CN101319169A - Quick and clean process for preparing biological diesel oil with esterification/ester exchange reaction - Google Patents
Quick and clean process for preparing biological diesel oil with esterification/ester exchange reaction Download PDFInfo
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- CN101319169A CN101319169A CNA2008100455815A CN200810045581A CN101319169A CN 101319169 A CN101319169 A CN 101319169A CN A2008100455815 A CNA2008100455815 A CN A2008100455815A CN 200810045581 A CN200810045581 A CN 200810045581A CN 101319169 A CN101319169 A CN 101319169A
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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
- 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
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Abstract
The invention relates to a novel process for preparing biodiesel through natural oil which has different acid numbers and a rapid esterification/ester interchange reaction with catalysts of minute quantity at an alcohol-oil consolute temperature. The process comprises the following steps of: taking animal and vegetable oil as raw materials, adding the oil and methanol into a reaction kettle according to an alkyd mol ratio of 2 to 1-10 to 1 for rapid esterification, and adding the acid catalyst of minute quality which is 0.01-1 per mille of the weight of the oil with reaction conditions of 120-200 DEG C, 2.0-8.0Mpa, and 10-30min; after neutralization deacidification, adding refined oil and methane into a high-pressure reaction kettle according to a mol ratio of 1 to 6-1 to 20 for rapid ester interchange, and adding a base catalyst of minute quality which is 0.01-1 per mille of the weight of the refined oil with reaction conditions of 140-200 DEG C, 2.0-8.0Mpa, and 5-20min; carrying out the sedimentation or centrifuge of a reaction product, and generating a qualified biodiesel product after removing methane through upper layer liquid phase distillation. The process uses minute quantity of catalysts and does not need separation with quick reaction and simple procedure without pollution and corrosion. The process has the advantages of mild conditions, environmental protection and remarkable efficiency.
Description
One, technical field
The present invention relates to the energy and chemical field, relate to a kind of production preparation of renewable energy source, belonging to cleaning green chemical industry process, is to prepare method of bio-diesel oil with the animal and plant grease in pre-esterification of trace acid catalyst catalysis and transesterification reaction under a kind of subcritical methyl alcohol phase condition.
Two, background technology
In recent years, the research and development of biomass fuel are subjected to increasing attention, and the production of biofuel is one of present most important biomass fuel.Biofuel is often referred to the mono alkyl ester of the longer chain fatty acid that is generated by animal-plant oil and short chain alcohol transesterify, if winner's fatty acid methyl ester is promoted in commercialization at present.Biofuel is nontoxic, cetane value is high, lubricity is good, can directly substitute petroleum diesel or uses with petroleum diesel, can directly enter existing fuel loading system, is the ideal alternative fuel.
The production method of biofuel is the transesterification reaction of carrying out grease and methyl alcohol under the effect of alkaline catalysts, and reaction equation is as follows:
Obtain the ester of low-carbon alcohol of longer chain fatty acid after the transesterify, molecular weight just drops to about 300, and more near the molecular weight of diesel oil, physico-chemical property approaches diesel oil, and fuel performance is with the diesel oil it makes no odds.The catalyzer of industrial use comprises: NaOH, KOH and alkoxide thereof, it is heavy by 1%～3% that catalyst levels is generally oil, be reflected under the normal pressure and carry out, because the methyl alcohol boiling point is 64.5 ℃, usually temperature of reaction is the methyl alcohol boiling temperature, in about 30～120 minutes of reaction times, can reach the transformation efficiency more than 95%.
Adopt alkali metal hydroxide to make catalyzer, the reaction efficiency height.The product that obtains is behind standing demix, and the upper strata is fatty acid methyl ester and glycerin layer, and unnecessary methyl alcohol is scattered in the two-phase.Owing in the product the residual base metal catalysts of part is arranged, must evolve through operations such as washing, dehydration, dryings, be lower than 98% situation for transformation efficiency, also must adopt alkali lye distillatory mode to purify and can obtain qualified biofuel product.For relatively poor glyceride stock, acid number is often very high, needs pre-treatment before the transesterification reaction, as alkali refining removal of impurities etc., has reduced the grease utilization ratio, has increased production cost.
