CN103044246A - Synthesis method of sec-butyl acetate - Google Patents
Synthesis method of sec-butyl acetate Download PDFInfo
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- CN103044246A CN103044246A CN2011103132827A CN201110313282A CN103044246A CN 103044246 A CN103044246 A CN 103044246A CN 2011103132827 A CN2011103132827 A CN 2011103132827A CN 201110313282 A CN201110313282 A CN 201110313282A CN 103044246 A CN103044246 A CN 103044246A
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Abstract
The invention relates to a synthesis method of sec-butyl acetate. Acetic acid and n-butene are used as raw materials to synthesize sec-butyl acetate. The catalyst is a composite supporter supporting heteropoly acid, wherein composite oxides are used as the supporter, and heteropoly acid is used as the active component, and the weight ratio of the heteropoly acid to the composite oxide supporter is 0.01:1-0.5:1; the composite oxide supporter is an aluminum-base composite oxide supporter; and the heteropoly acid comprises one or more of phosphotungstic acid, silicotungstic acid, arsenowolframic acid, germanotungtic acid, molybdophosphoric acid, silicomolybdic acid, arsenomolybdic acid, germanomolybdic acid and the like. The method provided by the invention solves the problems of catalyst deactivation and low conversion efficiency since the heteropoly acid structure in the supported heteropoly acid catalyst can be easily destroyed and the acid quantity in the supporter is reduced.
Description
Technical field
The present invention relates to a kind of synthetic method of 2-butyl acetate, particularly adopt the catalyzer of composite carrier load heteropolyacid, the method take acetic acid and n-butene as the acetic acid synthesized secondary butyl ester of catalytic material.
Technical background
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, and is water insoluble, can be miscible with ethanol, ether.Paint, plastics, medicine and perfume industry be can be widely used in, reactant medium, extraction agent, dewatering agent, and the component such as metal cleaner also can be used for simultaneously doing.Traditional method will certainly be brought the problems such as equipment corrosion and environmental pollution be serious take the vitriol oil as the Catalyst Production 2-butyl acetate.CN184187C is disclosed with super acids SO
4 2-/ Fe
2O
3-ZrO
2-SiO
2Be the reaction of catalyst acetic acid and butanols, because super acids is in reaction process, especially under the condition that has water to exist, SO
4 2-Run off easily the problem that has catalyst deactivation and be difficult to regenerate.
US6018076A and US5994578 have reported the method that generates N-BUTYL ACETATE with acidic ion exchange resin catalysis acetic acid and iso-butylene.What RU2176239 also used is that acidic ion exchange resin is as catalyzer.Resin catalyst brings catalyst deactivation and because the little and frangible problem of physical strength owing to sulfonic group runs off easily in reaction.
Heteropolyacid has higher activity as catalyzer, and is difficult for inactivation, has obtained application in the direct esterification of acetic acid and butylene reaction, but since in reaction process along with the generation of ester, heteropolyacid is separated out from solution gradually, causes the activity decreased of catalyzer.In order to address this problem, CN101293210A discloses take the single component porous medium as carrier loaded heteropolyacid catalyst, and is applied in the building-up reactions of 2-butyl acetate." petrochemical complex " the 12nd phase of the 36th volume in 2007 has been reported SiO
2Load phosphotungstic acid catalyst is used for the building-up reactions of 2-butyl acetate, and the structure of phospho-wolframic acid is damaged as a result, and L acid and B acid acid amount reduce on the catalyzer, and still exists the problem of catalyst deactivation.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of synthetic method of 2-butyl acetate, catalyzer is the catalyzer of composite carrier load heteropolyacid, it is good that the inventive method has good reactivity worth, particularly activity stability.
The synthetic method of 2-butyl acetate of the present invention comprises following content: take acetic acid and n-butene as the acetic acid synthesized secondary butyl ester of raw material, adopt the catalyzer of composite carrier load heteropolyacid, catalyzer is take composite oxides as carrier, take heteropolyacid as active ingredient, heteropolyacid and composite oxide carrier weight ratio are 0.01:1～0.5:1, be preferably 0.02:1～0.3:1, most preferably be 0.05:1～0.2:1.
