CN101289627A - Process for reduce acid number of biodiesel - Google Patents
Process for reduce acid number of biodiesel Download PDFInfo
- Publication number
- CN101289627A CN101289627A CNA2008100500331A CN200810050033A CN101289627A CN 101289627 A CN101289627 A CN 101289627A CN A2008100500331 A CNA2008100500331 A CN A2008100500331A CN 200810050033 A CN200810050033 A CN 200810050033A CN 101289627 A CN101289627 A CN 101289627A
- Authority
- CN
- China
- Prior art keywords
- acid
- lowering agent
- acid value
- deacidification
- fatty acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002253 acid Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000003225 biodiesel Substances 0.000 title claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims abstract description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 6
- 229930195729 fatty acid Natural products 0.000 claims abstract description 6
- 239000000194 fatty acid Substances 0.000 claims abstract description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 229960004418 trolamine Drugs 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 4
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical group NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000010561 standard procedure Methods 0.000 abstract description 2
- 239000013064 chemical raw material Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000002551 biofuel Substances 0.000 description 20
- 238000001125 extrusion Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 235000021588 free fatty acids Nutrition 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Liquid Carbonaceous Fuels (AREA)
- Fats And Perfumes (AREA)
Abstract
A method for reducing the acid value of biodiesel oil is characterized in that: rectification of crude fatty acid methyl ester or fatty acid ethyl ester is carried out; a deacidification agent occupying 0.02 to 4 percent of the total weight of fine fatty acid methyl ester or fatty acid ethyl ester is added after the rectification; the mixture is gradually heated up to 60 to 80 DEG C inside a stirring reaction kettle, and is put in a settling tank when the stirring reaction is carried out for 0.2 to 0.5 hours; after 2-hour settlement, the lower-layer deacidification agent is discharged; the acid value of an upper layer is measured, and the upper layer is put in a finished product tank after the acid value is up to standard; and the deacidification agent can be used repeatedly. The method is simple and does not need complex equipment; meanwhile, the method has low production cost and ideal deacidification effect, and the diesel oil manufactured by the method accords with national standard; the separated deacidification agent can be used repeatedly to produce naphthenic acid amide which is a chemical raw material and can increase the economic benefits of a biodiesel oil enterprise. Tests and a standard method adopted to measure the acid value of biodiesel oil before and after deacidification show that the acid value of biodiesel oil can be reduced more than 90 percent when deacidified through adopting the method.
Description
One, technical field
The present invention relates to a kind of method that reduces acid number in the biofuel.
Two, background technology
Minimizing year by year along with the mineral diesel storage capacity, reproducible bioenergy is all being sought by various countries, because fatty acid methyl ester is the most approaching at aspect such as combustionproperty, characteristic and mineral diesel, therefore, it is the raw material production biofuel that developed countries such as America and Europe all develop with the vegetables oil.
China also has the people to carry out the work in this respect, as Chinese patent application 92114795.3, does the Catalyst Production biofuel with natural fats and oils by alkali, and acid number can be up to standard, but can't produce use because of cost of material is high; Chinese patent application CN 1473907A, with reclaiming high acid value lipid acid production biofuel in the waste material, acid number also can only reach 4.5mgKOH/g, does not reach national BD 100 standards; Chinese patent application CN 1031070C, adopt acid to carry out pre-esterification for catalyzer, after reaction is finished, add in the pure and mild excess base again and an acidic catalyst and residual free fatty acids, residue alkali is as the production technique of transesterification reaction, but, adopt above-mentioned two-step approach catalysts consumption to increase, double process period, facility investment is big, energy consumption significantly rises, and in addition, needs basic catalyst is removed from product, have and contain the alkali waste water generation in a large number, contaminate environment reclaims the glycerine difficulty, and production cost is too high.
Three, summary of the invention
The technical problem to be solved in the present invention is: provide a kind of and reduce the method for acid number of biodiesel by adding acid lowering agent, make the biofuel of producing meet national standard, thereby solve high acid value biofuel etching problem to body in engine.
