CN101130700A - Novel method for producing biological diesel oil with solid alkali catalysis - Google Patents
Novel method for producing biological diesel oil with solid alkali catalysis Download PDFInfo
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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 discloses a making method of biological diesel catalyzed by new typed solid alkaline, which is characterized by the following: adopting plant oil as raw material to react with carbinol or alcohol; adding catalyst to make the biological diesel through ester changing reaction; using composite metal oxide as the solid alkaline catalyst; simplifying the making technique with wide source of raw material; separating catalyst simply; regenerating easily; eliminating adverse influence of saponifying reaction; improving the receiving rate of object product by 90%; possessing large adjustability of physicochemical index for solid alkaline catalyst; fitting for preparing different raw materials.
Description
Technical field
The present invention relates to the preparation method of biofuel, relate in particular to a kind of method of novel solid body base catalysis for preparing biodiesel oil.
Background technology
Biofuel is by to renewable resources soybean oil for example, rapeseed oil, peanut oil, leprosy fruit wet goods vegetables oil and pig, ox, animal oil such as sheep carry out transesterification reaction and the fatty acid ester that makes, have renewable, readily biodegradable, nontoxic, advantages such as the discharge of poisonous waste amount is little in the low and waste gas of sulphur content are environmentally friendly fuel.Along with the shortage of world petroleum resource and the raising of people's environmental consciousness impel people to go the alternate resources of development of new, biofuel is as a kind of cleaning, and reproducible fuel is received domestic and international common concern in recent years, promises to be a kind of novel energy.
The preparation method of bio-diesel oil mainly contains direct fusion method at present, pyrolysis method, and micro emulsion method and transesterification reaction method, the transesterification reaction method also claims alcoholysis method, mainly comprises the base-catalyzed transesterification reaction, acid-catalyzed transesterification reaction etc.Biofuel viscosity and petroleum diesel by each vegetable oil preparation are approaching.
The open CN1560197A of Chinese patent, CN1557913A, CN1559914A, CN1473907A and CN132762B have reported the technology of utilizing the transesterification reaction legal system to be equipped with biofuel, especially the trans-esterification processes research of acid-base catalysis is more, reaches its maturity.Acid catalyst comprises sulfuric acid, phosphoric acid, hydrochloric acid and organic sulfonic acid, but the acid catalysis transesterification reaction than base catalysis slowly many, in addition, carbonization phenomenon takes place in the acid catalyzed reaction process inevitably, influence the yield of product, general esterification yield is no more than 85%, in addition.Equipment corrosion, problems such as environmental pollution are also relatively more serious.Comparatively speaking, base catalyzed reactions more possesses advantage, uses NaOH, and KOH makes catalyzer with vegetable oil esters exchange preparation fatty acid methyl ester, and ethyl ester has very high yield.The base catalysis esterification is similar to saponification reaction, and is irreversible, and yield is higher, can at room temperature carry out, not etching apparatus.In industrial production, the base catalysis method is used more.
NaOH or KOH make catalyzer and normally participate in reacting in the homogeneous phase mode with reaction solution, thus give product refiningly bring certain complicacy, when fatty acid content was higher in the raw material, saponification reaction was serious, the yield of product is lower, emulsification is serious.With the homogeneous phase base catalysis comparatively speaking, adopt multiphase solid alkali to make catalyzer and have clear superiority: catalyzer is separated from product easily, easily regeneration; Little to equipment corrosion, environmental pollution is little, thus solid base catalyst to prepare biofuel be current research focus.
Summary of the invention
The object of the present invention is to provide a kind of method of novel solid body base catalysis for preparing biodiesel oil, this method has overcome the shortcoming that the homogeneous phase legal system is equipped with biofuel, and technology is simple, and byproduct is few, does not need the neutralization washing, can not produce trade effluent; Catalyzer can be repeatedly used simultaneously.