In the catalyzer that the inventive method is used, composite oxide carrier is the aluminium base composite oxides carrier, is specially MgO-Al
2O
3Composite oxides, TiO
2-Al
2O
3Composite oxides or ZrO
2-Al
2O
3Composite oxides etc.
In the catalyzer that the inventive method is used, heteropolyacid comprises: one or more in phospho-wolframic acid, silicotungstic acid, arsenowolframic acid, germanotungstic acid, phospho-molybdic acid, silicomolybdic acid, arsenic molybdic acid and the germanium molybdic acid etc.
In the catalyzer that the inventive method is used, by weight alumina content is 60%～90% in the composite oxide carrier, is preferably 70%～80%.
In the catalyzer that the inventive method is used, prepare first composite oxide carrier, then the method for the conventional dipping of employing to composite oxide carrier, obtains final catalyzer with loaded by heteropoly acid.
In this forwarding method, in the reaction of acetic acid and the acetic acid synthesized secondary butyl ester of n-butene, temperature of reaction is 60 ℃～150 ℃, is preferably 70 ℃～120 ℃, most preferably is 80 ℃～90 ℃; Reaction pressure is 1MPa～6MPa, is preferably 2MPa～4MPa, most preferably is 3MPa～4MPa; The mol ratio of n-butene and acetic acid is 10:1～1:10, is preferably 5:1～1:2, most preferably is 4:1～2:1.Reaction can be adopted batch operation, also can operate continuously.During periodical operation, catalyzer accounts for 0.5%～15% of n-butene and the total weight of material of acetic acid, and is preferred 1%～12%, and most preferably 2%～10%, the reaction times is 0.5～10h, is preferably 1～2.5h.When adopting the operate continuously mode, volume space velocity is 0.1 h during the liquid of n-butene and the total material of acetic acid
-1～2h
-1, be preferably 0.4 h
-1～1 h
-1
Shockingly find through research, according to composite carrier load heteropolyacid catalyst provided by the present invention, be that the raw material addition reaction is produced in the reaction of 2-butyl acetate at acetic acid and n-butene, solved heteropolyacid and from solution, separated out gradually, the problem that causes catalyst activity to reduce, so that heteropolyacid has kept stable structure at carrier, L acid and B acid acid amount can not reduce substantially on the catalyzer, and therefore, catalyst stability is good, improve reaction efficiency, reduce production costs.
Embodiment
Composite oxide carrier in the catalyzer that the inventive method is used can adopt the coprecipitation method preparation of this area routine, such as the following method preparation of concrete employing.
MgO-Al
2O
3The preparation of composite oxides: an amount of magnesium nitrate and aluminum nitrate are mixed with aqueous solution a with deionized water, be configured to the aqueous solution (or using ammonia soln) b with deionized water and an amount of potassium hydroxide, under the state that stirs, solution b joined and carry out precipitin reaction among a, obtain white pasty state precipitation, through washing, filter after, dry, roasting makes the Mg-Al composite oxide carrier.
The precipitin reaction time in above-mentioned Mg-Al composite oxide carrier preparation process is 1 hour～7 hours, preferentially selects 2 hours～6 hours, and override was selected 3 hours～5 hours.Drying temperature is 70 ℃～150 ℃, preferentially selects 80 ℃～140 ℃, and override is selected 80 ℃～130 ℃.Be 6 hours～24 hours time of drying, preferentially selected 8 hours～16 hours, and override was selected 8 hours～14 hours.Maturing temperature is 200 ℃～900 ℃, preferentially selects 300 ℃～800 ℃, and override is selected 400 ℃～600 ℃.Roasting time is 2 hours～24 hours, preferentially selects 4 hours～20 hours, and override was selected 6 hours～10 hours, made the Mg-Al composite oxide carrier.
