CN1858160A - Method for preparing biological diesel oil using nano solid acid or alkali catalyst - Google Patents

Method for preparing biological diesel oil using nano solid acid or alkali catalyst Download PDF

Info

Publication number
CN1858160A
CN1858160A CNA2006100192454A CN200610019245A CN1858160A CN 1858160 A CN1858160 A CN 1858160A CN A2006100192454 A CNA2006100192454 A CN A2006100192454A CN 200610019245 A CN200610019245 A CN 200610019245A CN 1858160 A CN1858160 A CN 1858160A
Authority
CN
China
Prior art keywords
nano
solid acid
diesel oil
nano solid
bio
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
Application number
CNA2006100192454A
Other languages
Chinese (zh)
Other versions
CN100503786C (en
Inventor
黄凤洪
郭萍梅
黄庆德
李文林
黄沁洁
杨湄
夏伏建
王江薇
钮琰星
刘昌盛
程小英
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oil Crops Research Institute of Chinese Academy of Agriculture Sciences
Original Assignee
Oil Crops Research Institute of Chinese Academy of Agriculture Sciences
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Oil Crops Research Institute of Chinese Academy of Agriculture Sciences filed Critical Oil Crops Research Institute of Chinese Academy of Agriculture Sciences
Priority to CNB2006100192454A priority Critical patent/CN100503786C/en
Publication of CN1858160A publication Critical patent/CN1858160A/en
Application granted granted Critical
Publication of CN100503786C publication Critical patent/CN100503786C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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

  • Fats And Perfumes (AREA)

Abstract

The present invention relates to process of preparing low carbon alkyl ester and biological diesel oil by means of nanometer solid acid or alkali catalyst. Under the action of catalyst in the amount of 1-20 wt% of animal and vegetable oil, low carbon alcohol and animal and vegetable oil in the molar ratio of 3.5-40 to 1 are reacted at the pressure from normal to 25 MPa and temperature of 40-100 deg.c to produce coarse methyl ester and glycerin, which are centrifugally separated and distilled to obtain low carbon alcohol, or neutral biological diesel oil and glycerin, separately. The present invention has biological diesel oil converting rate up to 96% and yield up to 99%, and the product meets the ASTM D 6751-02 standard. The nanometer solid acid or alkali catalyst may be used repeatedly for 3-100 times in producing biological diesel oil, and the product needs no neutralization and washing.

