CN102260595A - Process for producing fatty acid methyl ester with grease waste - Google Patents
Process for producing fatty acid methyl ester with grease waste Download PDFInfo
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- CN102260595A CN102260595A CN2010101826858A CN201010182685A CN102260595A CN 102260595 A CN102260595 A CN 102260595A CN 2010101826858 A CN2010101826858 A CN 2010101826858A CN 201010182685 A CN201010182685 A CN 201010182685A CN 102260595 A CN102260595 A CN 102260595A
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Abstract
The invention relates to a process for producing fatty acid methyl ester with grease wastes, which comprises the following steps of: by using grease wastes and methanol as raw materials and using solid acid as catalyst, carrying out countercurrent contact on methanol entered from a tower kettle of a catalytic distillation reactor and grease wastes entered from the top of the catalytic distillation reactor at a tower column of a catalytic distillation tower; reacting under the action of solid acid catalyst to generate fatty acid methyl ester; decompressing and distilling to obtain a fatty acid methyl ester product; and carrying out alkali catalytic ester exchange reaction on the rest triglyceride to prepare fatty acid methyl ester. The method has the advantages and effects of high product yield, high conversion rate of fatty acid, no need of pretreatment of grease wastes, simplification of process flow and prolongation of service life of catalyst.
Description
Technical field
The present invention relates to a kind of processing method of producing fatty acid methyl ester with fatty wastes, particularly is that catalyzer adopts the catalytic distillation reactor with the solid acid, makes the methyl esterification of fatty acid that dissociates in the fatty wastes prepare the processing method of fatty acid methyl ester.
Background technology
Fatty wastes is a series of oil-containing soap stocks that lose edibleness that produce in edible natural vegetables oil, animal tallow, catering trade waste oil and grease deep-processing process.Be commonly called as and be sewer oil.Calculate according to the expert, the amount of these discarded food oils accounts for 20～30% of edible oil total quantity consumed.In 2,100 ten thousand tons of the edible oil masses of the average annual consumption of China, then annual fatty wastes 400～8,000,000 ton of producing.The fatty wastes that can be used as resource has only about 4,000,000 tons, and at present, China's fatty wastes is edible rationally not to be utilized.Therefore, become a kind of environmental pollutant, and impact food safety.
Contain large amount of organic in the waste grease, have and pollute and the recycling dual nature.This is very important alternative petroleum resources.Face energy dilemma and environmental pollution in the whole world day by day under the serious situation; the reply fatty wastes is rationally recycled; utilize discarded food oils to prepare fatty acid methyl ester at present; also be biofuel; method is: at first to the fatty wastes pre-treatment of coming unstuck, decolour; be catalyzer then with sulfuric acid, adopt still reaction to carry out esterification reaction of organic acid, again reaction product is carried out molecular distillation and obtain fatty acid methyl ester.As catalyzer etching apparatus not only, and product needs to remove sulfuric acid through water elution, produce a large amount of contaminated wastewater environment with sulfuric acid.,, reported among the CN101338216A with solid super-strong acid ZrO according to reported in literature
2～TiO
2/ SO
4 2-Be catalyzer, at molar ratio of methanol to oil is under the condition of 70～95 ℃ of 16: 1, temperature, acidifying oil after handling through come unstuck matter and decolouring is carried out esterification reaction of organic acid prepare fatty acid methyl ester, in tank reactor, react among 4～8 hours CN101338214A then with storng-acid cation exchange resin A-15 and solid heteropoly acid H
3PO
4.12WO
3.XH
2O is a catalyzer, and the acidifying oil after handling through come unstuck matter and decolouring is carried out esterification reaction of organic acid in tank reactor, and underpressure distillation obtains fatty acid methyl ester then.
Aforesaid method though avoided liquid acid catalysts such as sulfuric acid that the still formula of conversion unit and water elution are removed process as catalyst liquid acid, exists raw material to need shortcomings such as pre-treatment, reaction alcohol oil rate are big, technical process length, energy consumption height; Lipid acid and methyl alcohol carry out can generating a part water when esterification generates fatty acid methyl ester in addition, and water and an acidic catalyst are present in the reaction system simultaneously, and fatty acid methyl ester can be hydrolyzed to lipid acid again, causes reaction product fatty acid methyl ester once through yield low.
