CN102807922A - Preparation method for fatty acid ester - Google Patents
Preparation method for fatty acid ester Download PDFInfo
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- CN102807922A CN102807922A CN2011101435435A CN201110143543A CN102807922A CN 102807922 A CN102807922 A CN 102807922A CN 2011101435435 A CN2011101435435 A CN 2011101435435A CN 201110143543 A CN201110143543 A CN 201110143543A CN 102807922 A CN102807922 A CN 102807922A
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- alcohol
- monohydroxy
- preparation
- grease
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Abstract
The invention relates to a preparation method for a fatty acid ester. The method comprises that: oil and an alkaline catalyst-containing C1-C6 monohydric alcohol enter a tube type reactor from the lower part in a form of a liquid phase, and flow upward, wherein the tube type reactor is arranged vertically, a liquid hourly volume space velocity is 0.1-0.5 h<-1>; and a fatty acid ester is collected from the material obtained from an upper outlet. The method of the present invention has advantages of simple reaction device, less investment, and mild reaction conditions, wherein oil conversion rate of the material obtained from the upper outlet of the reactor can be 100%.
Description
Technical field
The present invention relates to by grease and C
1-C
6The process method of monohydroxy-alcohol prepared in reaction fatty acid monoester (being biofuel).
Background technology
Biofuel can be carried out transesterification reaction through grease and monohydroxy-alcohol and made, and fatty ester is arranged in the reaction product, also has mono-glycerides, two sweet esters, glycerine, and unreacted pure and mild grease (being triglyceride level).
CN1850944 discloses the technology that the base catalysis two step method prepares biofuel: 1) add pure and mild alkaline catalysts, molar ratio of methanol to oil 5.5～8.3 in the vegetable and animals oils: 1, and alkali number be oily heavy by 0.5～1.6%; 25～45 ℃ of temperature of reaction, reaction is 0.5～2 hour under rotating speed 300-400r/min; Leave standstill or centrifugal layering 2) isolated upper strata bio-diesel layer, add pure and mild alkaline catalysts; Molar ratio of methanol to oil 6.1～9.7: 1, alkali number is that oil is heavy by 0.5～1.6%, 25～45 ℃ of temperature of reaction; Reaction is 0.5～2 hour under rotating speed 300-400r/min; Leave standstill or centrifugal layering, through steaming methyl alcohol, washing, the yield 97%～99% of biofuel.Above-mentioned base catalysis two step method, work flow is elongated, and facility investment, energy consumption obviously rise.
CN1111591C discloses the method for a kind of grease and monohydroxy-alcohol prepared in reaction fatty ester, and this method comprises methyl alcohol reacted with grease and obtain fatty ester that at 270～280 ℃, under 11～12Mpa condition, the fatty acid methyl ester production rate is 55～60%.This method need be carried out under HTHP, and the fatty acid methyl ester yield is not very high.
Summary of the invention
The present invention provides a kind of method for preparing fatty ester, and this method can obtain fatty ester with high yield under lower temperature and pressure.
The method for preparing fatty ester provided by the invention comprises: make grease and the C that contains basic catalyst
1-C
6Monohydroxy-alcohol gets into the bottom of liquid phase from the tubular reactor of vertical placement, upwards flows, and volume space velocity is 0.1h during liquid
-1～0.5h
-1, from the material that upper outlet obtains, collect fatty ester.
Said grease is fatty acid triglycercide (being commonly called as triglyceride), can derive from animal oil or vegetables oil, preferred VT 18, rapeseed oil, Oleum Gossypii semen, Oleum Cocois, palm wet goods vegetables oil.
Said C
1-C
6Monohydroxy-alcohol can be single Fatty Alcohol(C12-C14 and C12-C18), also can be the mixture of one or more Fatty Alcohol(C12-C14 and C12-C18), particular methanol and ethanol.
The reaction of grease of the present invention and monohydroxy-alcohol is a liquid phase reaction, and temperature of reaction and pressure should be kept monohydroxy-alcohol and keep liquid phase basically, and for example, if monohydroxy-alcohol is a methyl alcohol, temperature of reaction can be 20 ℃～100 ℃, is preferably 40 ℃～90 ℃, is preferably 50 ℃～70 ℃.Pressure can be 0.1MPa～1.5MPa, is preferably 0.4MPa～1.0MPa, is preferably 0.4MPa～0.7MPa.
Raw material in tubular reactor during liquid volume space velocity be 0.1h
-1～0.5h
-1, preferred 0.12h
-1～0.4h
-1, more preferably 0.14h
-1～0.3h
-1
Monohydroxy-alcohol and greasy mol ratio (abbreviation alcohol oil rate) are 3～12: 1, and preferred alcohol oil rate is 4～9: 1, is preferably 4～6: 1.