Solving the technical scheme that problem of the present invention takes is: with acid number is that crude fatty acid methyl ester or the fatty-acid ethyl ester of 1-5mgKOH/g carries out rectifying, after rectifying, add the acid lowering agent that accounts for smart fatty acid methyl ester or fatty-acid ethyl ester gross weight 0.02～4%, in stirred autoclave, be warming up under 60～80 ℃ gradually, stirring reaction was put into slurry tank in 0.2～0.5 hour, sedimentation separated in 2 hours emits lower floor's acid lowering agent, acid number is measured on the upper strata, is put into the finished product jar after qualified; Described acid lowering agent is thanomin, diethanolamine, trolamine, preferred trolamine; Isolated acid lowering agent can be reused.
Positively effect of the present invention is: method is simple, does not need complex apparatus, and production cost is low; It is effective to fall acid, uses the inventive method depickling artifact diesel oil acid number can reduce more than 90%, and the diesel oil of production meets national standard; Isolated acid lowering agent can be reused, and it is cycloalkanoimide that acid lowering agent repeatedly uses its product of back, and it is a kind of industrial chemicals, can increase the biofuel economic benefit of enterprises.
Four, embodiment
Embodiment one:
In 5L stirring reaction container, add biofuel 2Kg, its acid number is 2.1mgKOH/g, and acid lowering agent is a trolamine, with 0.056Kg, acid lowering agent divides three addings, and stir speed (S.S.) is 300rpm, heat temperature raising to 75 ℃, reacted 0.5 hour, sampling after cooling, measured reaction artifact diesel oil acid number is 0.176mgKOH/g, sour extrusion rate is 91.6%.
Embodiment two:
In 5L stirring reaction container, add biofuel 2Kg, its acid number is 2.1mgKOH/g, and acid lowering agent is the sediment among the embodiment one, once adds, stir speed (S.S.) is 300rpm, heat temperature raising to 75 ℃ reacted 0.5 hour, and the back sampling cools, measured reaction artifact diesel oil acid number is 0.52mgKOH/g, and sour extrusion rate is 75.2%.
Embodiment three:
In 5L stirring reaction container, add biofuel 2Kg, its acid number is 2.1mgKOH/g, and acid lowering agent is a thanomin, with the 0.056Kg acid lowering agent, divide three times and add, stir speed (S.S.) is 300rpm, heat temperature raising to 75 ℃, reacted 0.5 hour, cool behind the back sampling measured reaction, acid number of biodiesel is 0.29mgKOH/g, and sour extrusion rate is 86.2%.
Embodiment four:
In 5L stirring reaction container, add biofuel 2Kg, its acid number is 2.1mgKOH/g, acid lowering agent is embodiment three sediments, once adds, and stir speed (S.S.) is 300rpm, heat temperature raising to 75 ℃, reacted 0.5 hour, the back sampling measured reaction artifact diesel oil acid number that cools is 0.77mgKOH/g, and sour extrusion rate is 63.4%.
Embodiment five:
In 5L stirring reaction container, add biofuel 2Kg, its acid number is 2.1mgKOH/g, and acid lowering agent is a diethanolamine, divides three addings with the 0.056Kg acid lowering agent, stir speed (S.S.) is 300rpm, heat temperature raising to 75 ℃ reacted 0.5 hour, behind the back sampling measured reaction that cools, acid number of biodiesel is 0.21mgKOH/g, and sour extrusion rate is 90%.
Embodiment six:
In 5L stirring reaction container, add biofuel 2Kg, its acid number is 2.1mgKOH/g, acid lowering agent is embodiment five sediments, once adds, and stir speed (S.S.) is 300rpm, heat temperature raising to 75 ℃, reacted 0.5 hour, the back sampling measured reaction artifact diesel oil acid number that cools is 0.62mgKOH/g, and sour extrusion rate is 70.5%.
Use the inventive method, naphthenic acid and acid lowering agent generation chemical reaction that free fatty acids in the biofuel and acid catalysis are produced, the cycloalkanoimide that generates is nontoxic, so the acid lowering agent of small residue need not to remove fully from biofuel in the biofuel, exist in the biofuel, do not influence biofuel character, also have certain corrosion inhibition.It is cycloalkanoimide that acid lowering agent repeatedly uses its product of back, and it is a kind of industrial chemicals, can increase the biofuel economic benefit of enterprises.