Summary of the invention
Purpose of the present invention is just in order to overcome the above-mentioned shortcoming that oneself has a technology with not enough and to provide a kind of be catalyzer with the solid acid; adopt the catalytic distillation reactor; with the fatty wastes is the processing method of raw material production fatty acid methyl ester; thereby can turn waste into wealth, improve the ecological environment, alleviating energy crisis, promotion sustainable economic development.
The objective of the invention is to realize by following technical proposal:
Produce the processing method of fatty acid methyl ester with fatty wastes, it is a raw material with fatty wastes and methyl alcohol, with the solid acid is catalyzer, the mol ratio of methyl alcohol and fatty wastes is 2～4: 1, the catalytic distillation reactor that employing is made up of distillation tower still and catalytic distillation tower king-post, fatty wastes is from the catalytic distillation tower king-post jacking material of catalyzer that solid acid is housed, the king-post head temperature is 60～70 ℃, methyl alcohol is vaporized at distillation Tata still, temperature is 90～120 ℃, methyl alcohol after the vaporization enters the fatty wastes that enters with catalytic distillation tower king-post top in catalytic distillation tower king-post counter current contact from catalytic distillation tower king-post bottom, per hour charging quality of discarded food oils and king-post loading catalyst mass ratio are 0.5～1.0h
-1Reaction generates fatty acid methyl ester under the effect of solid acid catalyst, flow into the distillation tower still through the catalytic distillation tower king-post again, water and unreacted methanol that lipid acid and methyl alcohol reaction generate are flowed out by the catalytic distillation tower cat head, the tower still is the triglyceride that contains of reaction product fatty acid methyl ester and discarded food oils and the mixture of micro-phosphatide, colloid etc., tower kettle product just can obtain fatty acid methyl ester through underpressure distillation, and remaining triglyceride level can adopt base-catalyzed transesterification prepared in reaction fatty acid methyl ester.
Described catalytic distillation tower king-post tower is a packing tower, stage number is 20～35, solid acid catalyst is seated in catalytic distillation tower top, the top covers with solid porcelain ball, and described fatty wastes is a series of oil-containing soap stocks that lose edibleness that produce in edible natural vegetables oil, animal tallow, catering trade waste oil and grease deep-processing process.Described solid acid catalyst is storng-acid cation exchange resin, phosphorus heteropoly tungstic acid or solid super-strong acid; The reflux ratio of described cat head methyl alcohol input and output material is 3～4.
Method of the present invention is a raw material with fatty wastes and methyl alcohol, fatty wastes acid number 30～200mgKOH/g, it contains a large amount of lipid acid, after the methyl alcohol vaporization, under the solid acid catalyst effect, as storng-acid cation exchange resin, phosphorus heteropoly tungstic acid or solid super-strong acid, can generate fatty acid methyl ester for 90～120 ℃ in temperature, pump in the catalytic distillation king-post that solid acid catalyst is housed by volume pump by the catalytic distillation tower column top; Methyl alcohol is by the charging of catalytic distillation Tata still, methyl alcohol is vaporized after the catalytic distillation tower king-post flows from bottom to top at the tower still, with by the discarded food oils of cat head charging in catalytic distillation tower body counter current contact, reaction generates fatty acid methyl ester under the effect of solid acid catalyst, flows into catalytic distillation Tata still through the catalytic distillation tower king-post; Water and unreacted methanol that lipid acid and methyl alcohol reaction generate are flowed out by the catalytic distillation tower cat head, thereby have eliminated the hydrolysis of water generation reaction to the target product fatty acid methyl ester, improve the target product yield; The condensation in the catalytic distillation king-post of tower still methanol steam, backflow, the mol ratio that makes catalytic distillation king-post conversion zone methyl alcohol and lipid acid is much larger than charging methyl alcohol fatty wastes ratio, thereby increase substantially conversion rate of fatty acid, reduce the methyl alcohol fatty wastes ratio of reaction feed simultaneously, reduce the material benzenemethanol internal circulating load; Owing to adopt the catalytic distillation mode, catalyzer is subjected to the drip washing of methyl alcohol and reaction product fatty acid methyl ester continuously, trace impurity in the discarded food oils, can be as phosphatide, colloid attached on the catalyzer, thereby discarded food oils need not pretreatment dephosphorizing fat, colloid, and catalyzer prolongs work-ing life simultaneously; The tower still is the triglyceride that contains of reaction product fatty acid methyl ester and discarded food oils and the mixture of micro-phosphatide, colloid etc., tower kettle product just can obtain fatty acid methyl ester through underpressure distillation, remaining triglyceride level can adopt traditional base-catalyzed transesterification prepared in reaction fatty acid methyl ester, owing to adopt catalytic distillation technology, the conversion rate of fatty acid height, the lipid acid amount is low in the triglyceride, and base-catalyzed transesterification reacts completely.