The example of described alkaline metal cpds includes but not limited to oxyhydroxide, alcoholate, oxide compound, carbonate, supercarbonate and the C of IA and IIA element in the periodic table of elements
12～C
24In the soap one or more are like in sodium hydroxide, cesium hydroxide, calcium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, sodium methylate, potassium methylate, the potassium oleate etc. one or more.The basic cpd consumption can be 0.1～4.0 heavy % of grease weight, preferred 0.4～1.5 heavy %, more preferably 0.6～0.9 heavy %.
The inventive method reaction unit is simple, less investment, and also reaction conditions is gentle, and in the material that the reactor drum upper outlet obtains, the grease transformation efficiency can reach 100%.
Embodiment
Further specify the present invention through embodiment below, but the present invention is not limited to this.
Embodiment 1
With VT 18 and the bottom entering reactor drum of the methyl alcohol that contains Pottasium Hydroxide, upwards flow volume space velocity 0.19h during liquid from the reaction tubes of sky
-1, 64 ℃ of temperature of reactor are flowed out in outlet from reaction tubes top; Pressure 0.4MPa; Molar ratio of methanol to oil is 9: 1, and the add-on of Pottasium Hydroxide is 0.70% of a weight of oil, adopts the HP6890 gas chromatograph to carry out stratographic analysis from the material of upper outlet outflow reactor; Disregard methyl alcohol, the content of other material: the sweet ester of fatty acid methyl ester 99.5%, glycerine 0, mono-glycerides 0.4%, two 0, triglyceride 0.
Embodiment 2
Rapeseed oil and the bottom that contains behind the methyl alcohol thorough mixing of potassium methylate from the tubular reactor of sky are got into reactor drum, upwards flow volume space velocity 0.23h during liquid
-160 ℃ of temperature of reactor, pressure 0.11MPa, molar ratio of methanol to oil are 4.4: 1; The add-on of potassium methylate is 1.1% of a weight of oil; Adopt the HP6890 gas chromatograph to carry out stratographic analysis from the material of upper outlet outflow reactor, disregard methyl alcohol, the content of other material: the sweet ester of fatty acid methyl ester 99.3%, glycerine 0, mono-glycerides 0.6%, two 0, triglyceride 0.
Embodiment 3
With Oleum Gossypii semen and the bottom entering reactor drum of the methyl alcohol that contains potassium oleate, upwards flow volume space velocity 0.32h during liquid from the tubular reactor of sky
-169 ℃ of temperature of reactor, pressure 0.9MPa, molar ratio of methanol to oil are 4.6: 1; The add-on of potassium oleate is 3.8% of a weight of oil; Adopt the HP6890 gas chromatograph to carry out stratographic analysis from the material of upper outlet outflow reactor, disregard methyl alcohol, the content of other material: the sweet ester of glycerine 0.03%, fatty acid methyl ester 95.2%, mono-glycerides 3.5%, two 0.9%, triglyceride 0.
Embodiment 4
With Oleum Gossypii semen with contain the methyl alcohol thorough mixing of sodium hydroxide after, get into reactor drum from the bottom of the tubular reactor of sky, upwards flow volume space velocity 0.36h during liquid
-1, outlet is flowed out from reaction tubes top, and the reactor drum size is with embodiment 1; 60 ℃ of temperature of reactor, pressure 0.20MPa, molar ratio of methanol to oil are 5.2: 1; The add-on of sodium hydroxide is 1.2% of a weight of oil; Adopt the HP6890 gas chromatograph to carry out stratographic analysis from the material of upper outlet outflow reactor, disregard methyl alcohol, the content of other material: the sweet ester of glycerine 0.04%, fatty acid methyl ester 93.7%, mono-glycerides 4.9%, two 1.1%, triglyceride 0.
Embodiment 5
With Oleum Gossypii semen with contain the methyl alcohol thorough mixing of sodium hydroxide after, get into reactor drum from the bottom of the tubular reactor of sky, upwards flow volume space velocity 0.46h during liquid
-1, outlet is flowed out from reaction tubes top, and the reactor drum size is with embodiment 1; 60 ℃ of temperature of reactor, pressure 0.20MPa, molar ratio of methanol to oil are 5.2: 1; The add-on of sodium hydroxide is 1.2% of a weight of oil; Adopt the HP6890 gas chromatograph to carry out stratographic analysis from the material of upper outlet outflow reactor, disregard methyl alcohol, the content of other material: the sweet ester of glycerine 0.09%, fatty acid methyl ester 89.3%, mono-glycerides 7.6%, two 2.5%, triglyceride 0.
Comparative Examples 1
Compare with embodiment 2.
Rapeseed oil and the bottom that contains behind the methyl alcohol thorough mixing of potassium methylate from the tubular reactor of sky are got into reactor drum, upwards flow volume space velocity 0.55h during liquid
-160 ℃ of temperature of reactor, pressure 0.11MPa, molar ratio of methanol to oil are 4.4: 1; The add-on of potassium methylate is 1.1% of a weight of oil; Adopt the HP6890 gas chromatograph to carry out stratographic analysis from the material of upper outlet outflow reactor, disregard methyl alcohol, the content of other material: the sweet ester of fatty acid methyl ester 73.7%, glycerine 0.2%, mono-glycerides 5.1%, two 7.0%, triglyceride 13.3%.
