CN106675789A - Method for preparing biodiesel with low sulfur content from gutter oil - Google Patents
Method for preparing biodiesel with low sulfur content from gutter oil Download PDFInfo
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- CN106675789A CN106675789A CN201710062985.4A CN201710062985A CN106675789A CN 106675789 A CN106675789 A CN 106675789A CN 201710062985 A CN201710062985 A CN 201710062985A CN 106675789 A CN106675789 A CN 106675789A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/08—Refining
- C11C1/10—Refining by distillation
- C11C1/103—Refining by distillation after or with the addition of chemicals
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/06—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils with glycerol
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
-
- 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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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Microbiology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention discloses a method for preparing biodiesel with low sulfur content from gutter oil. The method comprises a series of procedures as follows: pretreatment, esterification reaction, vacuum impurity removal, transesterification, glycerin separation and dealcholization as well as distillation refining. According to the technology, sulfur-containing substances are not introduced into the whole technological process except raw gutter oil materials in production while concentrated sulfuric acid is commonly used as a catalyst in the esterification reaction in the prior art; the vacuum impurity removal process is added before the transesterification process, impurities (including sulfur-containing impurities) with low boiling point are removed in advance, so that the sulfur content of a product is further reduced, and content of ester is increased.
Description
Technical field
The invention belongs to technical field of biodiesel preparation, and in particular to a kind of waste oil prepares the side of low-sulfur point diesel oil
Method.
Background technology
Due to the increasingly depleted of non-renewable energy resources on the earth, people have begun to find the succedaneum of traditional energy.This
When, biodiesel is come into as a kind of renewable and the characteristics of effect on environment is little compared with conventional fossil new-type energy
The visual field of people.But tradition biodiesel processed is relatively costly, because the raw material of tradition biodiesel processed is oil crop
(such as Brassica campestris L, Semen sojae atricolor, Semen Helianthi etc.).This just makes the popularization of biodiesel receive obstruction, and then scientist proposes to utilize
The conception that waste oil is turned waste into wealth, it is exactly to be acidified to be developed so far common waste oil preparation method, alkalization, enzymology and supercritical
Ester-interchange method.
The catalyst that acid catalyzed process is used mainly has sulphuric acid, hydrochloric acid and phosphoric acid etc..Under acid catalysed conditions, free fatty
Esterification can occur, and esterification reaction rate will be far faster than ester exchange speed, therefore the method is applied to free fatty and water
The preparing biodiesel from lipid for dividing content high, its yield is high, but reaction temperature and pressure are high, and methanol usage is big, and response speed is slow,
Consersion unit needs stainless steel material or enamel material, seriously corroded, the industrialization acid catalyzed process degree of receiving publicity to be much smaller than
Base catalysiss method.The catalyst that base catalysiss method is adopted is generally sodium hydroxide, potassium hydroxide, organic amine etc..In the absence of water, alkali
Property catalyst exchange activity is generally high than acidic catalyst.Base catalysiss method can at low temperature obtain higher yields, but it is to raw material
Middle free fatty and water content but have higher requirements.During the course of the reaction, free fatty can occur saponification product with alkali
Raw emulsion, contained humidity can then cause ester hydrolysis, while it can also weaken catalyst activity, as a result can make glycerol phase and first
Ester mutually becomes to be difficult to separate, so that post-reaction treatment process becomes numerous and diverse.Enzyme catalysis method is used by lipase to animal oil
Fat and low-carbon alcohols carry out transesterification, prepare corresponding fatty acid methyl ester and ethyl ester.The mild condition of enzyme catalysis method, alcohol consumption
It is little, non-pollution discharge.But its conversion ratio to short chain alcohol such as methanol and ethanol is low, and short chain alcohol has certain toxicity to enzyme, enzyme
Service life is short, while the price of lipase is prohibitively expensive, greatly limit enzyme catalysis method and prepares the industrialized rule of biodiesel
Mould and process.A kind of method still in test during supercritical ester-interchange method, supercritical fluid has diffusivity strong and viscosity
It is little, and density it is larger the characteristics of thus be widely used in extraction.By the continuous change of solvent phase cause reactant, product,
Waste is swapped in a fluid, finally realizes the purification to product and to waste, the written notes of by-product, greatly reduces ring
Border is born, and unique problem is that this technology is stranded because waste oil composition itself is extremely complex so implementing also certain
It is difficult.
