CN100465249C - Method for preparing biodiesel oil - Google Patents
Method for preparing biodiesel oil Download PDFInfo
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- CN100465249C CN100465249C CNB2006101555243A CN200610155524A CN100465249C CN 100465249 C CN100465249 C CN 100465249C CN B2006101555243 A CNB2006101555243 A CN B2006101555243A CN 200610155524 A CN200610155524 A CN 200610155524A CN 100465249 C CN100465249 C CN 100465249C
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- 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
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- 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
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- 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
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Abstract
The invention discloses a making method of biological diesel, which comprises the following steps: (1) hydrolyzing grease under 250-370 deg. c at 2. 0-10.0Mpa in the reactor for 1-3h; separating to obtain the aliphatic acid phase; (2) adopting solid acid/alkali as catalyst to fix continuously in the reactor; reacting the aliphatic acid and low-grade alcohol with weight rate at 28-55 continuously to generate the biological diesel under 50-200 deg. c; (3) distilling through short path; separating; purifying the biological diesel.
Description
Technical field
The invention belongs to field of grease chemical technology, the preparation method of particularly a kind of mixture of higher fatty acid low-carbon-ester (biofuel).
Background technology
Biofuel is the mixture of higher fatty acid low-carbon-ester, is mainly made by animal and plant grease and lower alcohol generation transesterification reaction.In the biodiesel manufacture process, selection of catalysts is extremely important, at present, the transesterification legal system of bibliographical information is equipped with and mainly in the technology of biofuel adopts following four class catalyzer: the one, and inorganic liquid alkali (as sodium hydroxide, potassium hydroxide etc.) or rudimentary sodium alkoxide (sodium methylate, sodium ethylate etc.); The 2nd, solid acid/alkaline catalysts is as acid/basic resin or metal oxide, heteropolyacid etc.; The 3rd, overcritical no catalysis transesterification down; The 4th, biological enzyme.First kind catalyzer belongs to highly basic, and miscible better with grease and methyl alcohol, so this catalytic process more easily realizes, and condition is comparatively gentle, as react the yield that can reach more than 95% in 3-5 hour about 60 ℃.But there is the easy saponification inactivation of catalyzer in this technology, product emulsification is serious, aftertreatment bothers and aftertreatment produces the problem of large amount of sewage, thereby is restricted.In order to address the above problem, disclosing the second class catalyzer among the Chinese invention patent CN200510011269.0 is solid acid/this transesterification of alkaline catalysts catalysis.But because methyl alcohol and grease mutual solubility are relatively poor, and catalyzer is a solid phase, makes mass transfer difficulty in the reaction process.Although the more important thing is acid energy catalysis transesterification, but report (" Synthesis of Biodiesel via Acid Catalysis " is arranged, Industrial Engineering ChemicalResearch, 2005 (44): 5353-5363) show that its catalytic effect is far below alkaline catalysts, therefore when adopting the greasy transesterification of solid acid catalyst catalysis, reaction times is often very long, and condition is comparatively harsh, as needs comparatively high temps and pressure etc.; And existing solid base catalyst alkalescence is weak or less stable, although be useful on the patent report of biodiesel manufacture aspect, is difficult to realize industrialization.There is research to adopt supercritical methanol under no catalytic condition, to prepare biofuel recently with grease generation transesterification, transesterification reaction as six kind of plant greases in the research supercritical methanols such as Demirbas, temperature of reaction is 200-240 ℃, methyl alcohol and grease mol ratio surpass under 40 the condition, obtain productive rate when reacting 5 minutes and surpassed 90% fatty acid methyl ester (" Biodiesel from vegetableoils via transesterification in supercritical methanol ", Energy Conversion andManagement, 2002 (43): 2349-2356), Chinese invention patent 200410013430.3 discloses at 220-400 ℃, carry out transesterification reaction under the 8-25MPa, reacted 4-30 minute, and also can obtain methyl ester conversion rate preferably.Methyl alcohol and grease dissolve each other in the supercritical methanol system, make reaction become homogeneous phase, thereby solved the interphase mass transfer problem, thereby speed of response significantly improves the reaction times shortening.And reaction need not catalyzer, and aftertreatment is simple, but this technology is to equipment requirements condition height, and industrialization is difficulty comparatively.The 4th class catalyzer adopts biological enzyme then to have the cost height, and easy inactivation of enzyme and cost are high and be difficult to industrialization.