The concrete technical scheme that realizes the object of the invention is:
A kind of method of novel solid body base catalysis for preparing biodiesel oil, characteristics are: be raw material with the vegetables oil, with methyl alcohol or ethanol synthesis, add catalyzer, prepare biofuel through transesterification reaction; After the steps include: in batch reactor, to add vegetables oil, methyl alcohol or ethanol stirring, add solid base catalyst or solid base catalyst and cosolvent, carried out transesterification reaction 2～5 hours under 60-90 ℃, reaction back filtered while hot is isolated solid base catalyst; Filtrate standing demix, upper strata are major product, and lower floor is a byproduct; To get biofuel after the major product underpressure distillation of upper strata, lower floor's byproduct is a glycerine.
Described solid base catalyst is a composite oxide of metal, and obtains by following steps:
A, under 60～70 ℃, a kind of solution in lithium salts, magnesium salts, the zinc salt or two kinds of mixing solutionss are mixed with aluminum salt solution, with mixing solutions and stream or single titration of alkali and carbonate, the dropping time is 0.5～2h, and the pH value of solution is controlled between the 10-12, after dripping, continue to stir 4～6h, 60～100 ℃ of nucleation crystallization, cooling then, suction filtration, washing are to neutral, at 100 ℃ of down dry 5～10h, get solid product;
B, with the roasting 3～12 hours under 400-700 ℃ of condition of above-mentioned solid product, novel solid body base catalyst.
Described lithium salts, magnesium salts, in zinc salt and the aluminium mixed salt solution: the mol ratio of Li and Al is 4～8: 1, the mol ratio of Zn and Al is 3～6: 1; The mol ratio of Mg and Al is 1～3: 1; In magnesium salts, zinc salt and aluminium mixed salt solution, the solid content of zinc salt is 4～10%.
Described vegetables oil and methyl alcohol or alcoholic acid mol ratio are 4～20: 1; Catalyst levels is 0.5～5% of a vegetables oil weight; The cosolvent consumption is 10～30% of a vegetables oil weight.
Described cosolvent is a kind of in tetrahydrofuran (THF), hexanaphthene and the toluene.
The present invention compared with prior art, have the following advantages and the high-lighting effect: the present invention has overcome the used even phase catalyst separation difficulty of existing transesterification reaction, catalyzer is difficult for the regenerated defective, reduced the operating unit that separates and wash, eliminated the disadvantageous effect of saponification reaction, the yield of target product can reach 92.5%.Simultaneously, the physical and chemical index adjustability of this solid base catalyst is big, is applicable to different biodiesel manufacture raw materials.
The present invention has added cosolvent in preparation process, as tetrahydrofuran (THF) (THF), cyclohexane, toluene etc., its effect is to reduce the time of pure grease permutoid reaction under solid base catalyst and to a certain degree improving transformation efficiency down.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but embodiments of the present invention are not limited only to this.
Embodiment 1
The preparation of the first step LiAl composite oxides
Under magnetic agitation, with the 21.9g lithium nitrate, the ANN aluminium nitrate nonahydrate of 18.8g is dissolved in the deionized water of 90mL, is stirred to dissolving fully, is designated as solution A.With the sodium hydroxide of 28g, the yellow soda ash of 2.7g is dissolved in the deionized water of 100mL, is stirred to dissolving fully, is designated as solution B.Solution A, solution B are adopted the cocurrent process titration, and the pH=10 of regulator solution continues to stir 4h, 80 ℃ of nucleation crystallization, be cooled to normal temperature, suction filtration, washing, dry 8h in 100 ℃ baking oven again, products therefrom promptly gets the LiAl composite oxides in 550 ℃ of roasting 12h.
The second step LiAl composite oxide catalytic prepares biofuel
In the esterification device of taking back stream and water trap, the rapeseed oil that adds 101.4g, 19.2g methyl alcohol, magnetic agitation, adding weight is catalyzer for 1.5% heavy LiAl composite oxides of oil, reaction times 3h, temperature of reaction is 65 ℃ of methanol eddy temperature, and suction filtration while hot after reaction finishes is isolated solid base catalyst, methyl alcohol is reclaimed in distillation, with the static layering of spending the night of filtrate, the upper strata product is rough biofuel then, and lower floor is a glycerine, the further underpressure distillation of rough biofuel is purified, get biofuel.Through gas chromatographic detection, marker method is demarcated, and the content of gained fatty acid methyl ester is 92.4%.