Through test of many times, adopt standard method to measure the acid number of depickling front and back biofuel, prove and use the inventive method depickling artifact diesel oil acid number to reduce more than 90%.
Claims (1)
1, a kind of method that reduces acid number of biodiesel, it is characterized in that: with acid number is that crude fatty acid methyl ester or the fatty-acid ethyl ester of 1-5mgKOH/g carries out rectifying, after rectifying, add the acid lowering agent that accounts for smart fatty acid methyl ester or fatty-acid ethyl ester gross weight 0.02～4%, in stirred autoclave, be warming up under 60～80 ℃ gradually, stirring reaction was put into slurry tank in 0.2～0.5 hour, sedimentation 2 hours separates emits lower floor's acid lowering agent, and acid number is measured on the upper strata, is put into the finished product jar after qualified; Described acid lowering agent is thanomin or diethanolamine or trolamine, preferred trolamine; Contain acid lowering agent in the sediment, can reuse.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100500331A CN101289627B (en) | 2008-06-10 | 2008-06-10 | Process for reducing acid value of biodiesel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100500331A CN101289627B (en) | 2008-06-10 | 2008-06-10 | Process for reducing acid value of biodiesel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101289627A true CN101289627A (en) | 2008-10-22 |
| CN101289627B CN101289627B (en) | 2011-07-27 |
Family
ID=40034075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100500331A Expired - Fee Related CN101289627B (en) | 2008-06-10 | 2008-06-10 | Process for reducing acid value of biodiesel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101289627B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102533443A (en) * | 2011-12-30 | 2012-07-04 | 代洪达 | Method for refining cracking biodiesel to fuel oil of internal combustion engine |
| CN102682869A (en) * | 2012-04-11 | 2012-09-19 | 中国电力科学研究院 | Vegetable insulating oil, and preparation method of vegetable insulating oil |
| CN103013676A (en) * | 2011-09-20 | 2013-04-03 | 中国石油化工股份有限公司 | Method for reducing biodiesel crude product acid value, and biodiesel preparation method |
| CN101760225B (en) * | 2008-12-25 | 2013-09-04 | 中国石油化工股份有限公司 | Method for reduction of acid value of biodiesel |
| CN103421548A (en) * | 2012-05-14 | 2013-12-04 | 陕西德融新能源股份有限公司 | Preparation technology of biodiesel produced from non refined grease |
| CN110628612A (en) * | 2019-10-18 | 2019-12-31 | 湖州联创环保科技有限公司 | Process system for preparing biodiesel by adopting step counter-flow continuous enzymatic method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITMI20050723A1 (en) * | 2005-04-21 | 2006-10-22 | Consiglio Nazionale Ricerche | PRODUCTION METHOD OF BIODIESEL |
| CN100360644C (en) * | 2005-05-12 | 2008-01-09 | 中国石油化工股份有限公司 | Production process of biological diesel |
| CN100577785C (en) * | 2005-07-26 | 2010-01-06 | 中国石油化工股份有限公司 | Method of lowering acid value of oil and fat |
-
2008
- 2008-06-10 CN CN2008100500331A patent/CN101289627B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101760225B (en) * | 2008-12-25 | 2013-09-04 | 中国石油化工股份有限公司 | Method for reduction of acid value of biodiesel |
| CN103013676A (en) * | 2011-09-20 | 2013-04-03 | 中国石油化工股份有限公司 | Method for reducing biodiesel crude product acid value, and biodiesel preparation method |
| CN103013676B (en) * | 2011-09-20 | 2014-12-03 | 中国石油化工股份有限公司 | Method for reducing biodiesel crude product acid value, and biodiesel preparation method |
| CN102533443A (en) * | 2011-12-30 | 2012-07-04 | 代洪达 | Method for refining cracking biodiesel to fuel oil of internal combustion engine |
| CN102533443B (en) * | 2011-12-30 | 2013-12-04 | 代洪达 | Method for refining cracking biodiesel to fuel oil of internal combustion engine |
| CN102682869A (en) * | 2012-04-11 | 2012-09-19 | 中国电力科学研究院 | Vegetable insulating oil, and preparation method of vegetable insulating oil |
| CN103421548A (en) * | 2012-05-14 | 2013-12-04 | 陕西德融新能源股份有限公司 | Preparation technology of biodiesel produced from non refined grease |