Another problem of biodiesel manufacture is the separation and purification of product.The method of a kind of leaving standstill/centrifuging is disclosed in the Chinese invention patent 03135560.9, a kind of method of low temperature crystallization is disclosed in the Chinese invention patent 01107895.2, also can adopt (" the Catalytic production of biodiesel from soy-bean oil; used frying oil andtallow " such as methods of distillation or rectifying, Biomass and Bioenergy, 2000 (18): 515-527).Employing leaves standstill/and centrifugal filtering method separating bio diesel equipment is comparatively simple, but separate not thorough, biofuel and glycerine quality all are difficult to reach requirement, and adopt the method existence of rectifying to reduce the danger of yield owing to overstand in the high temperature causes the further polymerization of biofuel.
Summary of the invention
This patent provides a kind of constant product quality, quality better, yield height, process successive biodiesel oil preparing process.
A kind of preparation method of biofuel comprises the steps:
(1) grease, water are dropped into the high pressure stirred-tank reactor, in the reactor, carry out greasy hydrolysis.
Hydrolysis reaction is finished under near clinical water condition, and water is 1:0.9-4 with the oil quality ratio, and hydrolysis temperature is 250-370 ℃, and hydrolysis pressure is 2.0-10.0MPa, hydrolysis time 1-3h, and this moment, the percent hydrolysis of lipid acid reached 80-88%;
After hydrolysis reaction was finished, product was divided into two-phase, light part mutually be lipid acid be lipid acid mutually with unreacted grease mutually, heavy phase partly is the G ﹠ W phase.
The light phase that the first time, hydrolysis reaction obtained partly is that lipid acid can directly go to carry out esterification mutually, but in order to make the unreacted fat hydrolysis of light phase part thorough, water washing with 50-70 ℃, the washing water consumption is the 3%-8% of lipid acid/grease phase quality, and washing water merge with heavy phase (glycerin/water mutually) and can be used for the glycerine separation and purification.Light after the washing carried out the hydrolysis second time in the high pressure stirred-tank reactor.
Hydrolysis temperature is 250-370 ℃ for the second time, and hydrolysis pressure is 2.0-20.0MPa, hydrolysis time 1-3h, and this moment, the percent hydrolysis of lipid acid reached 94-99.5%; Isolate then lipid acid mutually with glycerin/water mutually, glycerin/water is used for the separation and purification of glycerine mutually.
Hydrolysis reaction can carry out in the stirring tank at intermittence, also can carry out in placed in-line continuous stirred tank.Do not allow reaction carry out thorough considered in hydrolysis for the second time, and hydrolysis pressure can slightly improve.
(2) be catalyzer in fixed-bed reactor continuously with solid acid/alkali, lipid acid and the lower alcohol that obtains in the step (1) carried out esterification generation biofuel.
Operational condition is: the mass ratio 1:1-4 of lower alcohol and lipid acid, and temperature of reaction 50-200 ℃, reflect mouth pressure 0.1-0.5MPa, reaction solution flow velocity 0.25-0.5BV/h, the one way reaction conversion ratio reaches 90-99%.
(3) by short-path distillation, with biofuel (lipid acid low-carbon-ester), lower alcohol/water mixture, and the separation of unreacted lipid acid, obtain biofuel.
The short-path distillation equipment that adopts is the two-stage short-path distillation.
One-level short-path distillation vacuum tightness 50-200Pa, 50 ℃-120 ℃ of temperature are collected and are gently obtained water and methyl alcohol mixed liquor mutually, further recyclable methyl alcohol recycling behind rectifying tower;
Secondary short-path distillation vacuum tightness 0.5-10Pa, temperature is 180-280 ℃, and collecting light phase component is fatty acid methyl ester, and purity surpasses 95%.The heavy phase component is the lipid acid that is mixed with little fat acid methyl esters, fatty acid content〉85%, can repeat to enter fixed bed after the collection and carry out esterification.
Two sections distillatory blade applicator rotating speeds are 350-600rpm, and cold-boundary temperature is 30-60 ℃.
Grease described in the present invention can be natural plant grease or animal tallow, also can be Vegetable oil lipoprotein or animal tallow after part is become sour.