The present invention adopts the catalytic distillation reactor of being made up of distillation Tata still and catalytic distillation tower king-post, and catalytic distillation tower king-post stage number is 20～35, and solid acid catalyst directly is deposited on the filler.
Owing to take technique scheme to make the technology of the present invention and have technology to compare to have the following advantages and effect:
(a) water of method esterification reaction generation of the present invention and unreacted methanol are flowed out by the catalytic distillation tower cat head, thereby have eliminated the hydrolysis of water generation reaction to the target product fatty acid methyl ester, improve the target product yield;
(b) methanol steam condensation in catalytic distillation tower, backflow, the mol ratio that makes catalytic distillation tower conversion zone methyl alcohol and lipid acid is much larger than the charging alcohol oil rate, thereby increase substantially conversion rate of fatty acid, reduce the alcohol oil rate of reaction feed simultaneously, reduce the material benzenemethanol internal circulating load;
(c) owing to adopt the catalytic distillation mode, catalyzer is subjected to the drip washing of methyl alcohol and reaction product fatty acid methyl ester continuously, trace impurity in the discarded food oils, can be as phosphatide, colloid attached on the catalyzer, thereby discarded food oils need not pretreatment dephosphorizing fat, colloid pre-treatment, simplify technical process, catalyzer prolongs work-ing life simultaneously;
(d) serialization production is enhanced productivity.
Embodiment
Following example will be further specified method provided by the invention, but therefore not limit the present invention.
Fatty wastes: the oil-containing soap stock that provides by Tianjin grease factory of COFCO, i.e. acidifying oil, acid number 134mgKOH/g;
Catering trade waste oil: biofuel company provides acid number 125mgKOH/g by green source, Hunan.
Embodiment 1
The oil-containing soap stock that fatty wastes provides from Tianjin grease factory of COFCO, be acidifying oil, acid number 134mgKOH/g and methyl alcohol are raw material, with A-15 macropore strong acid cation exchange resin 120 grams (butt) is the top of the packing tower of 20 of catalyst loading catalytic distillation tower king-post stage number, packing tower diameter 50mm, resin bed height 120mm, the resin top covers with solid porcelain ball, porcelain ball height 10mm; Acidifying oil is with the catalytic distillation tower king-post jacking material from catalyzer that solid acid is housed of charging 120g per hour, the king-post head temperature is 60 ℃, the cat head methanol eddy is than 2.0, methyl alcohol is vaporized at the distillation tower still, temperature is 120 ℃, methyl alcohol after the vaporization per hour 54g enters the acidifying oil that enters with catalytic distillation tower king-post top in catalytic distillation tower king-post counter current contact from catalytic distillation tower king-post bottom, per hour charging quality of discarded food oils and king-post loading catalyst mass ratio are 1.0h
-1Reaction generates fatty acid methyl ester under the effect of solid acid catalyst, flow into the distillation tower still through the catalytic distillation tower king-post again, water and unreacted methanol that lipid acid and methyl alcohol reaction generate are flowed out by the catalytic distillation tower cat head, the tower still is the triglyceride that contains of reaction product fatty acid methyl ester and acidifying oil and the mixture of micro-phosphatide, colloid etc., tower kettle product just can obtain fatty acid methyl ester through underpressure distillation, and remaining triglyceride level can adopt base-catalyzed transesterification prepared in reaction fatty acid methyl ester.The results are shown in Table 1.
Embodiment 2
Fatty wastes is a raw material with embodiment 1 and methyl alcohol, with A-15 macropore strong acid cation exchange resin 120 grams (butt) is the top of the packing tower of 25 of catalyst loading catalytic distillation tower king-post stage number, packing tower diameter 50mm, resin bed height 120mm, the resin top covers with solid porcelain ball, porcelain ball height 10mm; Acidifying oil is with the catalytic distillation tower king-post jacking material from catalyzer that solid acid is housed of charging 60g per hour, the king-post head temperature is 70 ℃, the cat head methanol eddy is than 3.0, methyl alcohol is vaporized at the distillation tower still, temperature is 120 ℃, methyl alcohol after the vaporization per hour 27g enters the acidifying oil that enters with catalytic distillation tower king-post top in catalytic distillation tower king-post counter current contact from catalytic distillation tower king-post bottom, per hour charging quality of discarded food oils and king-post loading catalyst mass ratio are 0.5h
-1Reaction generates fatty acid methyl ester under the effect of solid acid catalyst, flow into the distillation tower still through the catalytic distillation tower king-post again, water and unreacted methanol that lipid acid and methyl alcohol reaction generate are flowed out by the catalytic distillation tower cat head, the tower still is the triglyceride that contains of reaction product fatty acid methyl ester and acidifying oil and the mixture of micro-phosphatide, colloid etc., tower kettle product just can obtain fatty acid methyl ester through underpressure distillation, and remaining triglyceride level can adopt base-catalyzed transesterification prepared in reaction fatty acid methyl ester.The results are shown in Table 1.