According to country to the standard GB/T 20828-2007 of biofuel product " diesel-fuel blending with biofuel (BD100) " free acid content is stipulated acid number＜0.8mgKOH/g, i.e. free acid content＜500ppm, sulphur content＜0.05%; But national standard is not stipulated alkali content, and foreign standard is controlled at alkali content＜10mg/kg usually.Therefore, the conditional request transformation efficiency of transesterification reaction must reach more than 98%, and simultaneously, product must repetitive scrubbing just can reach the requirement of biofuel quality product.
Existing that there is following shortcoming in industrial process: the polished fat after 1) needs are made with extra care, to the ingredient requirement height; 2) there are a large amount of spent acid alkali dischargings and washes discharging in the production process, cause environmental problem; 3) product follow-up purification process complexity, production energy consumption and cost height.
Domestic and international research direction to biofuel concentrates on seeks new transesterification reaction system, comprises supercritical methanol technology, biological enzyme, solid catalyst method etc.At home, China Petrochemical Group Petrochemical Since Institute is the pilot plant of commerical test at first in the world at 2000 tons/year overcritical production of biodiesel pilot plant of Shijiazhuang refinery factory construction, Beijing University of Chemical Technology, Tsing-Hua University etc. have obtained achievement preferably aspect enzyme catalysis, units such as Sichuan University, Nanjing University of Technology have all carried out a large amount of work at aspects such as solid alkali, organic basess.The Esterfip-H technology of IFP exploitation, the solid catalyst of employing spinel structure.U.S.'s Clemson University adopts the Nafin film to carry out the research of acid-catalyzed transesterification reaction.
Existing research, the production cost of biological enzyme is higher, and solid catalyst exists life-span and activity problems, all also has certain distance from course of industrialization.Supercritical methanol technology just in course of industrialization, but supercritical methanol technology need High Temperature High Pressure (＞240 ℃,＞8MPa), energy consumption height, problem Project Realization difficulties such as the heating in the technology, equipment requirements height.
Purpose of the present invention, be a kind of new production of biodiesel technology that adopts a kind of be coupled catalyzed reaction and supercritical reaction, can realize quick esterification/ester exchange reaction under than the condition of supercritical reaction milder, be a kind of process for cleanly preparing that does not have the spent catalyst discharging.
Three, summary of the invention
The objective of the invention is at existing production of biodiesel technology, and disclosed and problem and shortage that the production technique reported and technology exist, provide a kind of with catalyzed reaction and the new production of biodiesel technology of supercritical reaction coupled, the key of this technology is to realize quick esterification and transesterification reaction by trace catalyst under than the condition of supercritical reaction device milder, this technology non-wastewater discharge, technical process is simple, and production cost is low.
The key of the technology of the present invention is to adopt to improve temperature of reaction reinforcement reaction, and in esterification and the ester-exchange reaction, methyl alcohol and grease do not dissolve each other, and along with the rising of temperature, two intermiscibilities increase, reaction rate accelerates.
Typical example be temperature to be increased to the methanol critical point be 239 ℃, 8.1MPa, speed of reaction is accelerated suddenly, just can finish in several minutes under the situation that does not have catalyzer to exist.
Along with grease ratio in methyl alcohol/grease binary system increases, following table is methyl alcohol/grease binary system changes stagnation point along with proportion of composing variation.
Table 1 methyl alcohol/grease binary system dissolves each other a little and stagnation point
| Methyl alcohol/grease | 268 | 217 | 161 | 108 | 54 |
| Dissolve each other temperature (℃) | 124.8 | 124.9 | 124.5 | 137.9 | 136.0 |
| Miscibility pressure (MPa) | 1.01 | 0.61 | 0.59 | 0.86 | 0.90 |
| Critical temperature (℃) | 248.3 | 249.6 | 251.6 | 271.7 | 314.0 |
| Emergent pressure (MPa) | 8.44 | 8.64 | 8.76 | 10.66 | 13.31 |
Can find out that from last table though critical temperature and emergent pressure increase and sharply increase with the grease ratio, the temperature of dissolving each other remains on 120～140 ℃ substantially, miscibility pressure also is lower than 1MPa.Therefore, under this temperature, two-phase can realize uniform mixing, and interphase mass transfer can satisfy the reaction requirement.