Described solid acid/alkaline catalysts is a synthetic zeolite, a kind of in molecular sieve, acid/alkaline metal oxide, strongly-acid macroporous resin or other the solid strong acid/alkaline catalysts etc. after modified.
Lower alcohol described in the step (2) refers to the Fatty Alcohol(C12-C14 and C12-C18) of short carbon chain, a kind of as in methyl alcohol, ethanol, propyl alcohol, Virahol or the propyl carbinol.
The present invention has changed the technology of available technology adopting grease transesterification, but it is decomposed into the esterification two-step reaction of greasy hydrolysis and lipid acid, the esterification rate of lipid acid in the presence of acid/alkaline catalysts be much larger than the transesterification speed of grease under same catalyst, thereby avoided the low problem of the greasy transesterification speed of traditional employing solid acid catalysis.This technology has following advantage specifically:
Adopt in the reaction process of near-critical water hydrolysate oil and need not to add acid base catalysator, no environmental protection pressure, the reaction times lacks, and consumes lowly, is easy to industrialization;
Adopt the esterification of solid acid/base catalysis lipid acid, no waste water produces, and process is continuous, stable, mild condition, and speed of reaction is very fast;
Adopt the short-path distillation technical point from final biofuel product, the hot residence time of product is short, thereby guarantees that product can not reduce because of pyrolytic decomposition makes quality.Make constant product quality, quality better, yield height, process is continuous, is suitable for large-scale production.
Description of drawings
Fig. 1 is the device synoptic diagram of the inventive method
Specific embodiment
10kg water and the commercially available soybean oil of 10kg are placed the high pressure stirred-tank reactor 1 of 80L, and the control hydrolysis temperature is 270 ℃, and pressure is 5.6MPa.Finish reaction behind the hydrolysis 2h, the percent hydrolysis that detects lipid acid reaches 88.0%; Enter the extraction kettle 2 of 80L after the product cooling, be divided into lipid acid/grease mutually and glycerin/water mutually, branch goes the glycerin/water phase, with the remaining lipid acid/grease phase of 50-70 ℃ water washing, the washing water consumption is 0.3kg, and finally obtaining lipid acid/grease phase quality is 9.54kg, glycerin/water phase 10.4kg.
9.54kg lipid acid/grease is placed 80L high pressure stirring tank 3 mutually, and add 10kg water and carry out the hydrolysis reaction second time, 270 ℃ of hydrolysis temperatures, hydrolysis pressure are 8MPa, in 2.5 hours reaction times, record the lipid acid total recovery and reach 99.1%.The extraction kettle 4 that enters 80L after after product cools off is finished in reaction, with 0.29kg water washing lipid acid, gets lipid acid 9.41kg, glycerin/water phase 10.1kg.
9.41kg lipid acid and 9.41kg methyl alcohol are fed in the fixed-bed reactor 5 60 ℃ of abundant down miscible backs, and fixed bed is of a size of
, be catalyzer with acidic resins NKA-9,60 ℃ of temperature of reaction reflect mouth pressure 0.15MPa, feeding liquid flow velocity 0.25BV/h.With the product that is detained in the 5kg washed with methanol bed, the final mixture that gets 23.82kg fatty acid methyl ester and methanol recorded conversion rate of fatty acid and reaches 97.5% after charging finished.
23.82kg fatty acid methyl ester and methanol mixture in short-path distillation equipment, are realized lipid acid low-carbon-ester, lower alcohol/water mixture, and the separation of unreacted lipid acid.The short-path distillation equipment that adopts is the secondary short-path distillation, and its operational condition is: two sections distillatory blade applicator rotating speeds are 550rpm, and cold-boundary temperature is 50 ℃; Vacuum tightness 10Pa, 120 ℃ of one-level short-path distillation equipment 6 temperature are collected and are gently obtained water and methyl alcohol mixed liquor 13.2kg mutually, further recyclable methyl alcohol recycling behind rectifying tower; Secondary short-path distillation equipment 7 temperature are 200 ℃, and collecting light phase component is fatty acid methyl ester 10.6kg, and detecting fatty acid methyl ester is 95.3%, collects heavy phase component 0.11kg, and this component can repeat to enter fixed bed and carry out esterification.