Embodiment 2
The preparation of the first step LiMgAl composite oxides
Under magnetic agitation, with the 10.9g lithium nitrate, the magnesium nitrate hexahydrate of 19.9g, 18.8g ANN aluminium nitrate nonahydrate are dissolved in the deionized water of 80mL, stir, and are designated as solution A.With the yellow soda ash of 2.7g, the sodium hydroxide of 18g is dissolved in the deionized water of 90mL, is designated as solution B.A is added drop-wise among the B, the single droplet method titration, pH value=11 of regulator solution are after titration finishes, continue to stir 6h, 100 ℃ of nucleation crystallization, be cooled to normal temperature then, suction filtration, washing are to neutral, at 100 ℃ of following dry 8h, products therefrom promptly gets the LiMgAl composite oxides in 600 ℃ of (roasting) 4h again.
The second step LiMgAl composite oxide catalytic prepares biofuel
In the esterification device of taking back stream and water trap, the rapeseed oil that adds 101.4g, 19.2g methyl alcohol, magnetic agitation, adding weight and be 1.8% heavy LiMgAl composite oxides of rapeseed oil is catalyzer, reaction times 2.5h, temperature of reaction is 65 ℃ of methanol eddy temperature, and suction filtration while hot after reaction finishes is isolated solid base catalyst, methyl alcohol is reclaimed in distillation, with the static layering of spending the night of filtrate, the upper strata product is rough biofuel then, and lower floor is a glycerine, the further underpressure distillation of rough biofuel is purified, get biofuel.Through gas chromatographic detection, marker method is demarcated, and the content of gained fatty acid methyl ester is 89.9%.
Embodiment 3
The preparation of the first step ZnAl composite oxides
Under magnetic agitation, with the 17.86g zinc nitrate hexahydrate, the ANN aluminium nitrate nonahydrate of 7.5g is dissolved in the deionized water of 80mL, is stirred to dissolving fully, is designated as solution A.Sodium hydroxide with 6.4, the yellow soda ash of 1.06g is dissolved in the deionized water of 90mL, is stirred to dissolving fully, is designated as solution B.Solution A, solution B are adopted the cocurrent process titration, and the pH=12 of regulator solution continues to stir 5h, 80 ℃ of nucleation crystallization, be cooled to normal temperature then, suction filtration, washing are to neutral, at 100 ℃ of following dry 10h, products therefrom promptly gets the ZnAl composite oxides in 550 ℃ of roasting 6h again.
The second step ZnAl composite oxide catalytic prepares biofuel
In the esterification device of taking back stream and water trap, the rapeseed oil that adds 101.4g, 19.2g methyl alcohol, magnetic agitation, adding weight and be 1.5% heavy ZnAl composite oxides of rapeseed oil is catalyzer, reaction times 5h, temperature of reaction is controlled at 65 ℃ of methanol eddy temperature, and suction filtration while hot after reaction finishes is isolated catalyzer, methyl alcohol is reclaimed in distillation, with the static layering of spending the night of filtrate, the upper strata product is rough biofuel then, and lower floor is a glycerine, the further underpressure distillation of rough biofuel is purified, get biofuel.Through gas chromatographic detection, marker method is demarcated, and the content of gained fatty acid methyl ester is 89.4%.
Embodiment 4
The preparation of the first step ZnMgAl composite oxides
Under magnetic agitation, with magnesium nitrate hexahydrate, the 15g ANN aluminium nitrate nonahydrate of 30.76g, the 1.48g zinc nitrate hexahydrate is dissolved in the deionized water of 80mL, stirs, and is designated as solution A.With the yellow soda ash of 2.7g, the sodium hydroxide of 18g is dissolved in the deionized water of 90ML, is designated as solution B.A is added drop-wise among the B, the single droplet method titration, pH value=13 of regulator solution are after titration finishes, after continuing to stir 4h, 70 ℃ of nucleation crystallization, be cooled to normal temperature, suction filtration, washing are to neutral, at 100 ℃ of following dry 10h, products therefrom promptly gets the ZnMgAl composite oxides in 500 ℃ of (roasting) 4h again.
