation method of low-grade aliphatic ester |
| CN101948385A (en) * | 2010-07-12 | 2011-01-19 | 江门谦信化工发展有限公司 | Method for composing butyl acetate |
-
2011
- 2011-08-01 CN CN201110217520.4A patent/CN102911044B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5866714A (en) * | 1997-09-30 | 1999-02-02 | Arco Chemical Technology, L.P. | Ester preparation |
| WO1999054276A1 (en) * | 1998-04-16 | 1999-10-28 | Arco Chemical Technology, L.P. | Tertiary alkyl ester preparation |
| EP1050526A1 (en) * | 1999-05-07 | 2000-11-08 | SUMIKA FINE CHEMICALS Co., Ltd. | Process for preparing tert-alkyl ester from carboxylic acid |
| CN101007759A (en) * | 2007-02-02 | 2007-08-01 | 胡先念 | Preparation method of low-grade aliphatic ester |
| CN101948385A (en) * | 2010-07-12 | 2011-01-19 | 江门谦信化工发展有限公司 | Method for composing butyl acetate |
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