10kg water and the commercially available soybean oil of 20kg are placed the high pressure stirred-tank reactor of 80L, and the control hydrolysis temperature is 300 ℃, and pressure is 8.65MPa.Finish reaction behind the hydrolysis 2.5h, the percent hydrolysis that detects lipid acid reaches 85.5%; Enter the extraction kettle of 80L after the product cooling, be divided into lipid acid/grease mutually and glycerin/water mutually, branch goes the glycerin/water phase, with the remaining lipid acid/grease phase of 50-70 ℃ water washing, the washing water consumption is 0.93kg, and finally obtaining lipid acid/grease phase quality is 18.5kg, glycerin/water phase 12.5kg.
18.5kg lipid acid/grease is placed 80L high pressure stirring tank mutually, and add 10kg water and carry out the hydrolysis reaction second time, 300 ℃ of hydrolysis temperatures, hydrolysis pressure are 2.5 hours 12MPa reaction times, record the lipid acid total recovery and reach 99.1%.After finishing, reaction, gets lipid acid 18.28kg, glycerin/water phase 10.34kg with 0.29kg water washing lipid acid.
18.28kg lipid acid and 9.14kg methyl alcohol are fed in the fixed-bed reactor 60 ℃ of abundant down miscible backs, and fixed bed is of a size of
, be catalyzer with acidic resins NKA-9,75 ℃ of temperature of reaction reflect mouth pressure 0.2MPa, feeding liquid flow velocity 0.35BV/h.With the product that is detained in the 5kg washed with methanol bed, the final mixture that gets 32.42kg fatty acid methyl ester and methanol recorded conversion rate of fatty acid and reaches 95.9% after charging finished.
32.42kg fatty acid methyl ester and methanol mixture in short-path distillation equipment, are realized lipid acid low-carbon-ester, lower alcohol/water mixture, and the separation of unreacted lipid acid.The short-path distillation equipment that adopts is the secondary short-path distillation, and its operational condition is: two sections distillatory blade applicator rotating speeds are 550rpm, and cold-boundary temperature is 50 ℃; Vacuum tightness 10Pa, 100 ℃ of one-level short-path distillation temperature are collected and are gently obtained water and methyl alcohol mixed liquor 11.67kg mutually, further recyclable methyl alcohol recycling behind rectifying tower; Secondary short-path distillation temperature is 250 ℃, and collecting light phase component is fatty acid methyl ester 20.54kg, and detecting fatty acid methyl ester is 95.3%, collects heavy phase component 0.21kg, and this component can repeat to enter fixed bed and carry out esterification.
10kg water and the commercially available soybean oil of 30kg are placed the high pressure stirred-tank reactor of 80L, and the control hydrolysis temperature is 325 ℃, and pressure is 9MPa.Finish reaction behind the hydrolysis 2.8h, the percent hydrolysis that detects lipid acid reaches 84.1%; Enter the extraction kettle of 80L after the product cooling, be divided into lipid acid/grease mutually and glycerin/water mutually, branch goes the glycerin/water phase, with the remaining lipid acid/grease phase of 50-70 ℃ water washing, the washing water consumption is 2.23kg, and finally obtaining lipid acid/grease phase quality is 27.85kg, glycerin/water phase 14.45kg.
27.85kg lipid acid/grease is placed 80L high pressure stirring tank mutually, and add 10kg water and carry out the hydrolysis reaction second time, 300 ℃ of hydrolysis temperatures, hydrolysis pressure are 15MPa, in 2.8 hours reaction times, record the lipid acid total recovery and reach 98.6%.After finishing, reaction, gets lipid acid 27.47kg, glycerin/water phase 12.54kg with 2.23kg water washing lipid acid.
27.47kg lipid acid and 9.16kg methyl alcohol are fed in the fixed-bed reactor 60 ℃ of abundant down miscible backs, and fixed bed is of a size of
, be catalyzer with acidic resins D-72,90 ℃ of temperature of reaction reflect mouth pressure 0.25MPa, feeding liquid flow velocity 0.35BV/h.With the product that is detained in the 5kg washed with methanol bed, the final mixture that gets 41.62kg fatty acid methyl ester and methanol recorded conversion rate of fatty acid and reaches 97.1% after charging finished.