The second step ZnMgAl composite oxide catalytic prepares biofuel
In the esterification device of taking back stream and water trap, the rapeseed oil that adds 50.7g, 19.2g methyl alcohol, magnetic agitation, adding weight and be 1.5% heavy ZnMgAl composite oxides of rapeseed oil is catalyzer, reaction times 3h, temperature of reaction is controlled at about 70 ℃, and suction filtration while hot after reaction finishes is isolated solid base catalyst, methyl alcohol is reclaimed in distillation, with the static layering of spending the night of filtrate, the upper strata product is rough biofuel then, and lower floor is a glycerine, the further underpressure distillation of rough biofuel is purified, get biofuel.Through gas chromatographic detection, marker method is demarcated, and the content of gained fatty acid methyl ester is 89.5%.
Embodiment 5
The first step is with embodiment 1
The second step LiAl composite oxide catalytic prepares biofuel
In the esterification device of taking back stream and water trap, add the soybean oil of 50.7g, 9.6g methyl alcohol, magnetic agitation, adding weight and be 1.5% heavy LiAl composite oxides of soybean oil is catalyzer, reaction times 4h, temperature of reaction is 70 ℃, and suction filtration while hot after reaction finishes is isolated solid base catalyst, methyl alcohol is reclaimed in distillation, with the static layering of spending the night of filtrate, the upper strata product is rough biofuel then, and lower floor is a glycerine, the further underpressure distillation of rough biofuel is purified, get biofuel.Through gas chromatographic detection, marker method is demarcated, and the content of gained fatty acid methyl ester is 90.6%.
Embodiment 6
The first step is with embodiment 1
The second step LiAl composite oxide catalytic prepares biofuel
In the esterification device of taking back stream and water trap, the rapeseed oil that adds 101.4g, 27.6g ethanol, magnetic agitation, adding weight and be 2% heavy LiAl composite oxides of rapeseed oil is catalyzer, reaction times 3.5h, temperature of reaction is 65 ℃ of alcohol reflux temperature, and reaction finishes the back filtered while hot, isolates solid base catalyst, ethanol is reclaimed in distillation, with the filtrate static layering, the upper strata product is rough biofuel then, and lower floor is a glycerine, the further underpressure distillation of rough biofuel is purified, get biofuel.Through gas chromatographic detection, the content of gained lipid acid second fat is 90.8%.
Embodiment 7
The first step is with embodiment 1
The second step LiAl composite oxide catalytic prepares biofuel
In the esterification device of taking back stream and water trap, add the rapeseed oil of 50.7g, 19.2g methyl alcohol, magnetic agitation, adding weight, to be about 2% heavy LiAl composite oxides of oil be catalyzer, reaction times 3.5h, temperature of reaction is 65 ℃, and reaction finishes the back filtered while hot, isolates solid base catalyst, methyl alcohol is reclaimed in distillation, with the filtrate standing demix, the upper strata product is rough biofuel then, and lower floor is a glycerine, the further underpressure distillation of rough biofuel is purified, get biofuel.Through gas chromatographic detection, the content of gained Fatty acid methyl ester is 92.5%.
Embodiment 8
The first step is with embodiment 1
The second step LiAl composite oxides, cosolvent catalysis for preparing biodiesel oil
In the esterification device of taking back stream and water trap, the rapeseed oil that adds 101.4g, 19.2g methyl alcohol, magnetic agitation, adding weight and be rapeseed oil heavy 1.5% LiAl composite oxides and weight is that rapeseed oil weighs 25% tetrahydrofuran (THF), reaction times 3h, 65 ℃ of temperature of reaction, reaction finish the back filtered while hot, isolate catalyzer, methyl alcohol is reclaimed in distillation, with the filtrate standing demix, the upper strata product is rough biofuel then, and lower floor is a glycerine, the further underpressure distillation of rough biofuel is purified, get biofuel.Through gas chromatographic detection, the content of gained Fatty acid methyl ester is 94.5%.