TiO
2-Al
2O
3The preparation of composite oxides: an amount of aluminum nitrate and titanium tetrachloride are mixed with solution c with deionized water, under the state that stirs, be added drop-wise to mentioned solution b and carry out precipitin reaction among the solution c, obtain white precipitate, through washing, filter after, dry, roasting makes titania-alumina mixed oxide.
The precipitin reaction time is 1 hour～10 hours in above-mentioned titania-alumina mixed oxide preparation process, preferentially selects 2 hours～8 hours, and override was selected 3 hours～5 hours.Drying temperature is 80 ℃～160 ℃, preferentially selects 90 ℃～140 ℃, and override is selected 100 ℃～130 ℃.Be 4 hours～24 hours time of drying, preferentially selected 6 hours～16 hours, and override was selected 8 hours～10 hours.Maturing temperature is 250 ℃～650 ℃, preferentially selects 300 ℃～600 ℃, and override is selected 350 ℃～550 ℃.Roasting time is 4 hours～24 hours, preferentially selects 6 hours～20 hours, and override was selected 8 hours～12 hours, made titania-alumina mixed oxide.
ZrO
2-Al
2O
3The preparation of composite oxides: an amount of aluminum nitrate and zirconium tetrachloride are mixed with solution d with deionized water, under the state that stirs, mentioned solution b is added to and carries out precipitin reaction among the solution d, obtain white precipitate, make the zirconia-alumina composite oxide carrier through washing, filtration, drying, roasting.
The precipitin reaction time in above-mentioned zirconia-alumina composite oxide carrier preparation process is 1 hour～10 hours, preferentially selects 2 hours～8 hours, and override was selected 3 hours～5 hours.Drying temperature is 60 ℃～180 ℃, preferentially selects 80 ℃～140 ℃, and override is selected 100 ℃～120 ℃.Be 2 hours～16 hours time of drying, preferentially selected 4 hours～12 hours, and override was selected 6 hours～8 hours.Maturing temperature is 250 ℃～850 ℃, preferentially selects 300 ℃～650 ℃, and override is selected 350 ℃～550 ℃.Roasting time is 4 hours～20 hours, preferentially selects 6 hours～16 hours, and override was selected 8 hours～10 hours, made the zirconia-alumina composite oxide carrier.
After obtaining the composite oxide carrier moulding, adopt the method for conventional dipping with on the heteropolyacid solution impregnation composite oxide carrier.Be 4 hours～24 hours with the dipping time of heteropolyacid solution impregnation composite oxide carrier, preferentially selected 6 hours～20 hours that override was selected 10 hours～16 hours.Macerate 60 ℃～160 ℃ lower dry 2～20 hours, preferentially select 70 ℃～140 ℃ lower dry 3～14 hours, override is selected at 80 ℃～120 ℃ lower dry 6～12 hours.Macerate made catalyzer in 2～10 hours 200 ℃～600 ℃ lower roastings, preferentially selected 250 ℃～500 ℃ lower roastings and made catalyzer in 3～8 hours, and override is selected 300 ℃～400 ℃ lower roastings and made composite oxide catalysts in 4～8 hours.Can adopt single-steeping or repeatedly the dipping, to obtain required loaded by heteropoly acid amount.
Embodiment 1
Get the 175g aluminum nitrate, the 39g magnesium nitrate is mixed with mixing solutions with deionized water, take ammonia soln as precipitation agent, coprecipitation reaction 3 hours, then filtration drying obtains solid support material, and dry after being shaped with conventional method extrusion, 450 ℃ of roastings obtained the Mg-Al composite oxide carrier in 3 hours.Be 10% phosphotungstic acid aqueous solution dipping 8 hours with weight concentration, 100 ℃ lower dry 8 hours, be prepared into catalyzer in 8 hours 350 ℃ of lower roastings again.Catalyzer is used for the reaction of acetic acid and the acetic acid synthesized secondary butyl ester of butylene, and reaction is carried out in autoclave, and temperature of reaction is 90 ℃, and reaction pressure is 3.5MPa, and the olefin(e) acid mol ratio is 3:1, and reaction result sees Table 1.