Claims (13)
1. the preparation method of a fatty ester comprises: make grease and the C that contains basic catalyst
1-C
6Monohydroxy-alcohol gets into the bottom of liquid phase from the tubular reactor of vertical placement, upwards flows, and volume space velocity is 0.1h during liquid
-1～0.5h
-1, from the material that upper outlet obtains, collect fatty ester.
2. according to the described preparation method of claim 1, said grease is a fatty acid triglycercide.
3. according to the described preparation method of claim 1, said C
1-C
6Monohydroxy-alcohol is a methyl alcohol.
4. according to claim 1 or 3 described preparing methods, wherein temperature of reaction is 20 ℃～100 ℃, and pressure is 0.1MPa～1.5MPa.
5. according to the described preparation method of claim 5, wherein temperature of reaction is 40 ℃～90 ℃, and pressure is 0.4MPa～1.0MPa.
6. according to the described preparation method of claim 1, raw material in tubular reactor during liquid volume space velocity be 0.12h
-1～0.4h
-1
7. according to the described preparation method of claim 1, raw material in tubular reactor during liquid volume space velocity be 0.14h
-1～0.3h
-1
8. according to the described preparation method of claim 1, monohydroxy-alcohol and greasy mol ratio are 3～12: 1.
9. according to the described preparation method of claim 1, monohydroxy-alcohol and greasy mol ratio are 4～9: 1.
10. according to the described preparation method of claim 1, basic catalyst is selected from oxyhydroxide, alcoholate, oxide compound, carbonate, supercarbonate and the C of IA, IIA family metallic element
12～C
24In the soap one or more.
11. according to the described preparation method of claim 1, basic catalyst is selected from one or more in sodium hydroxide, cesium hydroxide, calcium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, sodium methylate, potassium methylate, the potassium oleate.
12. according to the described preparation method of claim 1, the basic cpd consumption is 0.1～4.0 heavy % of grease weight.
13. according to the described preparation method of claim 1, the basic cpd consumption is 0.4～1.5 heavy % of grease weight.
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|---|---|---|---|
| CN2011101435435A CN102807922A (en) | 2011-05-31 | 2011-05-31 | Preparation method for fatty acid ester |
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|---|---|---|---|
| CN2011101435435A CN102807922A (en) | 2011-05-31 | 2011-05-31 | Preparation method for fatty acid ester |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273850A (en) * | 2014-05-29 | 2016-01-27 | 中国石油化工股份有限公司 | Biodiesel synthesis promoting method |
| CN105273851A (en) * | 2014-06-17 | 2016-01-27 | 中国石油化工股份有限公司 | Method for preparing fatty acid ester |
| CN105861162A (en) * | 2015-01-22 | 2016-08-17 | 中国石油化工股份有限公司 | Preparation method of aliphatic ester by using solid catalyst |
| CN105861163A (en) * | 2015-01-22 | 2016-08-17 | 中国石油化工股份有限公司 | Preparation method of aliphatic ester by using solid catalyst |
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| CN101070511A (en) * | 2006-05-12 | 2007-11-14 | 中国石油化工股份有限公司 | Process for preparing aliphatic ester |
| CN101089127A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Biodiesel oil producing process |
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| CN101724509A (en) * | 2009-11-03 | 2010-06-09 | 南京工业大学 | Method for continuously preparing fatty acid ester by using tower reactor |
| JP4504953B2 (en) * | 2006-07-18 | 2010-07-14 | 株式会社Ｊ−オイルミルズ | Production equipment for fatty acid ester for fuel from oil cake |
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| US4985358A (en) * | 1985-09-10 | 1991-01-15 | Fuji Oil Company, Ltd. | Method for processing glyceride fats and oils |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273850A (en) * | 2014-05-29 | 2016-01-27 | 中国石油化工股份有限公司 | Biodiesel synthesis promoting method |
| CN105273850B (en) * | 2014-05-29 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of promotion biodiesel synthetic method |
| CN105273851A (en) * | 2014-06-17 | 2016-01-27 | 中国石油化工股份有限公司 | Method for preparing fatty acid ester |
| CN105273851B (en) * | 2014-06-17 | 2019-01-08 | 中国石油化工股份有限公司 | A method of preparing aliphatic ester |
| CN105861162A (en) * | 2015-01-22 | 2016-08-17 | 中国石油化工股份有限公司 | Preparation method of aliphatic ester by using solid catalyst |
| CN105861163A (en) * | 2015-01-22 | 2016-08-17 | 中国石油化工股份有限公司 | Preparation method of aliphatic ester by using solid catalyst |
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Application publication date: 20121205 |