41.62kg fatty acid methyl ester and methanol mixture in short-path distillation equipment, are realized lipid acid low-carbon-ester, lower alcohol/water mixture, and the separation of unreacted lipid acid.The short-path distillation equipment that adopts is the secondary short-path distillation, and its operational condition is: two sections distillatory blade applicator rotating speeds are 550rpm, and cold-boundary temperature is 50 ℃; Vacuum tightness 10Pa, 120 ℃ of one-level short-path distillation temperature are collected and are gently obtained water and methyl alcohol mixed liquor 10.45kg mutually, further recyclable methyl alcohol recycling behind rectifying tower; Secondary short-path distillation temperature is 230 ℃, and collecting light phase component is fatty acid methyl ester 30.86kg, and detecting fatty acid methyl ester is 95.3%, collects heavy phase component 0.31kg, and this component can repeat to enter fixed bed and carry out esterification.
10kg water and the commercially available soybean oil of 40kg are placed the high pressure stirred-tank reactor of 80L, and the control hydrolysis temperature is 350 ℃, and pressure is 10MPa.Finish reaction behind the hydrolysis 3.0h, the percent hydrolysis that detects lipid acid reaches 83.2%; Enter the extraction kettle of 80L after the product cooling, be divided into lipid acid/grease mutually and glycerin/water mutually, branch goes the glycerin/water phase, with the remaining lipid acid/grease phase of 50-70 ℃ water washing, the washing water consumption is 2.98kg, and finally obtaining lipid acid/grease phase quality is 37.22kg, glycerin/water phase 15.78kg.
37.22kg lipid acid/grease is placed 80L high pressure stirring tank mutually, and add 10kg water and carry out the hydrolysis reaction second time, 350 ℃ of hydrolysis temperatures, hydrolysis pressure are 20MPa, in 3.0 hours reaction times, record the lipid acid total recovery and reach 98.9%.After finishing, reaction, gets lipid acid 36.68kg, glycerin/water phase 13.54kg with 2.98kg water washing lipid acid.
36.68kg lipid acid and 9.17kg methyl alcohol are fed in the fixed-bed reactor 60 ℃ of abundant down miscible backs, and fixed bed is of a size of
, be catalyzer with acidic resins D-72,90 ℃ of temperature of reaction reflect mouth pressure 0.25MPa, feeding liquid flow velocity 0.25BV/h.With the product that is detained in the 5kg washed with methanol bed, the final mixture that gets 50.85kg fatty acid methyl ester and methanol recorded conversion rate of fatty acid and reaches 98.5% after charging finished.
50.85kg fatty acid methyl ester and methanol mixture in short-path distillation equipment, are realized lipid acid low-carbon-ester, lower alcohol/water mixture, and the separation of unreacted lipid acid.The short-path distillation equipment that adopts is the secondary short-path distillation, and its operational condition is: two sections distillatory blade applicator rotating speeds are 550rpm, and cold-boundary temperature is 50 ℃; Vacuum tightness 10Pa, 120 ℃ of one-level short-path distillation temperature are collected and are gently obtained water and methyl alcohol mixed liquor 9.23kg mutually, further recyclable methyl alcohol recycling behind rectifying tower; Secondary short-path distillation temperature is 250 ℃, and collecting light phase component is fatty acid methyl ester 41.21kg, and detecting fatty acid methyl ester is 95.9%, collects heavy phase component 0.45kg, and this component can repeat to enter fixed bed and carry out esterification.
Claims (8)
1, a kind of preparation method of biofuel comprises the steps:
(1) grease, water are dropped into reactor, carry out hydrolysis reaction twice, separate the lipid acid phase that obtains hydrolysis for the first time after hydrolysis is for the first time finished, with 50-70 ℃ water washing, the lipid acid of the hydrolysis first time after the washing is carried out the hydrolysis second time mutually, obtain the lipid acid phase of hydrolysis for the second time; Wherein, hydrolysising reacting temperature is 250-370 ℃ for the first time, and pressure is 2.0-10.0MPa, time 1-3h, and hydrolysising reacting temperature is 250-370 ℃ for the second time, pressure is 2.0-20.0MPa, time 1-3h, water is 1:0.9-4 with the oil quality ratio;
(2) be catalyzer in fixed-bed reactor continuously with solid acid/alkali, the lipid acid of the hydrolysis second time that obtains in the step (1) is carried out esterification generation biofuel with methyl alcohol, the mass ratio of methyl alcohol and lipid acid is 1:1-4, temperature of reaction 50-200 ℃;
(3) separate the biofuel that generates in the purification step (2) by short-path distillation.