Embodiment 2
Get the 189g aluminum nitrate, the 19g titanium tetrachloride is mixed with mixing solutions with deionized water, and co-precipitation prepares titania-alumina mixed oxide, is shaped with conventional method extrusion, and other condition is identical with embodiment 1.Catalyzer is used for the reaction of acetic acid and the acetic acid synthesized secondary butyl ester of butylene, and reaction is carried out in autoclave, and temperature of reaction is 93 ℃, and reaction pressure is 3.6MPa, and the olefin(e) acid mol ratio is 3:1, and reaction result sees Table 1.
Embodiment 3
Get the 200g aluminum nitrate, the 10g zirconium tetrachloride is mixed with mixing solutions with deionized water, and coprecipitation method prepares the Mg-Al composite oxide carrier, and after being shaped with conventional method extrusion, other condition is identical with embodiment 1.Catalyzer is used for the reaction of acetic acid and the acetic acid synthesized secondary butyl ester of butylene, and reaction is carried out in autoclave, and temperature of reaction is 95 ℃, and reaction pressure is 3.8MPa, and the olefin(e) acid mol ratio is 3:1, and reaction result sees Table 1.
Embodiment 4
Get the 175g aluminum nitrate, the 39g magnesium nitrate, be mixed with mixing solutions with deionized water, coprecipitation method prepares the Mg-Al composite oxide carrier, after being shaped with the method extrusion of routine, be 15% silicon tungsten acid solution dipping 8 hours with concentration, 110 ℃ of lower dryings 6 hours, be prepared into catalyzer in 10 hours 400 ℃ of lower roastings again, other condition is with embodiment 1.Catalyzer is used for the reaction of acetic acid and the acetic acid synthesized secondary butyl ester of butylene, and reaction is carried out in autoclave, and temperature of reaction is 92 ℃, and reaction pressure is 3.5MPa, and the olefin(e) acid mol ratio is 3:1, and reaction result sees Table 1.
Embodiment 5
Get the 189g aluminum nitrate, the 19g titanium tetrachloride is mixed with mixing solutions with deionized water, and coprecipitation method prepares the Mg-Al composite oxide carrier, and after being shaped with conventional method extrusion, other process and condition are with embodiment 4.Catalyzer is used for the reaction of acetic acid and the acetic acid synthesized secondary butyl ester of butylene, and reaction is carried out in autoclave, and temperature of reaction is 92 ℃, and reaction pressure is 3.5MPa, and the olefin(e) acid mol ratio is 3:1, and reaction result sees Table 1.
Embodiment 6
Get the 200g aluminum nitrate, the 10g zirconium tetrachloride is mixed with mixing solutions with deionized water, and coprecipitation method prepares the Mg-Al composite oxide carrier, is shaped with conventional method extrusion, and other process is identical with embodiment 4 with condition.Catalyzer is used for the reaction of acetic acid and the acetic acid synthesized secondary butyl ester of butylene, and reaction is carried out in autoclave, and temperature of reaction is 95 ℃, and reaction pressure is 3.7MPa, and the olefin(e) acid mol ratio is 3:1, and reaction result sees Table 1.
Embodiment 7
Other condition is identical with embodiment 1, and it is 10% phosphorus molybdenum acid solution that dipping solution changes weight concentration into, and temperature of reaction is 92 ℃, and reaction pressure is 3.5MPa, and the olefin(e) acid mol ratio is 3:1, and reaction result sees Table 1.
Embodiment 8
Other conditions are identical with embodiment 2, and it is 10% phosphorus molybdenum acid solution that dipping solution changes weight concentration into, and temperature of reaction is 93 ℃, and reaction pressure is 3.6MPa, and the olefin(e) acid mol ratio is 3:1, and reaction result sees Table 1.
Embodiment 9
Other conditions are identical with embodiment 3, and it is 10% phosphorus molybdenum acid solution that dipping solution changes weight concentration into, and temperature of reaction is 90 ℃, and reaction pressure is 3.4MPa, and the olefin(e) acid mol ratio is 3:1, and reaction result sees Table 1.