It is to react fast to carry out that production technology proposed by the invention has adopted micro-catalyzer, but the used pre-esterification of this technology uses acid catalyst consumption (0.01 ‰～5 ‰) far below existing biodiesel processes catalyst levels (0.5%～3%); Transesterify uses alkaline catalysts consumption (0.01 ‰～1 ‰) far below existing biodiesel processes catalyst levels (1%～3%); Existing research and test-results show that reaction can be finished too in a short period of time under this low catalyst concentration.
Present technique invention production biofuel need not spent catalyst is carried out special purifying treatment, and technical process is simple.Studies show that no matter adopt liquid acid, alkaline catalysts, after reaction finishes, the catalyzer major part all remain in lower floor's glycerine mutually in.Following table is KOH and H
2SO
4Partition ratio in methyl esters/glycerol system is with the variation of methanol content.
Table 2 ternary system glycerine phase and middle mutually KOH of methyl esters and H
2SO
4Partition ratio
By partition ratio as can be known, along with the minimizing of methanol usage, no matter be homogeneous phase alkali or homogeneous acid, most residual catalyst all enters glycerin layer; Have only 1%～3% catalyzer to enter the methyl esters phase.Therefore, handle separating by-products glycerine or sour water by the plain sedimentation layering after, remain in the methyl esters layer and get catalyst content and will reduce to 10mg/kg, need not further aftertreatment.
The benefit of present technique invention is:
1), rather than under the critical temperature condition of methyl alcohol, react in methyl alcohol/greasy consolute temperature, the reaction conditions gentleness, reaction pressure is lower than 1MPa, reduces the facility investment of reactor and the energy consumption of reactive system greatly;
2) adopt micro-acid base catalysator, can make product just can satisfy the requirement of biofuel acid, alkali resistates without any washing or other special purifications.
3) whole process does not have spent catalyst discharging and discharge of wastewater problem, is eco-friendly production technique.
The technical scheme that realizes above-mentioned purpose is as follows:
With waste greases such as animal and plant grease such as rapeseed oil, soybean oil, Cortex jatrophae oil, lard, tallow and treated oil, crude oil, acidifying oil and recovery greases is raw material, methyl alcohol is that 2: 1～10: 1 ratio is mixed the quick esterification of realization in the adding reactor with stock oil in molar ratio of alcohol to acid, is added to oil in the reaction system and weighs 0.01 ‰～1 ‰ pre-esterified acid catalyst such as H
2SO
4, HCl, H
3PO
4, NaHSO
4, KHSO
4Deng mineral acid and be carried on TiO
2, SiO
2, Al
2O
3Deng the mineral acid on the carrier, or organic acid such as sulfonic acid, Phenylsulfonic acid, toluene sulfonic acide, temperature of reaction is 120～200 ℃, and pressure is 2.0～8.0MPa, and the reaction times is 10～30 minutes.Reaction finishes back grease dehydration, and the refining acid value of oil and fat of gained is lower than 1mgKOH/g.Grease and methyl alcohol after the pre-esterification are added in the autoclave with 1: 6～1: 20 ratio of mol ratio, in reaction system, add oil and heavily be 0.01 ‰～1 ‰ transesterification catalyst such as NaOH, KOH, LiOH, CsOH, Ba (OH)
2, Na
2CO
3, K
2CO
3, NaHCO
3, KHCO
3Deng mineral alkali and be carried on MgO, CaO, Al
2O
3Deng the mineral alkali on the carrier, be 140～200 ℃ in temperature of reaction, pressure is under 2.0～8.0MPa condition, the reaction times is 5～20 minutes.Reaction finishes afterreaction product gravity settling or centrifugation layering, and the upper strata is fatty acid methyl ester and methanol layer, and distillation is removed excessive methanol and obtained the methyl esters product; Lower floor is glycerine and methanol mixed layer, and distillation glycerine obtains methyl alcohol.This production technique grease transformation efficiency is not less than 90%, and the fatty acid methyl ester yield is not less than 90%.The biofuel product that the obtains GB/T20828-2007 that is up to state standards.