2, preparation method as claimed in claim 1 is characterized in that: the water consumption of the lipid acid phase of washing hydrolysis for the first time is the 3%-8% of lipid acid phase quality.
3, preparation method as claimed in claim 1 is characterized in that: the esterification top hole pressure 0.1-0.5MPa described in the step (2), reaction solution flow velocity 0.25-0.5BV/h.
4, preparation method as claimed in claim 1 is characterized in that: the short-path distillation described in the step (3) is the two-stage short-path distillation, one-level short-path distillation vacuum tightness 50-200Pa, 50 ℃-120 ℃ of temperature; Secondary short-path distillation vacuum tightness 0.5-10Pa, temperature is 180-280 ℃, the light phase component of collecting the secondary short-path distillation obtains biofuel.
5, preparation method as claimed in claim 4 is characterized in that: it is 350-600rpm that described two-stage short-path distillation all adopts rotating speed, and cold-boundary temperature is 30-60 ℃ a blade applicator.
6, preparation method as claimed in claim 4 is characterized in that: repeat after the heavy phase component of secondary short-path distillation is collected to enter in the fixed-bed reactor of step (2) and carry out esterification.
7, preparation method as claimed in claim 1 is characterized in that: described grease is the animal tallow after Vegetable oil lipoprotein after natural plant grease, animal tallow, part are become sour or part are become sour.
8, preparation method as claimed in claim 1 is characterized in that: the solid acid/alkaline catalysts described in the step (2) is a synthetic zeolite, molecular sieve, acid/alkaline metal oxide or strongly-acid macroporous resin after modified.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102352270A (en) * | 2011-07-20 | 2012-02-15 | 浙江大学 | Technology for preparing fuel by lightweight fraction obtained by bio-oil gradation |
| CN106318648A (en) * | 2015-06-30 | 2017-01-11 | 中国科学院大连化学物理研究所 | Transesterification method based on microchannel reactor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101440299B (en) * | 2008-12-09 | 2012-11-14 | 湘潭昭山油化科技有限公司 | Method for preparing -10 DEC C biodiesel from waste lipid by distillation process |
| DE102008060902A1 (en) | 2008-12-09 | 2010-06-10 | Grace Gmbh & Co. Kg | Preparing fatty acid alkyl ester from feed stock containing e.g. free fatty acids and fatty acid triglycerides, comprises esterifying feedstock with alkyl alcohol in presence of catalyst and transesterifying the free fatty acid feedstock |
| CN106337069A (en) * | 2015-07-13 | 2017-01-18 | 清华大学 | Fatty acid short chain ester two-step preparation technology |
| CN107034243A (en) * | 2015-07-13 | 2017-08-11 | 清华大学 | The preparation technology of fatty acid short-chain ester |
| CN107162931B (en) * | 2017-05-24 | 2019-07-16 | 国家电网公司 | A kind of preparation process and device of environmental protection insulating gas perfluoroalkyl nitrile |
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| CN1594504A (en) * | 2004-07-08 | 2005-03-16 | 武汉化工学院 | Process for supercritical preparation of biologic diesel oil |
| CN1680514A (en) * | 2005-01-27 | 2005-10-12 | 清华大学 | Solid alkali catalyst, preparation and use thereof |
| CN1827742A (en) * | 2006-04-06 | 2006-09-06 | 河南省商丘油脂化学厂 | Application of selective hydrolysis process in bio-diesel oil production |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1594504A (en) * | 2004-07-08 | 2005-03-16 | 武汉化工学院 | Process for supercritical preparation of biologic diesel oil |
| CN1680514A (en) * | 2005-01-27 | 2005-10-12 | 清华大学 | Solid alkali catalyst, preparation and use thereof |
| CN1827742A (en) * | 2006-04-06 | 2006-09-06 | 河南省商丘油脂化学厂 | Application of selective hydrolysis process in bio-diesel oil production |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102352270A (en) * | 2011-07-20 | 2012-02-15 | 浙江大学 | Technology for preparing fuel by lightweight fraction obtained by bio-oil gradation |
| CN102352270B (en) * | 2011-07-20 | 2014-08-13 | 浙江大学 | Technology for preparing fuel by lightweight fraction obtained by bio-oil gradation |
| CN106318648A (en) * | 2015-06-30 | 2017-01-11 | 中国科学院大连化学物理研究所 | Transesterification method based on microchannel reactor |
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