Embodiment result, gather as follows:
| Embodiment | Raw material | Fat content (g) | Alcohol quality (g) | Molar ratio of methanol to oil | Catalyzer | Agent-oil ratio (%) | Cosolvent | Reaction times (h) | Yield (%) |
| 1 | Rapeseed oil/methyl alcohol | 101.4 | 19.2 | 6∶1 | LiAl-LDO | 1.5 | Do not have | 3 | 92.4 |
| 2 | Rapeseed oil/methyl alcohol | 101.4 | 19.2 | 6∶1 | LiMgAl-LDO | 1.8 | Do not have | 2.5 | 89.9 |
| 3 | Rapeseed oil/methyl alcohol | 101.4 | 19.2 | 6∶1 | ZnAl-LDO | 1.5 | Do not have | 5 | 89.4 |
| 4 | Rapeseed oil/methyl alcohol | 50.7 | 19.2 | 12∶1 | ZnMgAl-LDO | 2 | Do not have | 3 | 89.5 |
| 5 | Soybean oil/methyl alcohol | 50.7 | 19.2 | 6∶1 | LiAl-LDO | 1.5 | Do not have | 3 | 90.6 |
| 6 | Rapeseed oil/ethanol | 101.4 | 9.6 | 6∶1 | LiAl-LDO | 2 | Do not have | 3.5 | 90.8 |
| 7 | Rapeseed oil/methyl alcohol | 50.7 | 27.6 | 12∶1 | LiAl-LDO | 2 | Do not have | 3.5 | 92.5 |
| 8 | Rapeseed oil/methyl alcohol | 101.4 | 19.2 | 6∶1 | LiAl-LDO | 1.5 | Tetrahydrofuran (THF) | 3 | 94.5 |
Claims (5)
1. the method for a novel solid body base catalysis for preparing biodiesel oil is characterized in that: be raw material with the vegetables oil, with methyl alcohol or ethanol synthesis, add catalyzer, prepare biofuel through transesterification reaction; After the steps include: in batch reactor, to add vegetables oil, methyl alcohol or ethanol stirring, add solid base catalyst or solid base catalyst and cosolvent, carried out transesterification reaction 2～5 hours under 60-90 ℃, reaction back filtered while hot is isolated solid base catalyst; Filtrate standing demix, upper strata are major product, will get biofuel after the major product underpressure distillation of upper strata.
2. method according to claim 1 is characterized in that described solid base catalyst is a composite oxide of metal, and obtains by following steps:
A, under 60～70 ℃, a kind of solution in lithium salts, magnesium salts, the zinc salt or two kinds of mixing solutionss are mixed with aluminum salt solution, with mixing solutions and stream or single titration of alkali and carbonate, the dropping time is 0.5～2h, and the pH value of solution is controlled between the 10-12, after dripping, continue to stir 4～6h, 60～100 ℃ of nucleation crystallization, cooling then, suction filtration, washing are to neutral, at 100 ℃ of down dry 5～10h, get solid product;
B, with the roasting 3～12 hours under 400-700 ℃ of condition of above-mentioned solid product, novel solid body base catalyst.
3. method according to claim 2 is characterized in that described lithium salts, magnesium salts, and in zinc salt and the aluminium mixed salt solution: the mol ratio of Li and Al is 4～8: 1; The mol ratio of Zn and Al is 3～6: 1; The mol ratio of Mg and Al is 1～3: 1; In magnesium salts, zinc salt and aluminium mixed salt solution, the solid content of zinc salt is 4～10%.
4. method according to claim 1 is characterized in that described vegetables oil and methyl alcohol or alcoholic acid mol ratio are 4～20: 1; Catalyst levels is 0.5～5% of a vegetables oil weight; The cosolvent consumption is 10～30% of a vegetables oil weight.