The useful result of the present invention exists:
1) the catalyzer add-on is that oil is heavy by 0.01 ‰～1 ‰.Reaction back methyl esters product acid number＜0.5mgKOH/g, i.e. free acid content＜500ppm, sulphur content＜0.05%, residual alkali number＜10mg/kg.Can obtain qualified biofuel product without the catalyst separating operation, no waste water, pollution-free, simplify the biofuel postprocessing working procedures, reduce production costs; And trace catalyst is little to equipment corrosion in process of production.
2) methyl alcohol pre-esterification of mutually subcritical trace catalyst catalysis and transesterification reaction are compared the shortening of solid catalyst technological reaction time; Reaction conditions is compared the super critical condition gentleness, and energy consumption is little, and facility investment is few, helps large-scale industrialization and uses.
Four, embodiment
Embodiment 1: getting acid number is the acidifying oil 70.0g of 50mgKOH/g, and quantity of methyl alcohol is pressed molar ratio of alcohol to acid and calculated at 10: 1, is 1.0g, catalyzer H
2SO
4Consumption is that oil is heavy by 1.5 ‰, i.e. 0.10g, and 120 ℃ of temperature of reaction, in 15 minutes reaction times, pre-conversion rate of esterification can reach 98%.Treated oil and 100.0g methanol mixed after the dehydration is even, and the pre-oil that adds weighs 1 ‰ NaOH in the methyl alcohol.With rapeseed oil and methyl alcohol adding volume is in the high temperature high pressure enclosed reactor of 300ml.Temperature of reaction is 200 ℃, and reaction pressure is 2.5MPa; React after 15 minutes, cool off reactor to room temperature, the underpressure distillation excessive methanol, standing demix in the product, the upper strata is the methyl esters layer, lower floor is a glycerin layer.The grease transformation efficiency is up to 95.0%, and glycerol content is lower than 1% in the methyl esters, and acid number is lower than 0.5mgKOH/g, sulphur content＜0.05%, alkali number＜10mg/kg.
Embodiment 2: with the pre-esterification catalyst H in the above-mentioned embodiment 1
2SO
4It is heavy by 0.7 ‰ that addition changes oil into, and other condition is constant, and it is 87% that experiment records pre-conversion rate of esterification.After the transesterify in the methyl esters glycerol content be lower than 1%, acid number is lower than 0.5mgKOH/g, sulphur content＜0.05%, alkali number＜10mg/kg.
Embodiment 3: it is heavy by 0.5 ‰ to change the transesterification catalyst NaOH addition in the above-mentioned embodiment 1 into oil, and other condition is constant, and it is 88.5% that experiment records the grease transformation efficiency, glycerol content is lower than 1% in the methyl esters, acid number is lower than 0.5mgKOH/g, sulphur content＜0.05%, alkali number＜10mg/kg.
Embodiment 4: with the pre-esterification catalyst H in the above-mentioned embodiment 1
2SO
4Change Phenylsulfonic acid into, other condition is constant, and it is 93.1% that experiment records the grease transformation efficiency, and glycerol content is lower than 1% in the methyl esters, and acid number is lower than 0.5mgKOH/g, sulphur content＜0.05%, alkali number＜10mg/kg.
Embodiment 5: change the transesterification catalyst NaOH in the above-mentioned embodiment 1 into KOH, other condition is constant, and it is 81.3% that experiment records the grease transformation efficiency, glycerol content is lower than 1% in the methyl esters, acid number is lower than 0.5mgKOH/g, sulphur content＜0.05%, alkali number＜10mg/kg.
Embodiment 6: with the transesterification catalyst H in the above-mentioned embodiment 1
2SO
4Change SO into
4 2-/ Al
2O
3, other condition is constant, and it is 83.3% that experiment records the grease transformation efficiency, and glycerol content is lower than 1% in the methyl esters, and acid number is lower than 0.5mgKOH/g, sulphur content＜0.05%, alkali number＜10mg/kg.