Description

Adopt nano solid acid or base catalysis to prepare method of bio-diesel oil
Technical field
The present invention relates to a kind ofly prepare lipid acid low-carbon alkyl---method of bio-diesel oil, belong to oil chemistry and Application in Chemical Engineering field with nanoscale solids acid or base catalysis.
Background technology
Biofuel is a kind of green regenerative energy sources, can be used as fine petrifaction diesel substitute.It is to be raw material with animal oil, vegetables oil, discarded edible wet goods, and (carbonatoms 1-4) carries out transesterification reaction under certain condition with low-carbon alcohol, and the product that obtains is biofuel (lipid acid low-carbon alkyl), and byproduct is a glycerine.What traditional homogeneous catalyst adopted usually is the liquid soda acid, mainly contain the vitriol oil, NaOH, KOH etc., the remarkable defective that these liquid catalysts exist is in the product needed of reaction back and washing, cause environmental pollution, byproduct glycerine is mutually impure more, is difficult for purifying, and catalyzer can not reclaim repeatedly and use.
Therefore, the research report of solid catalysis conversion biodiesel is more and more, at Chinese oil [.2004,29 (12) 68～70] in " tin tetrachloride is to high-acid value grease catalyzing esterification experimental study of effect " literary composition that Guo Ping plum etc. is delivered in, the esterification yield of tin tetrachloride that uses reaches more than 97%, but use properties is relatively poor repeatedly.In disclosed patented technology, as described in CN1580190A, CN1664072A, adopt common solid acid, base catalysis to prepare method of bio-diesel oil, can simplify technology, avoid pollution, but use properties is the problem that needs consideration repeatedly environment.Therefore, press for exploitation catalytic activity height, use properties is good repeatedly solid catalyst prepares biofuel.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that exists at above-mentioned prior art and provide a kind of and prepare method of bio-diesel oil with nano solid acid or base catalysis, and it has active high, the good characteristics of use properties repeatedly of catalyst.
The present invention is that to address the above problem the technical scheme that is adopted as follows: adopt nano solid acid or alkaline catalysts, the catalyzer add-on is 1～20% of a vegetable and animals oils weight, low-carbon alcohol and vegetable and animals oils mol ratio are 3.5～40: 1, the heated and stirred reaction, the pressure of retort: normal pressure～25Mp, temperature: 40-100 ℃, the centrifugation of reaction back goes out thick methyl esters and glycerine mutually, thick methyl esters is distilled out low-carbon alcohol respectively mutually with glycerine, promptly obtain neutral biofuel and glycerine.
Press such scheme, described nano solid acid or alkaline catalysts are to adopt preparation method of nano material such as vacuum condensation method, mechanical ball milling method, sol-gel method, original position method of formation, chemical precipitation method, hydrothermal synthesis method to be prepared from.Recyclable recirculation is again used after the centrifugation.
Described nano solid acid catalyst comprises: nano level oxide compound and composite oxides Al 2O 3, SiO 2, TiO 2, Al 2O 3-SiO 2, TiO 2-SiO 2Deng; Nano solid supper corrosive acid: ZrSO 4, ZrO 2/ SiO 2, SO 4 2-/ TiO 2, SO 4 2-/ Al 2O 3, SO 4 2-/ ZrO 2, SO 4 2-/ Fe 2O 3, SO 4 2-(S 2O 8 2-)/CoFe 2O 4, SO 4 2-/ ZrO 2-Fe 3O 4, SO 4 2-/ ZnFe 2O 4Deng; Nano-scale rare earth solid super-strong acid: SO 4 2-/ ZrO 2/ Ce 4+, SO 4 2-/ ZrO 2-CeO 2, SO 4 2-/ TiO 2/ La 3+, SO 4 2-/ Ti-La-O, SO 4 2-/ Fe 2O 3-Dy 2O 3Deng.Wherein, SO particularly 4 2-/ TiO 2, SO 4 2-/ Al 2O 3, ZrO 2/ SiO 2, TiO 2-SiO 2Show fabulous catalytic activity.
Described nano solid base catalyst is: nano level inorganic chemical ZnO, MgO, CaO, SrO and BaO, nano hydrotalcite (MgAl (O)/MgFe 2O 4) and houghite; Nano level mixture Mg-Al, MgO-NaOH, MgO-Na etc.; Nanometer level RE oxide La 2O 3, Y 2O 3, Nd 2O 3, Ce 2O 3Carrier or loaded article (metal oxide) are the loaded nano solid alkali of nanoparticle, as at nano level Al 2O 3, SiO 2, TiO 2Deng flooding K on the carrier 2CO 3Or KHCO 3, NaOH, KOH etc., perhaps metal oxide supported on various carriers with above-mentioned nanoparticle.Wherein, nano hydrotalcite (MgAl (O)/MgFe particularly 2O 4), K +/ Al 2O 3, K +/ SiO 2, K +/ gac shows fabulous catalytic activity.