| CN110628612A (en) * | 2019-10-18 | 2019-12-31 | 湖州联创环保科技有限公司 | Process system for preparing biodiesel by adopting step counter-flow continuous enzymatic method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101289627B (en) | 2011-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sarin | Biodiesel: production and properties | |
| CN101289627B (en) | Process for reducing acid value of biodiesel | |
| Sierra-Cantor et al. | Methods for improving the cold flow properties of biodiesel with high saturated fatty acids content: A review | |
| Moser | Biodiesel production, properties, and feedstocks | |
| Kay et al. | Biodiesel production from low quality crude jatropha oil using heterogeneous catalyst | |
| CN104830516B (en) | A kind of extreme pressure type aluminium sheet aluminium strip hot rolling emulsion and preparation method thereof | |
| CN102257108B (en) | Use of methanesulfonic acid for producing fatty acid esters | |
| Panchal et al. | Optimization and kinetics of tung nut oil transesterification with methanol using novel solid acidic ionic liquid polymer as catalyst for methyl ester synthesis | |
| CN104629868B (en) | Preparation method of low-sulfur diesel oil antiwear agent | |
| CN101785992B (en) | Preparation method of catalyst used for cracking and de-acidification of high-acid crude oil | |
| Hancsók et al. | Production of vegetable oil fatty acid methyl esters from used frying oil by combined acidic/alkali transesterification | |
| JPWO2008023728A1 (en) | Method for producing fatty acid ester from vegetable oil and diesel fuel containing the fatty acid ester | |
| Olutoye et al. | Synthesis of fatty acid ethyl ester from chicken fat using ZnO/SiO2 heterogeneous catalyst | |
| JP5452582B2 (en) | Method for producing glyceride composition for C heavy oil alternative fuel | |
| Pourvosoghi et al. | An optimized process for biodiesel production from high FFA spent bleaching earth | |
| CN101215482A (en) | Fluid fuel for alcohol hydrocarbon diesel engine and preparation method thereof | |
| Fauzi et al. | Recent Progress of Biodiesel Production | |
| Roschat | The optimized conditions of ethanolysis reaction of palm oil to biodiesel product using eggshells-derived CaO as a solid heterogeneous catalyst | |
| Trindade et al. | Use of protic ionic liquid ([deta][hx]) as co-solvent in biodiesel production | |
| Worapun et al. | Synthesis of biodiesel by two-step transesterification from crude jatropha curcus L. oil using ultrasonic irradiation assisted | |
| Ahmed et al. | Study of Reaction Conditions on a Conversion ratio of Castor Oil Fuel Production | |
| WO2021106619A1 (en) | Bio-fuel production method using flow-type reaction device | |
| CN102604663A (en) | Method for directly producing high-cetane-number diesel oil by using illegal cooking oil | |
| JP7045775B2 (en) | Biofuel production method using a distribution reactor | |
| CN104593159A (en) | Method for producing biodiesel by use of composite solid catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: HENAN YATAI ENERGY TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: HAINAN XINGHUO BIOLOGICAL ENERGY CO., LTD. Effective date: 20140604 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20140604 Address after: 476000 middle section of new 105 National Road, Shangqiu economic and Technological Development Zone, Henan (Asia Pacific Oil Corporation) Patentee after: Henan Yatai Energy Technology Co., Ltd. Address before: 476000 Henan Province, Shangqiu City Development Zone's permanent Shangbo high-speed entrance on the south side of the road west 100 meters Patentee before: Henan Xinghuo Biological Energy Co.,Ltd. |
|
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 476000 middle section of new 105 National Road, Shangqiu economic and Technological Development Zone, Henan (Asia Pacific Oil Corporation) Patentee after: HENAN ASIA PACIFIC ENERGY CO., LTD. Address before: 476000 middle section of new 105 National Road, Shangqiu economic and Technological Development Zone, Henan (Asia Pacific Oil Corporation) Patentee before: Henan Yatai Energy Technology Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110727 Termination date: 20160610 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |