CN101358141A - Method for preparing bio diesel oil by idesia polycarpa maxim. var. vestita diels oil catalysis using solid base as catalyst - Google Patents
Method for preparing bio diesel oil by idesia polycarpa maxim. var. vestita diels oil catalysis using solid base as catalyst Download PDFInfo
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- CN101358141A CN101358141A CNA2008100461958A CN200810046195A CN101358141A CN 101358141 A CN101358141 A CN 101358141A CN A2008100461958 A CNA2008100461958 A CN A2008100461958A CN 200810046195 A CN200810046195 A CN 200810046195A CN 101358141 A CN101358141 A CN 101358141A
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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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- 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 present invention discloses a technique which uses solid alkali to catalyze idesia polycarpa var.vestita bites to prepare biodiesel. After the extracted idesia polycarpa var.vestita bites is treated by the processes of degumming, alkali refining and deacidification and decolorization, solid alkali Mg-Al composite oxide is utilized to catalyze low-carbon alcohol, so that ester exchange reaction occurs between the low-carbon alcohol and the idesia polycarpa var.vestita bites to prepare crude biodiesel, and after depressurization and distilling, the light-colored refined biodiesel is produced. The yield of the biodiesel prepared by the technique is high, the product reaches the national standards, meanwhile, the production cost of the biodiesel can be reduced, the service life of equipment can be prolonged, the subsequent separation process can be simplified, and the drainage of industrial waste water can be reduced.
Description
Technical field
The invention belongs to Idesia polycarpa oil preparation biodiesel technology field, be specifically related to a kind of with catalyzed by solid base Idesia polycarpa oil preparation method of bio-diesel oil.
Background technology
High speed development along with world economy, the human energy that consumes is more and more, and non-renewable oil, coal storage are fewer and feweri, the problem in short supply of the energy, become the human cardinal task of being badly in need of solution, developing reproducible biomass energy becomes the common focus of paying close attention in countries in the world.
Alcohol fuel and biofuel become the main research object of biomass energy.According to the definition of American society association (ASTM), it is the long chain fatty acid monoesters of raw material production that biofuel (Biodiesel) is meant with renewable biological source such as animal-plant oil, can be used for the cleaning alternative fuel of self-igniton engine; It is that low-carbon alcohol such as grease and methyl alcohol are carried out the transesterification reaction generation under the effect of catalyzer such as acid, alkali or enzyme, have renewable, easy degraded, nontoxic, sulphur content is low and combustion exhaust in advantages such as noxious emission is few, be environmentally friendly fuel (patent publication No. CN101148600A, method for preparing biological diesel oil from waste animals and plants grease).
At present, concentrating on edible oil or depleted catering trade grease to the research majority of biofuel is the feedstock production aspect, not only there is the extremely limited problem that costs an arm and a leg and originate in these raw materials, and be the feedstock production biofuel with the inedible oil, as curcas oil, wild sylvic oil, rubber seed oil, hair corn wet goods, the fruit productive rate low for ubiquity again, few and the feasible or plantation of oil offtake low in economic efficiency, or the too high problem of the production cost of biofuel.To this, danger Wen Liang etc. just mentions raw materials cost and accounts for 70% of biofuel total cost in " analysis of strategies of China development energy oil crops " literary composition, make it to become a big obstacle of restriction biofuel industry development.
Idesia polycarpa (also claiming the water wax gourd) is the native country seeds of China, not only have drought-enduring, impoverishment tolerant, diseases and insect pests resistance is strong, the soil is required low outstanding advantage, (single plant yield is up to 200~300kg to the more important thing is Idesia polycarpa output height, the phase per mu yield of abounding with can reach more than the 2500kg, produce fruit for up to 70~100 years), Idesia polycarpa fruit oil length height (the dry fruit oil length is up to 36~38%), good (unsaturated fatty acids>82% wherein of Idesia polycarpa fruit oil quality, linolic acid>68%, linolenic acid>2%).China is that the research of water white gourd oil just began as far back as last century to Idesia polycarpa oil.1980, kingdom's gift, Zhang Zhi really the article of " research of lipid acid composition, smell component, refinery practice and the interim test of water white gourd oil " delivered (Chinese oil, 1981, (S1); Shaanxi science and technology message, 1980,12 phases, exercise question is " the synthetic study bulletin of water white gourd oil ") in just introduced the many-side research that the water white gourd oil is carried out, and, find that the linoleic acid content of seed oil reaches 81% by gas chromatographic analysis, pulp oil reaches 68%, thereby it is not only good edible oil, and can be as the raw material of producing the linolic acid preparation on the medicine industry.
In addition, ZL200410081444.9 also by improving method breeding idesia with hairy leaves, effectively reduces the cost of Idesia polycarpa fruit, and the fruit oil yield is higher, oil quality good.
These research and development are had laid a good foundation as the good raw material of preparation biofuel for the Idesia polycarpa fruit oil, make it to have very big development potentiality.
At present, the most frequently used is homogeneous phase alkaline catalysts catalyzed transesterification method with renewable biological source such as animal-plant oil for the raw material production method of bio-diesel oil, the catalyzer that this method adopts generally is sodium hydroxide and potassium hydroxide, its major advantage is that catalyzer is cheap and easy to get, less demanding to reaction conditions, speed of reaction is very fast.But the shortcoming that also has some, as easy generation saponification side reaction, the not easily separated purification of by-product glycerin, catalyzer can not reuse, serious to equipment corrosion, particularly in treating process, need the washing, thereby to bring a large amount of trade effluent etc.Coarse wool leaf idesia oil as the preparation biofuel is no exception, and also needing to carry out catalyzed transesterification just can become refining oil, and the catalyzer that adopts does not at present break away from traditional basic catalyst yet., the alkali refining agent changed into use soda ash in " introduction of water white gourd oil novel process for refining " (food science and technology, 1996, (06)) as Yang Shoujie, determined the suitable concentration that adds alkali number and alkali, found best alkali refining temperature, time, effect is fine.It is catalyzer that and for example Chinese invention patent application " prepare method of bio-diesel oil by the water white gourd oil " to have proposed with sodium hydroxide or potassium hydroxide, prepares method of bio-diesel oil (200610042737.5) with Purified Water white gourd oil (Idesia polycarpa oil) and methyl alcohol.The same year, people such as the Su Yin of Xibei Univ. of Agricultural ﹠ Forest Science ﹠ Technology spring have proposed the patent application (200610105380.0) of " a kind of water white gourd oil prepares method of bio-diesel oil ", technical scheme in this application still adopts traditional basic catalyst sodium hydroxide or potassium hydroxide, prepare biofuel with Purified Water white gourd oil (Idesia polycarpa oil) and methyl alcohol, just technical process is slightly different with last patent application.
In order to solve the problems referred to above that the preparation biofuel exists, in recent years, many investigators research and develop new technology, novel process to reduce pollution from multiple channel, make full use of the value of by-product glycerin.Wherein the catalyst technology of development of new, environmental protection becomes one of research focus.Solid base catalyst is exactly the catalyzer of grew up in recent years a kind of novel, environmental protection, this catalyzer has the reaction conditions gentleness, product is easy to separate, easily be automated, serialization, advantage such as can be recycled, be expected to become eco-friendly catalytic material of new generation (Song Huamin etc., " progress of preparing biological diesel oil catalyzed by solid base " Anhui agricultural sciences; 2008,36 (5)).
Summary of the invention
The objective of the invention is problem, provide a kind of, to reach purposes such as reducing production of biodiesel cost, simplification follow-up separation process, minimizing industrial wastewater discharge with catalyzed by solid base Idesia polycarpa oil preparation method of bio-diesel oil at the prior art existence.
The solid alkali of using provided by the invention is that the processing step of this method and condition are with the oil of the Mg-Al composite oxide catalytic Idesia polycarpa in solid alkali preparation method of bio-diesel oil specifically:
(1) with the Idesia polycarpa oil of squeezing under 70~80 ℃ of temperature, add and to count 5~7% same warm water by the weight of Idesia polycarpa oil and carry out hydration degum 30~40min;
(2) oil after will coming unstuck carries out after drying dewaters, and heating also control oil temperature is stirred to add down and pressed elaeometer 6~8% at 70~80 ℃, and concentration is that 19% homogeneous phase alkaline solution carries out alkali-refining deacidification 40~50min,
(3) the Idesia polycarpa oil behind the alkali refining is under 90~100 ℃ of temperature, and adding by elaeometer is 5~6% pre-activated decoloration 40~50min prior to 150 ℃ of following activation 2h.
(4) will count 1~3% solid alkali Mg-Al composite oxides by decolouring back grease weight, adding mol ratio is in 6: 1~9: 1 the low-carbon alcohol and the greasy mixed solution that decolours, and at 50~70 ℃ of following stirring reaction 2~4h of temperature, after reaction finishes, unreacted low-carbon alcohol is reclaimed in distillation, reaction liquid phase filtered while hot, and isolate catalyst solid alkali and reuse, with the filtrate standing demix, the upper strata product is coarse biodiesel then.
(5)-0.080~-vacuum tightness of 0.095MPa under, add by coarse biodiesel weight and count 0.1~0.2% stopper boric acid in coarse biodiesel and distill, collect cut, promptly obtain refining biodiesel.
Wherein the used homogeneous phase alkali of this method is sodium hydroxide or potassium hydroxide; Used low-carbon alcohol is any in methyl alcohol, ethanol, the Virahol.
Compared with the prior art the present invention has the following advantages:
1, because the present invention produces biofuel with catalyzed by solid base Idesia polycarpa oil, thereby avoided a series of problems of using traditional strong basicity sodium hydroxide or potassium hydroxide catalyst to be brought, in the work-ing life of prolonged mechanical equipment, reduced production costs.
2, because the solid alkali Mg-Al composite oxides that the present invention selects for use have stronger catalytic capability; not only make the biofuel yield height that obtains; product is up to state standards; and this catalyzer is easy to separate with product especially; can reuse, thereby simplified follow-up separation process, avoid adding acid neutralization and washing in the treating process; significantly reduce the discharging of trade effluent, met green industry and requirement on environmental protection.
Embodiment
Provide embodiment below so that the present invention will be described in more detail; it is important to point out that following examples can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field must belong to protection scope of the present invention according to the invention described above content to some nonessential improvement and the adjustment that the present invention did.
Embodiment 1
(1) with the Idesia polycarpa oil of 70.10g squeezing under 75 ℃, add oil and weigh 7% same warm water and carry out hydration degum 30min;
(2) oil after will coming unstuck carries out after drying dewaters, heating also control oil temperature at 80 ℃, stir add down oil heavy 6%, concentration is that 19% sodium hydroxide solution carries out alkali-refining deacidification 50min;
(3) the Idesia polycarpa oil behind the alkali refining is under 95 ℃, add oil heavy 5% and in advance prior to 150 ℃ of activated decoloration 40min of activation 2h down;
(4) with 50.10g decolouring back grease, after 12.53g methyl alcohol (molar ratio of methanol to oil is 6: 1) mixes, add again by decolouring back grease weight and count 1.0% Mg-Al composite oxides, and at 60 ℃ of lower magnetic force stirring reactions of temperature 2h, after reaction finishes, unreacted methanol is reclaimed in distillation, reaction liquid phase filtered while hot is isolated catalyzer and is reused, and then filtrate is poured into standing demix in the separating funnel, the upper strata is coarse biodiesel, and lower floor is a glycerin layer;
(5)-0.080~-0.095MPa vacuum tightness under, add by coarse biodiesel weight and count 0.1% stopper boric acid in coarse biodiesel (to prevent unsaturated composition generation polymerization) and distill, collect cut, obtain refining biodiesel.Present embodiment biofuel yield 82.7%.
Embodiment 2
(1) with the Idesia polycarpa oil of 69.50g squeezing under 70 ℃, add oil and weigh 5% same warm water and carry out hydration degum 40min;
(2) oil after will coming unstuck carries out after drying dewaters, heating also control oil temperature at 75 ℃, stir add down oil heavy 7%, concentration is that 19% potassium hydroxide solution carries out alkali-refining deacidification 40min;
(3) the Idesia polycarpa oil behind the alkali refining is under 90 ℃, add oil heavy 5.5% and in advance prior to 150 ℃ of activated decoloration 45min of activation 2h down;
(4) with 51.30g decolouring back grease, after 25.41g ethanol (molar ratio of methanol to oil is 9: 1) mixes, add again by decolouring back grease weight and count 3.0% Mg-Al composite oxides, and at 70 ℃ of lower magnetic force stirring reactions of temperature 3h, after reaction finishes, unreacted ethanol is reclaimed in distillation, reaction liquid phase filtered while hot is isolated catalyzer and is reused, and then filtrate is poured into standing demix in the separating funnel, the upper strata is coarse biodiesel, and lower floor is a glycerin layer;
(5)-0.080~-0.095MPa vacuum tightness under, add by coarse biodiesel weight and count 0.15% stopper boric acid in coarse biodiesel (to prevent unsaturated composition generation polymerization) and distill, collect cut, obtain refining biodiesel.Present embodiment biofuel yield 84.2%.
Embodiment 3
(1) with the Idesia polycarpa oil of 110.50g squeezing under 80 ℃, add oil and weigh 6% same warm water and carry out hydration degum 35min;
(2) oil after will coming unstuck carries out after drying dewaters, heating also control oil temperature at 70 ℃, stir add down oil heavy 8%, concentration is that 19% sodium hydroxide solution carries out alkali-refining deacidification 45min;
(3) the Idesia polycarpa oil behind the alkali refining is under 100 ℃, add oil heavy 6% and in advance prior to 150 ℃ of activated decoloration 50min of activation 2h down;
(4) with 50.52g decolouring back grease, after 27.20g Virahol (molar ratio of methanol to oil is 7.5: 1) mixes, add again by decolouring back grease weight and count 3.0% Mg-Al composite oxides, and at 50 ℃ of lower magnetic force stirring reactions of temperature 4h, after reaction finishes, unreacted Virahol is reclaimed in distillation, reaction liquid phase filtered while hot is isolated catalyzer and is reused, and then filtrate is poured into standing demix in the separating funnel, the upper strata is coarse biodiesel, and lower floor is a glycerin layer;
(5)-0.080~-0.095MPa vacuum tightness under, add by coarse biodiesel weight and count 0.2% stopper boric acid in coarse biodiesel (to prevent unsaturated composition generation polymerization) and distill, collect cut, obtain refining biodiesel.Present embodiment biofuel yield 85.6%.
Embodiment 4
(1) with the Idesia polycarpa oil of 80.00g squeezing under 70 ℃, add oil and weigh 7% same warm water and carry out hydration degum 35min;
(2) oil after will coming unstuck carries out after drying dewaters, heating also control oil temperature at 80 ℃, stir add down oil heavy 7%, concentration is that 19% sodium hydroxide solution carries out alkali-refining deacidification 50min;
(3) the Idesia polycarpa oil behind the alkali refining is under 100 ℃, add oil heavy 6% and in advance prior to 150 ℃ of activated decoloration 40min of activation 2h down;
(4) with 51.05g decolouring back grease, after 12.76g methyl alcohol (molar ratio of methanol to oil is 6: 1) mixes, add again by decolouring back grease weight and count 2.0% Mg-Al composite oxides, and at 60 ℃ of lower magnetic force stirring reactions of temperature 3h, after reaction finishes, unreacted methanol is reclaimed in distillation, reaction liquid phase filtered while hot is isolated catalyzer and is reused, and then filtrate is poured into standing demix in the separating funnel, the upper strata is coarse biodiesel, and lower floor is a glycerin layer;
(5)-0.080~-0.095MPa vacuum tightness under, add by coarse biodiesel weight and count 0.15% stopper boric acid in coarse biodiesel (to prevent unsaturated composition generation polymerization) and distill, collect cut, obtain refining biodiesel.Present embodiment biofuel yield 86.9%.
Embodiment 5
(1) with the Idesia polycarpa oil of 75.50g squeezing under 75 ℃, add oil and weigh 6% same warm water and carry out hydration degum 40min;
(2) oil after will coming unstuck carries out after drying dewaters, heating also control oil temperature at 75 ℃, stir add down oil heavy 6%, concentration is that 19% potassium hydroxide solution carries out alkali-refining deacidification 40min;
(3) the Idesia polycarpa oil behind the alkali refining is under 95 ℃, add oil heavy 5.5% and in advance prior to 150 ℃ of activated decoloration 50min of activation 2h down;
(4) with 50.25g decolouring back grease, after 27.06g Virahol (molar ratio of methanol to oil is 7.5: 1) mixes, add again by decolouring back grease weight and count 2.0% Mg-Al composite oxides, and at 70 ℃ of lower magnetic force stirring reactions of temperature 2h, after reaction finishes, unreacted Virahol is reclaimed in distillation, reaction liquid phase filtered while hot is isolated catalyzer and is reused, and then filtrate is poured into standing demix in the separating funnel, the upper strata is coarse biodiesel, and lower floor is a glycerin layer;
(5)-0.080~-0.095MPa vacuum tightness under, add by coarse biodiesel weight and count 0.1% stopper boric acid in coarse biodiesel (to prevent unsaturated composition generation polymerization) and distill, collect cut, obtain refining biodiesel.Present embodiment biofuel yield 84.8%.
Embodiment 6
(1) with the Idesia polycarpa oil of 85.20g squeezing under 80 ℃, add oil and weigh 5% same warm water and carry out hydration degum 30min;
(2) oil after will coming unstuck carries out after drying dewaters, heating also control oil temperature at 70 ℃, stir add down oil heavy 8%, concentration is that 19% potassium hydroxide solution carries out alkali-refining deacidification 45min;
(3) the Idesia polycarpa oil behind the alkali refining is under 90 ℃, add oil heavy 5% and in advance prior to 150 ℃ of activated decoloration 45min of activation 2h down;
(4) with 50.73g decolouring back grease, after 25.15g ethanol (molar ratio of methanol to oil is 9: 1) mixes, add again by decolouring back grease weight and count 1.0% Mg-Al composite oxides, and at 50 ℃ of lower magnetic force stirring reactions of temperature 4h, after reaction finishes, unreacted ethanol is reclaimed in distillation, reaction liquid phase filtered while hot is isolated catalyzer and is reused, and then filtrate is poured into standing demix in the separating funnel, the upper strata is coarse biodiesel, and lower floor is a glycerin layer;
(5)-0.080~-0.095MPa vacuum tightness under, add by coarse biodiesel weight and count 0.2% stopper boric acid in coarse biodiesel (to prevent unsaturated composition generation polymerization) and distill, collect cut, obtain refining biodiesel.Present embodiment biofuel yield 83.4%.
Claims (3)
1, a kind of with catalyzed by solid base Idesia polycarpa oil preparation method of bio-diesel oil, the processing step of this method and condition are:
(1) with the Idesia polycarpa oil of squeezing under 70~80 ℃ of temperature, add and to count 5~7% same warm water by the weight of Idesia polycarpa oil and carry out hydration degum 30~40min;
(2) oil after will coming unstuck carries out after drying dewaters, and heating also control oil temperature is stirred to add down and pressed elaeometer 6~8% at 70~80 ℃, and concentration is that 19% homogeneous phase alkaline solution carries out alkali-refining deacidification 40~50min,
(3) the Idesia polycarpa oil behind the alkali refining is under 90~100 ℃ of temperature, and adding by elaeometer is 5~6% pre-activated decoloration 40~50min prior to 150 ℃ of following activation 2h.