Described vegetable and animals oils is animal oil and/or vegetables oil, comprises lard, butter, sheep oil, rapeseed oil, soybean oil, sesame oil, peanut oil, plam oil, discarded edible oil; Described low-carbon alcohol is methyl alcohol, ethanol, propyl alcohol, butanols, or both mixing arbitrarily, and the recyclable recirculation of the unnecessary low-carbon alcohol that distills out after the reaction is used.
Press such scheme, the transesterification reaction catalysis time after adding catalyzer and the low-carbon alcohol is 0.1～10 hour.
The invention has the beneficial effects as follows:
1, adopt nano solid acid or alkaline catalysts catalysis animal-plant oil transesterification reaction, the biofuel transformation efficiency reaches more than 96%, and yield is more than 99%, and technical target of the product meets ASTM D 6751-02 standard.
2, compare with common solid catalyst, adopt the usability repeatedly of nano solid acid or alkaline catalysts to be greatly enhanced,, can use 3～100 artifact diesel oil transformation efficiencys repeatedly still about 96% without any activation treatment.
3, adopt nano solid acid or the alkali catalyst for ester exchange reaction as vegetable and animals oils and low-carbon alcohol, the product that obtains does not need the neutralization washing to wait aftertreatment, without sewage discharge.Solved traditional liquid phase acid or liquid phase alkaline catalysts and prepared in the biofuel, problems such as the corrodibility to equipment, the aftertreatment of existence is loaded down with trivial details, the difficult purification of byproduct glycerine.
At catalytic field, nano catalytic material presents fabulous catalytic activity, and nano material is meant that microstructures such as crystal grain and crystal boundary can both reach the material of nano level yardstick, and the nanoparticle particle diameter is generally between 1～100nm.Its surface atom number increases considerably along with the minimizing of nano-particles size with the ratio of total atom number, particle surface energy and surface tension are also along with increase, the serious mismatch of huge specific surface area and key attitude, many active centre occur, thereby show much better than chemical catalysis activity than common catalytic material.
Description of drawings
Fig. 1 is the workflow block diagram of one embodiment of the invention.
Embodiment
Further specify embodiments of the invention below in conjunction with accompanying drawing.
Embodiment 1:
Raw material: cold rolling vegetable seed crude oil, methyl alcohol, nano hydrotalcite (MgAl (O)/MgFe 2O 4);
By weight cold rolling vegetable seed crude oil of 200g and 60g methyl alcohol are added in three mouthfuls of round-bottomed flasks of 500ml, place the electrically heated constant temperature sleeve, stir, add 5g nano hydrotalcite (MgAl (O)/MgFe again 2O 4), being heated to 70 ℃, the methanol eddy stirring reaction stopped heated and stirred after 5 hours.Then reactant is poured in the Centrifuge Cup, centrifugal thick methyl esters and the raw glycerine told, the decompression rotary distillation removes methyl alcohol and obtains the 198.67g biofuel, yield 99.34%, obtain glycerine 19.87g, adopt GB/T 13216.6-91 to record glycerol content 98%, theoretical glycerine output is 20g, and promptly the biofuel transformation efficiency is more than 97.36%.Fatty acid methyl ester absolute content in the biofuel product that the employing gas Chromatographic Determination obtains, measurement result is approaching with the biofuel transformation efficiency that obtains with the glycerol content evaluation, is 97.11%.
According to technical process in the accompanying drawing nano hydrotalcite is used 8 times repeatedly without any activation treatment, estimate the biofuel transformation efficiency with the glycerine yield, its catalytic activity is still more than 96% after 8 times.The result is as follows.
The number of occurrence 1 time 2 times 3 times 4 times 5 times 6 times 7 times 8 times
Transformation efficiency (%) 97.36 96.41 96.21 96.33 96.15 96.12 96.15 96.08
Compare with USS ASTM D 6751-02, measuring method is all measured according to the requirement on the ASTM D 6751.
Sequence number Index name U.S. ASTM6751 standard ※ The product measured value
1 Flash-point (method of remaining silent), ℃ 130(Min) 176
2 Moisture and impurity, % 0.05(Max) 0.042
3 Kinetic viscosity (40 ℃), mm 2/s 1.9~6.0 4.1
4 Sulphated ash (weight), % 0.02(Max) /
5 Sulphur content (weight), % 0.05(Max) 0.01
6 Cetane value 47(Min) 48
7 Acid value, mmKOH/g 0.8(Max) 0.75
8 Free glycerol, % 0.02(Max) 0.015
9 Total glycerine, % 0.24(Max) 0.234
10 Phosphorus content, % 0.001(Max) 0.001
11 90% steams temperature, ℃ 360(Max) 351
From measurement result as can be seen, the biofuel product index that obtains all reaches ASTM D 6751-02 standard.
Embodiment 2:
Raw material: the soybean oil of coming unstuck, methyl alcohol, K +/ nanometer Al 2O 3, K +/ common Al 2O 3
By weight 200g is come unstuck in three mouthfuls of round-bottomed flasks of soybean oil and 60g methyl alcohol adding 500ml, place the electrically heated constant temperature sleeve, stir, add 5g nano-solid catalyzer: K again +/ nanometer Al2O3 is heated to 70 ℃, and the methanol eddy stirring reaction stopped heated and stirred after 5 hours.Then reactant is poured in the Centrifuge Cup, centrifugal thick methyl esters and the raw glycerine told, the decompression rotary distillation removes methyl alcohol and obtains the 199.50g biofuel, yield 99.75%, obtain glycerine 19.69g, adopt GB/T 13216.6-91 to record glycerol content 97.98%, theoretical glycerine output is 20g, and promptly the biofuel transformation efficiency 96.46%.Adopt fatty acid methyl ester absolute content in the gas Chromatographic Determination biofuel product, measurement result is approaching with the biofuel transformation efficiency that obtains with the glycerol content evaluation, is 96.05%.
Catalyzer K +/ nanometer Al 2O 3After using 10 times repeatedly, obtain the biofuel conversion rate of products still about 96%.
Every determination of quality index reaches ASTM D 6751-02 standard after measured with embodiment 1.
Under identical reaction conditions, with K +/ common Al 2O 3Be catalyzer, one time transformation efficiency reaches 96.68%, but obviously descending appears in transformation efficiency after using 2 times repeatedly, is about 89%.
Embodiment 3:
The discarded edible oil of raw material: acid value 24mgKOH/g, methyl alcohol, nano solid supper corrosive acid: ZrO 2/ SiO 2, common solid super-strong acid: ZrO 2/ SiO 2
The discarded edible oil that to collect by weight earlier through sedimentation, filter and obtain foreign matter content less than 0.1% raw oil material, measure its acid value, be 24mgKOH/g.In three mouthfuls of round-bottomed flasks of 500ml, add discarded edible oil and the 60g methyl alcohol that 200g handles well, stir, add 5g nano solid supper corrosive acid: ZrO again 2/ SiO 2Be heated to the methanol eddy temperature, stirring reaction stopped heated and stirred after 5 hours, pour out the reactant centrifugation, the thick methyl esters and the raw glycerine that obtain are removed methyl alcohol, obtain biofuel product 199.86g, yield 99.93%, byproduct glycerine 19.81g, glycerol content 97.08%, biofuel transformation efficiency 96.16%.Methyl esters absolute content 96.09% in the gas Chromatographic Determination biofuel product.
Nano solid supper corrosive acid ZrO 2/ SiO 2After using 9 times repeatedly, the biofuel conversion rate of products is still about 96%.Every quality index evaluation all reaches ASTM D 6751 standards with embodiment 1.
Under the same terms typical catalyst is tested repeatedly, the result shows and is using the 3rd artifact diesel oil transformation efficiency to drop to 90% repeatedly.
Embodiment 4:
Raw material: lard, methyl alcohol, nanometer K +/ gac, common K +/ gac
By weight 200g lard and 60g methyl alcohol are added in three mouthfuls of round-bottomed flasks of 500ml, add 5g nanometer K while stirring +/ gac, being heated to the methanol eddy temperature picks up counting, react and stop heated and stirred after 5 hours, pour out the reactant centrifugation, the thick methyl esters and the raw glycerine that obtain are removed methyl alcohol, obtain biofuel product 198.95g, yield 99.48%, byproduct glycerine 19.79g, glycerol content 97.19%, biofuel transformation efficiency 96.17%.Methyl esters absolute content 96.04% in the gas Chromatographic Determination biofuel product.
Nanometer K +After/gac used 8 times repeatedly, the biofuel conversion rate of products was still about 96%.Every quality index evaluation all reaches ASTM D 6751 standards with embodiment 1.
Under the same terms to common K +/ gac is tested repeatedly, and the result shows and using the 3rd artifact diesel oil transformation efficiency to drop to 89% repeatedly.

Claims (9)

1. one kind is adopted nano solid acid or base catalysis to prepare method of bio-diesel oil, it is characterized in that adopting nano solid acid or alkaline catalysts, the catalyzer add-on is 1～20% of a vegetable and animals oils weight, low-carbon alcohol and vegetable and animals oils mol ratio are 3.5～40: 1, heated and stirred reaction, the pressure of retort: normal pressure～25Mp, temperature: 40-100 ℃, the centrifugation of reaction back goes out thick methyl esters and glycerine mutually, and thick methyl esters is distilled out low-carbon alcohol respectively mutually with glycerine, promptly obtains neutral biofuel and glycerine.
2. employing nano solid acid according to claim 1 or base catalysis prepare method of bio-diesel oil, it is characterized in that described nano solid acid or alkaline catalysts are to adopt preparation method of nano material such as vacuum condensation method, mechanical ball milling method, sol-gel method, original position method of formation, chemical precipitation method, hydrothermal synthesis method to be prepared from.
3. employing nano solid acid according to claim 1 and 2 or base catalysis prepare method of bio-diesel oil, it is characterized in that described nano solid acid or alkaline catalysts are the materials that crystal grain and crystal boundary microstructure can both reach the nano level yardstick, the nanoparticle particle diameter is between 1～100nm.
4. employing nano solid acid according to claim 1 and 2 or base catalysis prepare method of bio-diesel oil, it is characterized in that described nano solid acid catalyst comprises: nano level oxide compound and composite oxides Al 2O 3, SiO 2, TiO 2, Al 2O 3-SiO 2, TiO 2-SiO 2Nano solid supper corrosive acid: ZrSO 4, ZrO 2/ SiO 2, SO 4 2-/ TiO 2, SO 4 2-/ Al 2O 3, SO 4 2-/ ZrO 2, SO 4 2-/ Fe 2O 3, SO4 2-(S 2O 8 2-)/CoFe 2O 4, SO 4 2-/ ZrO 2-Fe 3O 4, SO 4 2-/ ZnFe 2O 4Nano-scale rare earth solid super-strong acid: SO 4 2-/ ZrO 2/ Ce 4+, SO 4 2-/ ZrO 2-CeO 2, SO 4 2-/ TiO 2/ La 3+, SO 4 2-/ Ti-La-O, SO 4 2-/ Fe 2O 3-Dy 2O 3
5. employing nano solid acid according to claim 1 and 2 or base catalysis prepare method of bio-diesel oil, it is characterized in that described nano solid base catalyst is: nano level inorganic chemical ZnO, MgO, CaO, SrO and BaO, nano hydrotalcite (MgAl (O)/MgFe 2O 4) and houghite; Nano level mixture Mg-Al, MgO-NaOH, MgO-Na; Nanometer level RE oxide La 2O 3, Y 2O 3, Nd 2O 3, Ce 2O 3Carrier or loaded article (metal oxide) are the loaded nano solid alkali of nanoparticle.
6. employing nano solid acid according to claim 1 and 2 or base catalysis prepare method of bio-diesel oil, it is characterized in that described vegetable and animals oils is animal oil and/or vegetables oil.
7. employing nano solid acid according to claim 1 and 2 or base catalysis prepare method of bio-diesel oil, it is characterized in that described low-carbon alcohol is methyl alcohol, ethanol, propyl alcohol, butanols, or both mixing arbitrarily, the low-carbon alcohol that steams recycling use again.
8. employing nano solid acid according to claim 1 and 2 or base catalysis prepare method of bio-diesel oil, and the transesterification reaction catalysis time that it is characterized in that adding after catalyzer and the low-carbon alcohol is 0.1～10 hour.。
9. employing nano solid acid according to claim 1 and 2 or base catalysis prepare method of bio-diesel oil, and nano solid acid after the centrifugation or alkaline catalysts reclaim recirculation again and use.
CNB2006100192454A 2006-06-02 2006-06-02 Method for preparing biological diesel oil using nano solid acid or alkali catalyst Expired - Fee Related CN100503786C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2006100192454A CN100503786C (en) 2006-06-02 2006-06-02 Method for preparing biological diesel oil using nano solid acid or alkali catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2006100192454A CN100503786C (en) 2006-06-02 2006-06-02 Method for preparing biological diesel oil using nano solid acid or alkali catalyst

Publications (2)

Publication Number Publication Date
CN1858160A true CN1858160A (en) 2006-11-08
CN100503786C CN100503786C (en) 2009-06-24

Family

ID=37297118

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2006100192454A Expired - Fee Related CN100503786C (en) 2006-06-02 2006-06-02 Method for preparing biological diesel oil using nano solid acid or alkali catalyst

Country Status (1)

Country Link
CN (1) CN100503786C (en)

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009046636A1 (en) * 2007-09-29 2009-04-16 Huazhong Agricultural University Method for producing biodiesel using solid acid-base bifunctional catalyst
CN101230309B (en) * 2008-01-11 2010-04-07 四川大学 Method for preparing biodiesel by lowering value of high acid palm oil
US7897798B2 (en) 2006-08-04 2011-03-01 Mcneff Research Consultants, Inc. Methods and apparatus for producing alkyl esters from lipid feed stocks and systems including same
CN101294096B (en) * 2008-05-22 2011-04-20 渤海大学 Process for producing biological diesel oil
US7943791B2 (en) 2007-09-28 2011-05-17 Mcneff Research Consultants, Inc. Methods and compositions for refining lipid feed stocks
CN101293209B (en) * 2007-04-29 2011-05-25 华中农业大学 Nano-solid heteropoly acid, heteropolybase catalyst suitable for producing biological diesel oil and application thereof
CN101353589B (en) * 2008-09-05 2011-06-08 中国林业科学研究院林产化学工业研究所 Method for preparing biodiesel by catalysis of nano magnetic sulphonated coal
CN102134514A (en) * 2011-01-26 2011-07-27 李恒全 Synthetic biodiesel and preparation method thereof
US8017796B2 (en) 2007-02-13 2011-09-13 Mcneff Research Consultants, Inc. Systems for selective removal of contaminants from a composition and methods of regenerating the same
CN101294093B (en) * 2007-04-29 2012-10-10 华中农业大学 Integrated preparation method for biological diesel oil and isolated plant
CN101492603B (en) * 2008-01-23 2012-11-28 华中农业大学 Method for producing biodiesel by using tallowseed oil and special solid catalyst thereof
US8361174B2 (en) 2008-10-07 2013-01-29 Sartec Corporation Catalysts, systems, and methods for producing fuels and fuel additives from polyols
US8445709B2 (en) 2006-08-04 2013-05-21 Mcneff Research Consultants, Inc. Systems and methods for refining alkyl ester compositions
CN103301855A (en) * 2013-07-04 2013-09-18 南通宝聚颜料有限公司 Preparation method of titanium dioxide loaded spherical solid super acid
DE112011102947T5 (en) 2011-03-04 2013-10-17 Tianjin Polytechnic University A catalytic composite membrane used for the catalysis of the esterification and their preparation
US8585976B2 (en) 2007-02-13 2013-11-19 Mcneff Research Consultants, Inc. Devices for selective removal of contaminants from a composition
US9102877B2 (en) 2008-11-12 2015-08-11 Sartec Corporation Systems and methods for producing fuels from biomass
CN104923301A (en) * 2015-05-13 2015-09-23 安徽金邦医药化工有限公司 High-temperature-resistant cryolite-based composite solid acid catalyst and preparation method therefor
CN105130812A (en) * 2015-09-06 2015-12-09 安徽增源生物能源有限公司 Synthetic method for isopropyl palmitate
CN107115853A (en) * 2017-05-15 2017-09-01 中国海洋石油总公司 Mg Al houghite catalyst for handling residual oil and extra heavy oil raw material and preparation method thereof
CN107930658A (en) * 2017-11-24 2018-04-20 湘潭大学 A kind of method of short nano bar-shape structure solid base catalysis biodiesel synthesis
US10239812B2 (en) 2017-04-27 2019-03-26 Sartec Corporation Systems and methods for synthesis of phenolics and ketones
US10544381B2 (en) 2018-02-07 2020-01-28 Sartec Corporation Methods and apparatus for producing alkyl esters from a reaction mixture containing acidified soap stock, alcohol feedstock, and acid
CN111250113A (en) * 2018-11-30 2020-06-09 中国科学院大连化学物理研究所 Application of super acidic catalyst in direct synthesis of adiponitrile from adipic acid
US10696923B2 (en) 2018-02-07 2020-06-30 Sartec Corporation Methods and apparatus for producing alkyl esters from lipid feed stocks, alcohol feedstocks, and acids
CN112206759A (en) * 2020-11-18 2021-01-12 山东理工大学 Low-cost recyclable CaO/Al2O3Process for preparing solid base catalyst
CN116836757A (en) * 2023-08-14 2023-10-03 平湖市晨星科技实业有限公司 Method for producing biodiesel by utilizing rare earth compound and solid super acidic catalyst

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1180881C (en) * 2002-07-23 2004-12-22 北京化工大学 Magnetic nano solid base catalyst and its preparnig method
CN1580190A (en) * 2004-05-21 2005-02-16 北京化工大学 Method for preparing biodiesel by solid acid-base catalyst
CN1317357C (en) * 2005-01-27 2007-05-23 清华大学 Solid alkali catalyst, preparation and use thereof

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8686171B2 (en) 2006-08-04 2014-04-01 Mcneff Research Consultants, Inc. Methods and apparatus for producing alkyl esters from lipid feed stocks and systems including same
US8445709B2 (en) 2006-08-04 2013-05-21 Mcneff Research Consultants, Inc. Systems and methods for refining alkyl ester compositions
US7897798B2 (en) 2006-08-04 2011-03-01 Mcneff Research Consultants, Inc. Methods and apparatus for producing alkyl esters from lipid feed stocks and systems including same
US8017796B2 (en) 2007-02-13 2011-09-13 Mcneff Research Consultants, Inc. Systems for selective removal of contaminants from a composition and methods of regenerating the same
US8585976B2 (en) 2007-02-13 2013-11-19 Mcneff Research Consultants, Inc. Devices for selective removal of contaminants from a composition
CN101293209B (en) * 2007-04-29 2011-05-25 华中农业大学 Nano-solid heteropoly acid, heteropolybase catalyst suitable for producing biological diesel oil and application thereof
CN101294093B (en) * 2007-04-29 2012-10-10 华中农业大学 Integrated preparation method for biological diesel oil and isolated plant
US7943791B2 (en) 2007-09-28 2011-05-17 Mcneff Research Consultants, Inc. Methods and compositions for refining lipid feed stocks
US8466305B2 (en) 2007-09-28 2013-06-18 Mcneff Research Consultants, Inc. Methods and compositions for refining lipid feed stocks
WO2009046636A1 (en) * 2007-09-29 2009-04-16 Huazhong Agricultural University Method for producing biodiesel using solid acid-base bifunctional catalyst
CN101861372B (en) * 2007-09-29 2013-06-19 华中农业大学 Method for producing biodiesel using solid acid-base bifunctional catalyst
CN101230309B (en) * 2008-01-11 2010-04-07 四川大学 Method for preparing biodiesel by lowering value of high acid palm oil
CN101492603B (en) * 2008-01-23 2012-11-28 华中农业大学 Method for producing biodiesel by using tallowseed oil and special solid catalyst thereof
CN101294096B (en) * 2008-05-22 2011-04-20 渤海大学 Process for producing biological diesel oil
CN101353589B (en) * 2008-09-05 2011-06-08 中国林业科学研究院林产化学工业研究所 Method for preparing biodiesel by catalysis of nano magnetic sulphonated coal
US8361174B2 (en) 2008-10-07 2013-01-29 Sartec Corporation Catalysts, systems, and methods for producing fuels and fuel additives from polyols
US9102877B2 (en) 2008-11-12 2015-08-11 Sartec Corporation Systems and methods for producing fuels from biomass
CN102134514A (en) * 2011-01-26 2011-07-27 李恒全 Synthetic biodiesel and preparation method thereof
CN102134514B (en) * 2011-01-26 2013-11-13 宁海鹏静再生资源科技有限公司 Synthetic biodiesel and preparation method thereof
DE112011102947T5 (en) 2011-03-04 2013-10-17 Tianjin Polytechnic University A catalytic composite membrane used for the catalysis of the esterification and their preparation
CN103301855A (en) * 2013-07-04 2013-09-18 南通宝聚颜料有限公司 Preparation method of titanium dioxide loaded spherical solid super acid
CN104923301A (en) * 2015-05-13 2015-09-23 安徽金邦医药化工有限公司 High-temperature-resistant cryolite-based composite solid acid catalyst and preparation method therefor
CN105130812A (en) * 2015-09-06 2015-12-09 安徽增源生物能源有限公司 Synthetic method for isopropyl palmitate
US10239812B2 (en) 2017-04-27 2019-03-26 Sartec Corporation Systems and methods for synthesis of phenolics and ketones
CN107115853A (en) * 2017-05-15 2017-09-01 中国海洋石油总公司 Mg Al houghite catalyst for handling residual oil and extra heavy oil raw material and preparation method thereof
CN107930658A (en) * 2017-11-24 2018-04-20 湘潭大学 A kind of method of short nano bar-shape structure solid base catalysis biodiesel synthesis
CN107930658B (en) * 2017-11-24 2020-11-20 湘潭大学 Method for catalytically synthesizing biodiesel by using short nano rod-shaped structure solid base
US10544381B2 (en) 2018-02-07 2020-01-28 Sartec Corporation Methods and apparatus for producing alkyl esters from a reaction mixture containing acidified soap stock, alcohol feedstock, and acid
US10696923B2 (en) 2018-02-07 2020-06-30 Sartec Corporation Methods and apparatus for producing alkyl esters from lipid feed stocks, alcohol feedstocks, and acids
CN111250113A (en) * 2018-11-30 2020-06-09 中国科学院大连化学物理研究所 Application of super acidic catalyst in direct synthesis of adiponitrile from adipic acid
CN112206759A (en) * 2020-11-18 2021-01-12 山东理工大学 Low-cost recyclable CaO/Al2O3Process for preparing solid base catalyst
CN116836757A (en) * 2023-08-14 2023-10-03 平湖市晨星科技实业有限公司 Method for producing biodiesel by utilizing rare earth compound and solid super acidic catalyst