Embodiment 7: change the transesterification catalyst NaOH in the above-mentioned embodiment 1 into the Zn/Al composite oxides, other condition is constant, and it is 84.5% that experiment records the grease transformation efficiency, glycerol content is lower than 1% in the methyl esters, acid number is lower than 0.5mgKOH/g, sulphur content＜0.05%, alkali number＜10mg/kg.
Embodiment 8: change the pre-esterification temperature in the above-mentioned embodiment 1 into 200 ℃ from 120 ℃, other condition is constant, and it is 93.7% that experiment records the grease transformation efficiency, glycerol content is lower than 1% in the methyl esters, acid number is lower than 0.5mgKOH/g, sulphur content＜0.05%, alkali number＜10mg/kg.
Embodiment 9: change the transesterification reaction 100.0g methyl alcohol in the above-mentioned embodiment 1 into 75.0g methyl alcohol, other condition is constant, and it is 87.7% that experiment records the grease transformation efficiency, glycerol content is lower than 1% in the methyl esters, acid number is lower than 0.5mgKOH/g, sulphur content＜0.05%, alkali number＜10mg/kg.
Embodiment 10: change the pre-esterification reactor 1.0g methyl alcohol in the above-mentioned embodiment 1 into 0.5g methyl alcohol, other condition is constant, and it is 88.4% that experiment records the grease transformation efficiency, glycerol content is lower than 1% in the methyl esters, acid number is lower than 0.5mgKOH/g, sulphur content＜0.05%, alkali number＜10mg/kg.
Embodiment 11: the refining rapeseed oil that the acidifying oil of the 50mgKOH/g in the above-mentioned embodiment 1 is changed into 2.5mgKOH/g, pre-esterification methanol usage changes 0.3g into, other condition is constant, it is 92.4% that experiment records the grease transformation efficiency, glycerol content is lower than 1% in the methyl esters, acid number is lower than 0.5mgKOH/g, sulphur content＜0.05%, alkali number＜10mg/kg.
Embodiment 12: change the high temperature high pressure enclosed reactor in the above-mentioned embodiment 1 into the continous way fixed-bed reactor, transesterification catalyst NaOH changes Zn/Al composite oxide catalysts particle into, other condition is constant, it is 84.8% that experiment records the grease transformation efficiency, glycerol content is lower than 1% in the methyl esters, acid number is lower than 0.5mgKOH/g, sulphur content＜0.05%, alkali number＜10mg/kg.
Claims (4)
1. described in the invention is a kind ofly can prepare the novel process of biofuel at dissolve each other quick esterification/ester exchange reaction that next trace catalyst of temperature carries out of pure oil with the natural fats and oils of different acid numbers, it is characterized in that:
(1) described natural fats and oils is meant with animal grease and Vegetable oil lipoprotein, comprises using treated oil, crude oil, acidifying oil and reclaiming grease etc., and its acid number can change between 0-150mgKOH/g;
(2) the described temperature of dissolving each other is meant that the methyl alcohol in the reaction system forms the temperature of dissolving each other mutually with grease, free fatty acids, between 120-200 ℃;
(3) described quick esterification is characterized as, and is higher than the raw oil material of 1mgKOH/g for acid number, and raw material need carry out esterification with methyl alcohol and acid number is dropped to below the 1mgKOH/g.Its reaction conditions is: methyl alcohol/free fatty acids mol ratio is 2: 1～10: 1, and oil weighs 0.01 ‰～1 ‰ an acidic catalyst, and temperature of reaction is 120～200 ℃, and pressure is 2.0～8.0MPa, and the reaction times is 10～30 minutes;
(4) described quick transesterification reaction is characterized as, and is lower than the raw oil material of 1mgKOH/g for acid number, or passes through the esterification grease of the 1mgKOH/g after esterification described in above-mentioned (3) and the purifying treatment, carries out transesterification reaction with methyl alcohol.Its reaction conditions is: methyl alcohol/grease mol ratio is 6: 1～20: 1,0.01 ‰～1 ‰ alkaline catalysts, and temperature of reaction is 140～200 ℃, and pressure is 2.0～8.0MPa, and the reaction times is 5～20 minutes.