Due to the simplest containing acid catalyzed process technique compared with juicy and free fatty, is added in waste oil, so mesh
Front biodiesel commercial production usually adopts acid catalyzed process, is suitable for compared with juicy and free-fat as catalyst using concentrated sulphuric acid
The preparing biodiesel from lipid of acid, productivity ratio is higher, but in production process in can produce a large amount of Waste Sulfuric Acids, Waste Sulfuric Acid is directly arranged
Putting to pollute, using in alkali liquor and increase cost, while sulfur content is also too high in the biodiesel for preparing, put goods on the market
Using rear and to environment.
The content of the invention
It is an object of the invention to provide a kind of method that waste oil prepares low-sulfur decomposing biological diesel oil, not only can become give up into
Treasured, and prevented lawless person and process as food oil waste oil to sell, the health care belt for giving people is endangering.
Realizing the technical scheme of the object of the invention is:A kind of method that waste oil prepares low-sulfur decomposing biological diesel oil, its feature
It is:
(1) pretreatment
Mechanical admixture is removed after waste oil is precipitated, vacuum dehydration is obtained under conditions of 80 DEG C -120 DEG C of temperature after coarse filtration
Raw oil, raw oil proceeds to reactor;
(2) esterification
0.02-0.05Mpa of vacuum in control reactor;It is 180-230 DEG C to control the reaction temperature in reactor;
Add glycerol into reactor, control the constant temperature esterification response time for 2-3.5 hours;
(3) vacuum remove impurity
Reactor interior reaction temperature is kept, vacuum is improved to more than 0.090Mpa, is continued to be reacted and evaporate simultaneously de- drop not
Reaction organic impuritiess, maintain above-mentioned condition 10-30 minute, after product cooling transesterification reactor to be proceeded to;
(5) ester exchange reaction
The reaction temperature for controlling transesterification reactor is 60-67 DEG C, and methanol and catalysis are added in transesterification reactor
Agent, seals agitating heating, reacts 1.0-2.5 hours, terminating reaction;
(4) glycerol dealcoholysis is separated
Add phosphoric acid, temperature to rise to 100-130 DEG C and boil off unreacted methanol in transesterification reactor, take off methanol
Cooling afterwards stops stirring static layering.Lower floor glycerin layer is released, upper-layer fat acid methyl ester layer is isolated and is proceeded to filler distillation column and treat
Distillation.
(6) distill refined
Control filler distillation column 0.097-0.099Mpa of vacuum, slow heating heats up, by drop temperature 165-200
DEG C, 201-225 DEG C, 226-260 DEG C collect fraction respectively, obtain fatty acid methyl ester fraction before, during and after different quality.
It is 6 that raw oil is controlled in the step (2) with glycerol proportioning:1 to 15:1.
It is 1 that methanol and esterised oil proportioning are controlled in the step (3):7 to 5.5:7..
Vacuum is improved to 0.090-0.099Mpa in reactor in the step (3).
Product proceeds to transesterification reactor after being cooled to 65 DEG C in the step (3).
Step (4) catalyst is the potassium hydroxide of esterifying liquid quality 0.5%.
Oils and fatss temperature is kept to be 45 DEG C -55 DEG C in the step (1) in waste oil filter process.
Above-mentioned technical proposal is employed, the present invention has following beneficial effect:(1) technique of the invention ensure that card life
In product in addition to waste oil raw material, (the conventional concentrated sulphuric acid conduct of esterification of sulfur-bearing component substances is not introduced in whole technical process
Catalyst), increasing increase before ester exchange process vacuum impurity removal process, and lower boiling impurity is removed in advance (including sulfur-bearing
Impurity), product sulfur-bearing is further reduced, ester content increases.
(2) technique of the invention does not introduce catalyst in esterification reaction process, reduces in subsequent technique to catalyst
Extraction operation, simplify production technology.
(3) loss of the concentrated sulphuric acid to equipment is inventive process avoids, while also less acid removal process, reduces life
Produce cost.