Embodiment 10
Other conditions are identical with embodiment 4, and it is 15% silicomolybdic acid solution that dipping solution changes weight concentration into, and temperature of reaction is 92 ℃, and reaction pressure is 3.6MPa, and the olefin(e) acid mol ratio is 3:1, and reaction result sees Table 1.
Embodiment 11
Other conditions are identical with embodiment 5, and it is 15% silicomolybdic acid solution that dipping solution changes weight concentration into, and temperature of reaction is 95 ℃, and reaction pressure is 3.8MPa, and the olefin(e) acid mol ratio is 3:1, and reaction result sees Table 1.
Embodiment 12
Other conditions are identical with embodiment 6, and it is 10% germanotungstic acid acid solution that dipping solution changes weight concentration into, and temperature of reaction is 94 ℃, and reaction pressure is 3.6MPa, and the olefin(e) acid mol ratio is 3:1, and reaction result sees Table 1.
Embodiment 13
Other conditions are identical with embodiment 2, and it is 15% arsenic molybdenum acid solution that dipping solution changes weight concentration into, and temperature of reaction is 93 ℃, and reaction pressure is 3.6MPa, and the olefin(e) acid mol ratio is 3:1, and reaction result sees Table 1.
Comparative example 1
Be 5% phosphotungstic acid aqueous solution dipping Al with weight concentration
2O
3Carrier 8 hours, drying is 8 hours under 110 ℃, is prepared into catalyzer in 8 hours 400 ℃ of lower roastings again.Catalyzer is used for the reaction of embodiment 1, and temperature of reaction is 95 ℃, and reaction pressure is 3.9MPa, and the olefin(e) acid mol ratio is 3:1, and reaction result sees Table 1.
Comparative example 2
Be 5% phospho-molybdic acid aqueous solution dipping SiO with weight concentration
2Carrier 8 hours, drying is 8 hours under 110 ℃, is prepared into catalyzer in 8 hours 400 ℃ of lower roastings again.Catalyzer is used for the reaction of embodiment 1, and temperature of reaction is 94 ℃, and reaction pressure is 3.8MPa, and the olefin(e) acid mol ratio is 3:1, and reaction result sees Table 1.
The reaction result of table 1 embodiment and comparative example (transformation efficiency and selectivity are calculated with mole).
| Numbering | Catalyst property 1* | Catalyst property 2* | Acetic acid transformation efficiency first, % | Selectivity first, % | Repeat 5 times the acetic acid transformation efficiency, % | Repeat 5 times selectivity, % |
| Embodiment 1 | 80 | 1：32 | 87.2 | 95.3 | 87.1 | 96.1 |
| Embodiment 2 | 85 | 1：24 | 93.1 | 94.5 | 91.4 | 95.4 |
| Embodiment 3 | 90 | 1：24 | 90.5 | 94.4 | 90.3 | 95.5 |
| Embodiment 4 | 80 | 1：19 | 88.3 | 96.9 | 87.0 | 96.0 |
| Embodiment 5 | 85 | 1：19 | 92.6 | 95.7 | 91.4 | 94.3 |
| Embodiment 6 | 90 | 1：16 | 89.5 | 96.4 | 90.7 | 96.4 |
| Embodiment 7 | 80 | 1：32 | 79.8 | 93.2 | 71.8 | 95.7 |
| Embodiment 8 | 85 | 1：32 | 89.7 | 92.1 | 86.0 | 93.3 |
| Embodiment 9 | 90 | 1：19 | 87.9 | 96.0 | 82.2 | 97.1 |
| Embodiment 10 | 80 | 1：16 | 82.4 | 95.3 | 75.3 | 97.0 |
| Embodiment 11 | 85 | 1：13 | 86.1 | 91.7 | 86.4 | 96.6 |
| Embodiment 12 | 90 | 1：13 | 74.4 | 95.6 | 60.7 | 97.2 |
| Embodiment 13 | 85 | 1：16 | 75.5 | 95.2 | 63.0 | 96.7 |
| Comparative example 1 | / | 1：24 | 77.5 | 94.6 | 35.0 | 94.3 |
| Comparative example 2 | / | 1：32 | 71.4 | 95.0 | 41.0 | 94.5 |
* catalyst property 1: the weight percentage of aluminum oxide in the composite oxide carrier;
* catalyst property 2: heteropolyacid and composite oxide carrier weight ratio in the catalyzer.