Also Published As

Publication number Publication date
CN100503786C (en) 2009-06-24

Similar Documents

Publication Publication Date Title
CN100503786C (en) Method for preparing biological diesel oil using nano solid acid or alkali catalyst
EP2043972B1 (en) Biodiesel production using composite catalysts
Madhuvilakku et al. Biodiesel synthesis by TiO2–ZnO mixed oxide nanocatalyst catalyzed palm oil transesterification process
CN1317357C (en) Solid alkali catalyst, preparation and use thereof
Rattanaphra et al. Simultaneous conversion of triglyceride/free fatty acid mixtures into biodiesel using sulfated zirconia
CN101319169B (en) Quick and clean process for preparing biological diesel oil with esterification/ester exchange reaction
EP2049461B1 (en) Process for the production of biodiesel
CN101230309B (en) Method for preparing biodiesel by lowering value of high acid palm oil
CN1664072A (en) Method for producing biological diesel oil by using solid base catalyst
CN1861750A (en) Process of preparing biological diesel
Siregar et al. Synthesis and characterization of sodium silicate produced from corncobs as a heterogeneous catalyst in biodiesel production
CN1928018A (en) Method of preparing biological diesel oil using solid base catalyst
Pan et al. Functional nanomaterials-catalyzed production of biodiesel
CN1737086A (en) Method for preparing bio- diesel oil
Halek et al. Biodiesel production from waste edible oil with heterogeneous catalysts (nanoclay-based nanocatalysts)
Zhu et al. Preparation and characterization of a novel bifunctional heterogeneous Sr–La/wollastonite catalyst for biodiesel production
Peng et al. Magnetic graphene oxide supported tin oxide (SnO) nanocomposite as a heterogeneous catalyst for biodiesel production from soybean oil
Asri et al. Synthesis of biodiesel from kesambi (Schleichera oleosa L.) oil using carbon nanotube-supported zinc oxide heterogeneous catalyst
Hayyan et al. Production of biodiesel from sludge palm oil by esterification process
CN100375780C (en) Production of biological diesel oil with solid alkali
WO2012059323A1 (en) Process for preparation of supported catalysts and use of the catalyst for the esterification of free fatty acids in vegetable oil
CN102974370A (en) Solid acid catalyst and use thereof
CN101045878A (en) Two-step solid acid and solid alkali catalyzing process for producing biodiesel oil
Asri et al. Development of heterogeneous alumina supported base catalyst for biodiesel production.
CN101913638B (en) Micrometer calcium oxide, preparation method thereof and use thereof in preparation of biodiesel

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
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20090624

Termination date: 20180602

CF01 Termination of patent right due to non-payment of annual fee