Specific embodiment
(embodiment 1)
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the invention, rather than the embodiment of whole.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
In the embodiment of the present invention, a kind of method that waste oil prepares low-sulfur decomposing biological diesel oil, including:
(1) pretreatment
Mechanical admixture is removed after waste oil is precipitated, vacuum dehydration is obtained under conditions of 80 DEG C -120 DEG C of temperature after coarse filtration
Raw oil;
(2) esterification
Take above-mentioned raw materials oil 628g (acid number 113mgKoH/g, sulfur-bearing 212ppm) to add in 1000ml there-necked flasks, then add
Enter 7% glycerol 43.96g of trench oil quality, stir temperature reaction, at 180-230 DEG C, vacuum degree control exists temperature control
0.02-0.05Mpa, reacts 2-3.5 hours, and acid number is down to 2.56mgKOH/g by 113mgKOH/g.
(3) fine vacuum remove impurity
Reaction temperature is kept, vacuum is improved to 0.090-0.099Mpa, continuing to react while evaporating de- drop unreacted has
Machine impurity, maintains above-mentioned condition 10-30 minutes, and acid number drops to 0.89mgKOH/g, and cooling terminates reaction.
(4) ester exchange reaction
Above-mentioned esterifying liquid is cooled to into 65 DEG C, the methanol and esterifying liquid quality of esterifying liquid quality 20% are added under agitation
0.5% metallic compound (potassium hydroxide) catalyst, seals agitating heating, and temperature control is fully reacted at 60-67 DEG C
1.0-2.5 hours.Acid number 0.11mgKOH/g, terminating reaction of lowering the temperature.
(5) glycerol dealcoholysis is separated
Above-mentioned reactant liquor is transferred to into static layering in 1000ml separatory funnels, point sub-cloud glycerin layer, upper-layer fat acid
Methyl ester layer is poured in 1000ml flasks, and heat up separating methanol under 0.08-0.09Mpa of vacuum, and temperature rises to 100-130 DEG C,
Take off and cooled down after methanol, obtained crude fatty acid methyl ester 602g.
(6) distill refined
Above-mentioned crude fatty acid methyl ester is distilled under the high vacuum condition of 0.097-0.099Mpa, by drop temperature 165-
200 DEG C, 201-225 DEG C, 226-260 DEG C are collected respectively fraction, fatty acid methyl ester fraction 35.6g before, during and after obtaining, 461g,
61.2g, unevaporated plant asphalt residue 43.9g.
Product quality:Middle fraction fatty acid methyl ester light yellow transparent liquid, acid number 0.35mgKOH/g, sulfur-bearing 7.02ppm,
Ester content 97.1%, wherein total glycerol content 0.033%, free glycerol content 0.011%.
Mixed methyl aliphatic ester light yellow clear liquid in front and back, acid number 0.40mgKOH/g, sulfur-bearing 29.8ppm, ester content
96.6%, total glycerol content 0.153%, wherein free glycerol content 0.011%.
(embodiment 2)
A kind of method that waste oil prepares low-sulfur decomposing biological diesel oil, including:
(1) pretreatment
Mechanical admixture is removed after waste oil is precipitated, vacuum dehydration is obtained under conditions of 80 DEG C -120 DEG C of temperature after coarse filtration
Raw oil;
(2) esterification
By waste oil coarse filtration, vacuum dehydration (80-120 DEG C);Measure 10.5 tons of above-mentioned waste oil (acid number 107mgKoH/g,
Sulfur-bearing 198ppm) 20m3 stainless steel cauldrons are added, add 6.8% glycerol 714kg of trench oil quality, stirring heats up anti-
Should, temperature control at 180-230 DEG C, in 0.02-0.05Mpa react 2-3.5 hours by vacuum degree control, reactant liquor acid number by
107mgKOH/g is down to 2.81mgKOH/g.
(3) fine vacuum remove impurity
Reaction temperature is kept, reactor vacuum is improved to 0.090-0.099Mpa, is continued to be reacted and evaporate simultaneously de- drop not
Reaction organic impuritiess, maintain above-mentioned condition 10-30 minutes, and reactant liquor acid number continues to drop to 0.96mgKOH/g, and cooling terminates anti-
Should.