Claims (10)
1. the synthetic method of a 2-butyl acetate, take acetic acid and n-butene as the acetic acid synthesized secondary butyl ester of raw material, it is characterized in that: the catalyzer that adopts the composite carrier load heteropolyacid, catalyzer is take composite oxides as carrier, take heteropolyacid as active ingredient, heteropolyacid and composite oxide carrier weight ratio are 0.01:1～0.5:1, composite oxide carrier is the aluminium base composite oxides carrier, and heteropolyacid comprises one or more in phospho-wolframic acid, silicotungstic acid, arsenowolframic acid, germanotungstic acid, phospho-molybdic acid, silicomolybdic acid, arsenic molybdic acid and the germanium molybdic acid etc.
2. it is characterized in that in accordance with the method for claim 1: heteropolyacid and composite oxide carrier weight ratio are 0.02:1～0.3:1.
3. it is characterized in that in accordance with the method for claim 1: heteropolyacid and composite oxide carrier weight ratio are 0.05:1～0.2:1.
4. it is characterized in that in accordance with the method for claim 1: composite oxide carrier is MgO-Al
2O
3Composite oxides, TiO
2-Al
2O
3Composite oxides or ZrO
2-Al
2O
3Composite oxides.
5. according to claim 1 or 4 described methods, it is characterized in that: by weight alumina content is 60%～90% in the composite oxide carrier.
6. according to claim 1 or 4 described methods, it is characterized in that: by weight alumina content is 70%～80% in the composite oxide carrier.
7. in accordance with the method for claim 1, it is characterized in that: in the catalyzer of composite carrier load heteropolyacid, prepare first composite oxide carrier, then the method for the conventional dipping of employing to composite oxide carrier, obtains final catalyzer with loaded by heteropoly acid.
8. in accordance with the method for claim 1, it is characterized in that: in the reaction of acetic acid and the acetic acid synthesized secondary butyl ester of n-butene, temperature of reaction is 60 ℃～150 ℃, and reaction pressure is 1MPa～6MPa, and the mol ratio of n-butene and acetic acid is 10:1～1:10.
9. according to claim 1 or 8 described methods, it is characterized in that: batch operation is adopted in reaction, and catalyzer accounts for 0.5%～15% of n-butene and the total weight of material of acetic acid, and the reaction times is 0.5～10h.
10. according to claim 1 or 8 described methods, it is characterized in that: the operate continuously mode is adopted in reaction, and volume space velocity is 0.1 h during the liquid of n-butene and the total material of acetic acid
-1～2h
-1
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358112A (en) * | 1999-06-03 | 2002-07-10 | 昭和电工株式会社 | Catalyst for use in producing lower fatty acid ester, process for producing the catalyst, and process for producing lower fatty acid ester using the catalyst |
| CN101293210A (en) * | 2007-04-25 | 2008-10-29 | 中国科学院大连化学物理研究所 | Composite catalyst for preparing sec-butyl acetate with direct esterification of ethyl ester and butylene |
| CN102909042A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Composite carrier loaded heteropoly acid catalyst and application thereof |
-
2011
- 2011-10-17 CN CN2011103132827A patent/CN103044246A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358112A (en) * | 1999-06-03 | 2002-07-10 | 昭和电工株式会社 | Catalyst for use in producing lower fatty acid ester, process for producing the catalyst, and process for producing lower fatty acid ester using the catalyst |
| CN101293210A (en) * | 2007-04-25 | 2008-10-29 | 中国科学院大连化学物理研究所 | Composite catalyst for preparing sec-butyl acetate with direct esterification of ethyl ester and butylene |
| CN102909042A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Composite carrier loaded heteropoly acid catalyst and application thereof |
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Application publication date: 20130417 |