Embodiment 3
Fatty wastes is a raw material with embodiment 1 and methyl alcohol, with A-15 macropore strong acid cation exchange resin 120 grams (butt) is the top of the packing tower of 25 of catalyst loading catalytic distillation tower king-post stage number, packing tower diameter 50mm, resin bed height 120mm, the resin top covers with solid porcelain ball, porcelain ball height 10mm; Acidifying oil is with the catalytic distillation tower king-post jacking material from catalyzer that solid acid is housed of charging 96g per hour, the king-post head temperature is 65 ℃, the cat head methanol eddy is than 4.0, methyl alcohol is vaporized at the distillation tower still, temperature is 110 ℃, methyl alcohol after the vaporization per hour 43.2g enters the acidifying oil that enters with catalytic distillation tower king-post top in catalytic distillation tower king-post counter current contact from catalytic distillation tower king-post bottom, per hour charging quality of discarded food oils and king-post loading catalyst mass ratio are 0.8h
-1Reaction generates fatty acid methyl ester under the effect of solid acid catalyst, flow into the distillation tower still through the catalytic distillation tower king-post again, water and unreacted methanol that lipid acid and methyl alcohol reaction generate are flowed out by the catalytic distillation tower cat head, the tower still is the triglyceride that contains of reaction product fatty acid methyl ester and acidifying oil and the mixture of micro-phosphatide, colloid etc., tower kettle product just can obtain fatty acid methyl ester through underpressure distillation, and remaining triglyceride level can adopt base-catalyzed transesterification prepared in reaction fatty acid methyl ester.The results are shown in Table 1.
Embodiment 4
Fatty wastes is a raw material with embodiment 1 and methyl alcohol, with A-15 macropore strong acid cation exchange resin 120 grams (butt) is the top of the packing tower of 35 of catalyst loading catalytic distillation tower king-post stage number, packing tower diameter 50mm, resin bed height 120mm, the resin top covers with solid porcelain ball, porcelain ball height 10mm; Acidifying oil with charging 120g per hour from the catalytic distillation tower king-post jacking material of solid acid catalyst is housed, the king-post head temperature is 60 ℃, the cat head methanol eddy is than 3.0, methyl alcohol is vaporized at the distillation tower still, temperature is 100 ℃, methyl alcohol after the vaporization per hour 40.3g enters the acidifying oil that enters with catalytic distillation tower king-post top in catalytic distillation tower king-post counter current contact from catalytic distillation tower king-post bottom, per hour charging quality of discarded food oils and king-post loading catalyst mass ratio are 1.0h
-1Reaction generates fatty acid methyl ester under the effect of solid acid catalyst, flow into the distillation tower still through the catalytic distillation tower king-post again, water and unreacted methanol that lipid acid and methyl alcohol reaction generate are flowed out by the catalytic distillation tower cat head, the tower still is the triglyceride that contains of reaction product fatty acid methyl ester and acidifying oil and the mixture of micro-phosphatide, colloid etc., tower kettle product just can obtain fatty acid methyl ester through underpressure distillation, and remaining triglyceride level can adopt base-catalyzed transesterification prepared in reaction fatty acid methyl ester.The results are shown in Table 1.