2. may further comprise the steps according to the described preparation production of biodiesel of claim 1 technology: esterification, sour water separation, methanol wash, transesterify, glycerine separation, fractionation by adsorption etc.It is characterized in that:
(1) the described esterification of claim 2 is meant that (3) money is described in the claim 1;
(2) the described sour water of claim 2 separates the mixture that is meant esterification after product water and spent acid catalyst, do not dissolve each other with the esterification grease, can separate through means such as sedimentation or centrifugal or filtrations, the esterification grease is behind the excessive methyl alcohol of flash distillation recovery part, temperature drops to below 60 ℃, two phase solubilities reduce, and carry out two and are separated;
(3) the described methanol wash of claim 2, be meant esterification and remove esterification grease behind the sour water after be separated, utilize immiscible characteristics under methyl alcohol and the esterification oil at low temperature, use methanol wash, residual acid catalyst enters that methyl alcohol reclaims mutually and as the esterification methanol feedstock in the esterification grease, be lower than 1mg/KOH through acid number in the esterification grease of methanol wash, acid catalyst content is lower than 10PPM;
(4) the described transesterify of claim 2 is meant that (4) money is described in the claim 1;
(5) the described sour water separation of claim 2 is meant that transesterify after product glycerine and biofuel product fatty acid methyl ester do not dissolve each other, can separate through means such as sedimentation or centrifugal or filtrations, the esterification grease is behind the excessive methyl alcohol of flash distillation recovery part, temperature drops to below 60 ℃, two phase solubilities reduce, and carry out two and are separated;
(6) the described fractionation by adsorption of claim 2 is meant the micro-alkaline catalysts that adopts in the special adsorbents adsorb separating bio diesel product, and the catalyst metal ion content＜10PPM after the fractionation by adsorption meets the biofuel requirement.
3. according to the described acid catalyst of claim 1 (3) money, be meant H
2SO
4, HCl, H
3PO
4, NaHSO
4, KHSO
4Deng mineral acid and be carried on TiO
2, SiO
2, Al
2O
3Deng the mineral acid on the carrier, or sulfonic acid, Phenylsulfonic acid, organic acids such as toluene sulfonic acide can trace add or once add slowly and discharge.
4. according to the described alkaline catalysts of claim 1 (4) money, be meant NaOH, KOH, LiOH, CsOH, Ba (OH)
2, Na
2CO
3, K
2CO
3, NaHCO
3, KHCO
3Deng mineral alkali and be carried on MgO, CaO, Al
2O
3Deng the mineral alkali on the carrier, can add or once add slowly release by trace.
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| CN102229864A (en) * | 2011-04-28 | 2011-11-02 | 辽宁省能源研究所 | Method for producing biodiesel with hogwash oil of high acid value |
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| CN102753263A (en) * | 2010-02-08 | 2012-10-24 | 再生控股有限公司 | Method and apparatus for esterifying fatty acid |
| CN101787332A (en) * | 2010-03-12 | 2010-07-28 | 江苏卡特新能源有限公司 | Method for preparing fatty acid mixed ester |
| CN101787332B (en) * | 2010-03-12 | 2012-05-16 | 江苏卡特新能源有限公司 | Method for preparing fatty acid mixed ester |
| CN102373109A (en) * | 2010-08-12 | 2012-03-14 | 中国石油化工股份有限公司 | Denitrogenation method for biodiesel |
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| CN102952647A (en) * | 2011-08-24 | 2013-03-06 | 江苏洁净环境科技有限公司 | Production process for 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 |
| CN103540411A (en) * | 2012-07-13 | 2014-01-29 | 中国石油化工股份有限公司 | Refining method of high-impurity oil |
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| CN105154240A (en) * | 2015-08-10 | 2015-12-16 | 苏州丰倍生物科技有限公司 | Method for producing environment-friendly fatty acid methyl ester with glycerol method |
| CN111423936A (en) * | 2020-02-12 | 2020-07-17 | 常州市金坛区维格生物科技有限公司 | Method for reducing acid of waste oil at low temperature |
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