(4) will count 1~3% solid alkali Mg-Al composite oxides by decolouring back grease weight, adding mol ratio is in 6: 1~9: 1 the low-carbon alcohol and the greasy mixed solution that decolours, and at 50~70 ℃ of following stirring reaction 2~4h of temperature, after reaction finishes, unreacted low-carbon alcohol is reclaimed in distillation, reaction liquid phase filtered while hot, and isolate catalyst solid alkali and reuse, with the filtrate standing demix, the upper strata product is coarse biodiesel then.
(5)-0.080~-vacuum tightness of 0.095MPa under, add by coarse biodiesel weight and count 0.1~0.2% stopper boric acid in coarse biodiesel and distill, collect cut, promptly obtain refining biodiesel.
2, according to claim 1 with catalyzed by solid base Idesia polycarpa oil preparation method of bio-diesel oil, used homogeneous phase alkali is sodium hydroxide or potassium hydroxide in this method.
3, according to claim 1 and 2 with catalyzed by solid base Idesia polycarpa oil preparation method of bio-diesel oil, used low-carbon alcohol is any in methyl alcohol, ethanol, the Virahol in this method.
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Cited By (7)
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CN102212416A (en) * | 2011-04-26 | 2011-10-12 | 刘长根 | Biodiesel prepared from mixed oil of Idesia polycarpa var.vestita Diels oil and waste cooking oil and preparation method thereof |
CN102212415A (en) * | 2011-04-26 | 2011-10-12 | 刘长根 | Biodiesel prepared from Idesia polycarpa var.vestita Diels oil and preparation method thereof |
CN102212414A (en) * | 2011-04-26 | 2011-10-12 | 刘长根 | Biodiesel prepared from Idesia polycarpa var.vestita Diels oil and waste oil under alkali catalysis and preparation method thereof |
CN102533453A (en) * | 2011-12-26 | 2012-07-04 | 深圳清华大学研究院 | Biodiesel production method |
WO2012111023A1 (en) | 2011-02-14 | 2012-08-23 | Council Of Scientific & Industrial Research (An Indian Registered Body Incorporated Under The Registration Of Societies Act (Act Xxxi Of 1860) | Improved process for the preparation of fatty acid alkyl esters (biodiesel) from triglyceride oils using eco-friendly solid base catalysts |
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WO2012111023A1 (en) | 2011-02-14 | 2012-08-23 | Council Of Scientific & Industrial Research (An Indian Registered Body Incorporated Under The Registration Of Societies Act (Act Xxxi Of 1860) | Improved process for the preparation of fatty acid alkyl esters (biodiesel) from triglyceride oils using eco-friendly solid base catalysts |
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CN102212416A (en) * | 2011-04-26 | 2011-10-12 | 刘长根 | Biodiesel prepared from mixed oil of Idesia polycarpa var.vestita Diels oil and waste cooking oil and preparation method thereof |
CN102212415A (en) * | 2011-04-26 | 2011-10-12 | 刘长根 | Biodiesel prepared from Idesia polycarpa var.vestita Diels oil and preparation method thereof |
CN102212414A (en) * | 2011-04-26 | 2011-10-12 | 刘长根 | Biodiesel prepared from Idesia polycarpa var.vestita Diels oil and waste oil under alkali catalysis and preparation method thereof |
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CN102212415B (en) * | 2011-04-26 | 2013-08-14 | 四川志宇生物能源科技股份有限公司 | Biodiesel prepared from Idesia polycarpa var.vestita Diels oil and preparation method thereof |
CN102533453A (en) * | 2011-12-26 | 2012-07-04 | 深圳清华大学研究院 | Biodiesel production method |
CN102533453B (en) * | 2011-12-26 | 2013-08-14 | 深圳清华大学研究院 | Biodiesel production method |
CN111100721A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Lubricating oil base oil and preparation method thereof |
CN109880696A (en) * | 2019-03-04 | 2019-06-14 | 扬州中天利新材料股份有限公司 | A method of biodiesel is prepared using waste grease |
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