5. according to claim 1 or 4 described methods, it is characterized in that described cosolvent is a kind of in tetrahydrofuran (THF), hexanaphthene and the toluene.
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| CNA2007100471156A CN101130700A (en) | 2007-10-17 | 2007-10-17 | Novel method for producing biological diesel oil with solid alkali catalysis |
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| CNA2007100471156A CN101130700A (en) | 2007-10-17 | 2007-10-17 | Novel method for producing biological diesel oil with solid alkali catalysis |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302433A (en) * | 2008-06-20 | 2008-11-12 | 华东理工大学 | Method for preparing biodiesel by super base-catalyzed ester exchange reaction of lipid and low-carbon alcohol |
| CN101250105B (en) * | 2008-03-28 | 2010-06-09 | 华东师范大学 | Method for synthesizing bio-diesel by using p-toluenesulfonic acid formaldehyde condensation polymer |
| CN101863771A (en) * | 2009-11-05 | 2010-10-20 | 齐齐哈尔大学 | Method for synthesizing methyl ethyl carbonate |
| CN102199493A (en) * | 2010-03-23 | 2011-09-28 | 华东理工大学 | Environmentally-friendly preparation method for biological diesel oil under catalysis of solid base |
| CN101705154B (en) * | 2009-11-11 | 2012-07-25 | 合肥工业大学 | Method for preparing ethyl ester biodiesel by cotton seed oil |
| CN106609189A (en) * | 2015-10-23 | 2017-05-03 | 中国石油化工股份有限公司 | Aliphatic ester preparation method |
| CN111517949A (en) * | 2020-04-22 | 2020-08-11 | 常州大学 | Method for synthesizing ethylene glycol phenyl ether methacrylate |
| CN114717056A (en) * | 2022-04-25 | 2022-07-08 | 广东省农业科学院农业质量标准与监测技术研究所 | Method for methyl esterification of oil by acid catalysis |
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- 2007-10-17 CN CNA2007100471156A patent/CN101130700A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250105B (en) * | 2008-03-28 | 2010-06-09 | 华东师范大学 | Method for synthesizing bio-diesel by using p-toluenesulfonic acid formaldehyde condensation polymer |
| CN101302433A (en) * | 2008-06-20 | 2008-11-12 | 华东理工大学 | Method for preparing biodiesel by super base-catalyzed ester exchange reaction of lipid and low-carbon alcohol |
| CN101863771A (en) * | 2009-11-05 | 2010-10-20 | 齐齐哈尔大学 | Method for synthesizing methyl ethyl carbonate |
| CN101863771B (en) * | 2009-11-05 | 2013-08-28 | 齐齐哈尔大学 | Method for synthesizing hydrotalcite like compound catalyst of methyl ethyl carbonate |
| CN101705154B (en) * | 2009-11-11 | 2012-07-25 | 合肥工业大学 | Method for preparing ethyl ester biodiesel by cotton seed oil |
| CN102199493A (en) * | 2010-03-23 | 2011-09-28 | 华东理工大学 | Environmentally-friendly preparation method for biological diesel oil under catalysis of solid base |
| CN106609189A (en) * | 2015-10-23 | 2017-05-03 | 中国石油化工股份有限公司 | Aliphatic ester preparation method |
| CN111517949A (en) * | 2020-04-22 | 2020-08-11 | 常州大学 | Method for synthesizing ethylene glycol phenyl ether methacrylate |
| CN111517949B (en) * | 2020-04-22 | 2022-09-27 | 常州大学 | Method for synthesizing ethylene glycol phenyl ether methacrylate |
| CN114717056A (en) * | 2022-04-25 | 2022-07-08 | 广东省农业科学院农业质量标准与监测技术研究所 | Method for methyl esterification of oil by acid catalysis |
| CN114717056B (en) * | 2022-04-25 | 2023-07-18 | 广东省农业科学院农业质量标准与监测技术研究所 | Method for acid-catalyzed methyl esterification of grease |
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