(4) ester exchange reaction
Above-mentioned esterifying liquid is cooled to into 65 DEG C, in being transferred to 20m3 rustless steel ester interchange vessels, is added prepare under agitation
(metallic compound (potassium hydroxide) catalysis of the methanol of esterifying liquid quality 20% and esterifying liquid quality 0.5% of alcohol aqueous slkali
Agent), agitating heating, temperature control remains that methanol has a small amount of backflow at 63-67 DEG C, fully reacts 1.0-2.5 hours.
Acid number 0.08mgKOH/g, terminating reaction.
(5) glycerol dealcoholysis is separated
Appropriate phosphoric acid is added in transesterification reactor, methanol eddy is switched to into discharging, heating boils off unreacted
Methanol, when reacting liquid temperature is raised to 120-130 DEG C of methanol zero discharges, cooling stops stirring static layering.Release lower floor's glycerol
Layer, totally 10.05 tons of upper-layer fat acid methyl ester layer, moves into filler distillation column to be distilled.
(6) distill refined
Control filler distillation column 0.097-0.099Mpa of vacuum, slow heating heats up, by drop temperature 165-200
DEG C, 201-225 DEG C, 226-260 DEG C collect fraction respectively, by front and rear fatty acid methyl ester merge, merge fat before and after must neutralizing
Fatty acid methyl esters fraction 7638kg, 1402kg, the plant asphalt residue net weight 801kg not steamed.
Product quality:Middle fraction fatty acid methyl ester light yellow transparent liquid, acid number 0.31mgKOH/g, sulfur-bearing 8.2ppm, ester
Content 97.4%, wherein total glycerol content 0.033%, free glycerol content 0.011%.
Merge fatty acid methyl ester light yellow clear liquid, acid number 0.46mgKOH/g, sulfur-bearing 27.9ppm in front and back.
Particular embodiments described above, has been carried out further in detail to the purpose of the present invention, technical scheme and beneficial effect
Describe in detail it is bright, should be understood that the foregoing is only the present invention specific embodiment, be not limited to the present invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., should be included in the guarantor of the present invention
Within the scope of shield.
Claims (6)
1. a kind of method that waste oil prepares low-sulfur decomposing biological diesel oil, it is characterised in that:
(1) pretreatment
Mechanical admixture is removed after waste oil is precipitated, vacuum dehydration obtains raw material under conditions of 80 DEG C -120 DEG C of temperature after coarse filtration
Oil, raw oil proceeds to reactor;
(2) esterification
0.02-0.05Mpa of vacuum in control reactor;It is 180-230 DEG C to control the reaction temperature in reactor;To anti-
Addition glycerol in kettle is answered, the constant temperature esterification response time is controlled for 2-3.5 hours;
(3) vacuum remove impurity
Reactor interior reaction temperature is kept, vacuum is improved to more than 0.090Mpa, is continued to be reacted and evaporate simultaneously de- drop unreacted
Organic impuritiess, maintain above-mentioned condition 10-30 minute, after product cooling transesterification reactor to be proceeded to;
(4) ester exchange reaction
The reaction temperature for controlling transesterification reactor is 60-67 DEG C, and methanol and catalyst are added in transesterification reactor, close
Envelope agitating heating, reacts 1.0-2.5 hours, terminating reaction;
(5) glycerol dealcoholysis is separated
Add phosphoric acid, temperature to rise to 100-130 DEG C and boil off unreacted methanol in transesterification reactor, taken off and dropped after methanol
Temperature stops stirring static layering.Lower floor glycerin layer is released, isolating upper-layer fat acid methyl ester layer, to proceed to filler distillation column to be distilled.
(6) distill refined
Control filler distillation column 0.097-0.099Mpa of vacuum, slow heating heat up, by 165-200 DEG C of drop temperature,
201-225 DEG C, 226-260 DEG C are collected respectively fraction, obtain fatty acid methyl ester fraction before, during and after different quality.
2. the method that a kind of waste oil according to claim 1 prepares low-sulfur decomposing biological diesel oil, it is characterised in that:The step
Suddenly it is 6 that raw oil is controlled in (2) with glycerol proportioning:1 to 15:1.