Embodiment 5
Fatty wastes is a catering trade waste oil, and biofuel company provides by green source, Hunan, and acid number 125mgKOH/g and methyl alcohol are raw material, with solid super-strong acid ZrO
2-TiO
2/ SO
4 2-A-15120 gram (butt) is the top of the packing tower of 30 of catalyst loading catalytic distillation tower king-post stage number, packing tower diameter 50mm, and resin bed height 120mm, the resin top covers with solid porcelain ball, porcelain ball height 10mm; Catering trade waste oil with charging 120g per hour from the catalytic distillation tower king-post jacking material of solid acid catalyst is housed, the king-post head temperature is 60 ℃, the cat head methanol eddy is than 3.0, methyl alcohol is vaporized at the distillation tower still, temperature is 100 ℃, methyl alcohol after the vaporization per hour 53.7g enters the catering trade waste oil that enters with catalytic distillation tower king-post top in catalytic distillation tower king-post counter current contact from catalytic distillation tower king-post bottom, per hour charging quality of catering trade waste oil and king-post loading catalyst mass ratio are 1.0h
-1Reaction generates fatty acid methyl ester under the effect of solid acid catalyst, flow into the distillation tower still through the catalytic distillation tower king-post again, water and unreacted methanol that lipid acid and methyl alcohol reaction generate are flowed out by the catalytic distillation tower cat head, the tower still is the triglyceride that contains of reaction product fatty acid methyl ester and catering trade waste oil and the mixture of micro-phosphatide, colloid etc., tower kettle product just can obtain fatty acid methyl ester through underpressure distillation, and remaining triglyceride level can adopt base-catalyzed transesterification prepared in reaction fatty acid methyl ester.The results are shown in Table 1.
Embodiment 6
Fatty wastes is with embodiment 5 and methanol feedstock, with D-06 macropore strong acid cation exchange resin 120 grams (butt) is the top of the packing tower of 20 of catalyst loading catalytic distillation tower king-post stage number, packing tower diameter 50mm, resin bed height 120mm, the resin top covers with solid porcelain ball, porcelain ball height 10mm; Catering trade waste oil with charging 120g per hour from the catalytic distillation tower king-post jacking material of solid acid catalyst is housed, the king-post head temperature is 70 ℃, the cat head methanol eddy is than 3.0, methyl alcohol is vaporized at the distillation tower still, temperature is 120 ℃, methyl alcohol after the vaporization per hour 53.7g enters the catering trade waste oil that enters with catalytic distillation tower king-post top in catalytic distillation tower king-post counter current contact from catalytic distillation tower king-post bottom, per hour charging quality of catering trade waste oil and king-post loading catalyst mass ratio are 1.0h
-1Reaction generates fatty acid methyl ester under the effect of solid acid catalyst, flow into the distillation tower still through the catalytic distillation tower king-post again, water and unreacted methanol that lipid acid and methyl alcohol reaction generate are flowed out by the catalytic distillation tower cat head, the tower still is the triglyceride that contains of reaction product fatty acid methyl ester and catering trade waste oil and the mixture of micro-phosphatide, colloid etc., tower kettle product just can obtain fatty acid methyl ester through underpressure distillation, and remaining triglyceride level can adopt base-catalyzed transesterification prepared in reaction fatty acid methyl ester.The results are shown in Table 1.
Embodiment 7
Fatty wastes is with embodiment 5 and methanol feedstock, with D-06 macropore strong acid cation exchange resin 120 grams (butt) is the top of the packing tower of 20 of catalyst loading catalytic distillation tower king-post stage number, packing tower diameter 50mm, resin bed height 120mm, the resin top covers with solid porcelain ball, porcelain ball height 10mm; Catering trade waste oil with charging 120g per hour from the catalytic distillation tower king-post jacking material of solid acid catalyst is housed, the king-post head temperature is 70 ℃, the cat head methanol eddy is than 3.0, methyl alcohol is vaporized at the distillation tower still, temperature is 120 ℃, methyl alcohol after the vaporization per hour 53.7g enters the catering trade waste oil that enters with catalytic distillation tower king-post top in catalytic distillation tower king-post counter current contact from catalytic distillation tower king-post bottom, per hour charging quality of catering trade waste oil and king-post loading catalyst mass ratio are 1.0h
-1Reaction generates fatty acid methyl ester under the effect of solid acid catalyst, flow into the distillation tower still through the catalytic distillation tower king-post again, water and unreacted methanol that lipid acid and methyl alcohol reaction generate are flowed out by the catalytic distillation tower cat head, the tower still is the triglyceride that contains of reaction product fatty acid methyl ester and catering trade waste oil and the mixture of micro-phosphatide, colloid etc., tower kettle product just can obtain fatty acid methyl ester through underpressure distillation, and remaining triglyceride level can adopt base-catalyzed transesterification prepared in reaction fatty acid methyl ester.The results are shown in Table 1.