3. the method that a kind of waste oil according to claim 1 prepares low-sulfur decomposing biological diesel oil, it is characterised in that:The step
Suddenly it is 1 that methanol and esterised oil proportioning are controlled in (3):7 to 5.5:7..
4. the method that a kind of waste oil according to claim 1 prepares low-sulfur decomposing biological diesel oil, it is characterised in that:The step
Suddenly vacuum is improved to 0.090-0.099Mpa in reactor in (3).
5. the method that a kind of waste oil according to claim 1 prepares low-sulfur decomposing biological diesel oil, it is characterised in that:The step
Suddenly product proceeds to transesterification reactor after being cooled to 65 DEG C in (3).
6. the method that a kind of waste oil according to claim 1 prepares low-sulfur decomposing biological diesel oil, it is characterised in that:The step
Suddenly (4) catalyst is the potassium hydroxide of esterifying liquid quality 0.4-1.0%.
According to the method that a kind of described in claim 1 waste oil prepares low-sulfur decomposing biological diesel oil, it is characterised in that:The step
(1) oils and fatss temperature is kept to be 45 DEG C -55 DEG C in waste oil filter process.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107254361A (en) * | 2017-08-10 | 2017-10-17 | 唐山金利海生物柴油股份有限公司 | Produce the device and method of super-low sulfur biodiesel |
CN108977281A (en) * | 2018-07-05 | 2018-12-11 | 浙江恒翔化工有限公司 | A method of methyl esters is prepared using high acid value poor oil rouge |
CN111349491A (en) * | 2018-12-21 | 2020-06-30 | 中国石油化工股份有限公司 | Modified vegetable oil fatty acid methyl ester and preparation method and application thereof |
CN112646664A (en) * | 2019-10-12 | 2021-04-13 | 常州市金坛区维格生物科技有限公司 | Method for preparing low-sulfur biodiesel from acidized oil |
CN113862085A (en) * | 2021-09-09 | 2021-12-31 | 江苏英汇能源科技有限公司 | Process for producing methyl ester by using waste oil |
CN114214121A (en) * | 2021-12-14 | 2022-03-22 | 浙江东江能源科技有限公司 | High-quality low-sulfur-content biodiesel preparation device and preparation method |
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107254361A (en) * | 2017-08-10 | 2017-10-17 | 唐山金利海生物柴油股份有限公司 | Produce the device and method of super-low sulfur biodiesel |
WO2019028571A1 (en) * | 2017-08-10 | 2019-02-14 | 唐山金利海生物柴油股份有限公司 | Device and method for producing ultra-low sulfur biodiesel |
CN107254361B (en) * | 2017-08-10 | 2019-08-02 | 唐山金利海生物柴油股份有限公司 | Produce the device and method of super-low sulfur biodiesel |
US10865430B2 (en) | 2017-08-10 | 2020-12-15 | Tangshan Jinlihai Biodiesel Corporation Limited | Device and method of producing ultra-low sulfur biodiesel |
CN108977281A (en) * | 2018-07-05 | 2018-12-11 | 浙江恒翔化工有限公司 | A method of methyl esters is prepared using high acid value poor oil rouge |
CN111349491A (en) * | 2018-12-21 | 2020-06-30 | 中国石油化工股份有限公司 | Modified vegetable oil fatty acid methyl ester and preparation method and application thereof |
CN111349491B (en) * | 2018-12-21 | 2022-04-08 | 中国石油化工股份有限公司 | Modified vegetable oil fatty acid methyl ester and preparation method and application thereof |
CN112646664A (en) * | 2019-10-12 | 2021-04-13 | 常州市金坛区维格生物科技有限公司 | Method for preparing low-sulfur biodiesel from acidized oil |
CN113862085A (en) * | 2021-09-09 | 2021-12-31 | 江苏英汇能源科技有限公司 | Process for producing methyl ester by using waste oil |
CN114214121A (en) * | 2021-12-14 | 2022-03-22 | 浙江东江能源科技有限公司 | High-quality low-sulfur-content biodiesel preparation device and preparation method |
CN114214121B (en) * | 2021-12-14 | 2024-02-20 | 浙江东江能源科技有限公司 | Preparation device and preparation method of high-quality low-sulfur biodiesel |
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