Table 1: embodiment result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Acid number, mgKOH/g | 4.32 | 0.56 | 0.85 | 1.10 | 0.94 | 1.23 | 0.73 |
| The fatty acid methyl ester yield, % | 97.5 | 99.6 | 98.8 | 98.4 | 98.6 | 98.3 | 99.2 |
Claims (5)
1. processing method of producing fatty acid methyl ester with fatty wastes, it is characterized in that: it is a raw material with fatty wastes and methyl alcohol, with the solid acid is catalyzer, the mol ratio of methyl alcohol and fatty wastes is 2～4: 1, the catalytic distillation reactor that employing is made up of distillation tower still and catalytic distillation tower king-post, fatty wastes is from being equipped with the catalytic distillation tower king-post jacking material of solid acid catalyst, the king-post head temperature is 60～70 ℃, methyl alcohol is vaporized at distillation Tata still, temperature is 90～120 ℃, methyl alcohol after the vaporization enters the fatty wastes that enters with catalytic distillation tower king-post top in catalytic distillation tower king-post counter current contact from catalytic distillation tower king-post bottom, per hour charging quality of discarded food oils and king-post loading catalyst mass ratio are 0.5～1.0h
-1Reaction generates fatty acid methyl ester under the effect of solid acid catalyst, flow into the distillation tower still through the catalytic distillation tower king-post again, water and unreacted methanol that lipid acid and methyl alcohol reaction generate are flowed out by the catalytic distillation tower cat head, the tower still is the triglyceride that contains of reaction product fatty acid methyl ester and discarded food oils and the mixture of micro-phosphatide, colloid etc., tower kettle product just can obtain fatty acid methyl ester through underpressure distillation, and remaining triglyceride level can adopt base-catalyzed transesterification prepared in reaction fatty acid methyl ester.
2. according to the described processing method of producing fatty acid methyl ester with fatty wastes of claim 1, it is characterized in that: described catalytic distillation tower king-post tower is a packing tower, stage number is 20～35, and solid acid catalyst is seated in catalytic distillation tower top, and the top covers with solid porcelain ball.
3. according to the described processing method of producing fatty acid methyl ester with fatty wastes of claim 1, it is characterized in that: described fatty wastes is a series of oil-containing soap stocks that lose edibleness that produce in edible natural vegetables oil, animal tallow, catering trade waste oil and grease deep-processing process.
4. according to the described processing method of producing fatty acid methyl ester with fatty wastes of claim 1, it is characterized in that: described solid acid catalyst is storng-acid cation exchange resin, phosphorus heteropoly tungstic acid or solid super-strong acid.
5. according to the described processing method of producing fatty acid methyl ester with fatty wastes of claim 1, it is characterized in that: the reflux ratio of described cat head methyl alcohol input and output material is 3～4.
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| CN115043726A (en) * | 2022-07-06 | 2022-09-13 | 安徽富瑞雪化工科技股份有限公司 | Preparation method of mixed fatty acid ester for fertilizer anti-caking agent and fertilizer anti-caking agent |
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| CN105542970A (en) * | 2016-01-20 | 2016-05-04 | 定陶县地元生化制品有限公司 | Method and device for continuously producing biological diesel oil |
| CN108329207A (en) * | 2018-05-03 | 2018-07-27 | 凯瑞环保科技股份有限公司 | A kind of device and method producing fatty acid methyl ester using catalytic distillation technology |
| CN108329207B (en) * | 2018-05-03 | 2023-12-26 | 凯瑞环保科技股份有限公司 | Device and method for producing fatty acid methyl ester by catalytic distillation technology |
| CN114214122A (en) * | 2021-12-21 | 2022-03-22 | 常州市金坛区维格生物科技有限公司 | Method for preparing low-sulfur fatty acid methyl ester from high-acid-value waste oil by medium-low pressure method |
| CN114214122B (en) * | 2021-12-21 | 2023-09-26 | 常州市金坛区维格生物科技有限公司 | Method for preparing low-sulfur fatty acid methyl ester from high-acid value waste grease by low-pressure method |
| CN115043726A (en) * | 2022-07-06 | 2022-09-13 | 安徽富瑞雪化工科技股份有限公司 | Preparation method of mixed fatty acid ester for fertilizer anti-caking agent and fertilizer anti-caking agent |
| CN115322838A (en) * | 2022-08-29 | 2022-11-11 | 浙江工业大学 | Method for preparing fatty acid methyl ester by using waste oil |
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