CN103725423A - Method for producing biodiesel by utilizing swill-cooked dirty oil - Google Patents
Method for producing biodiesel by utilizing swill-cooked dirty oil Download PDFInfo
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- CN103725423A CN103725423A CN201310732030.7A CN201310732030A CN103725423A CN 103725423 A CN103725423 A CN 103725423A CN 201310732030 A CN201310732030 A CN 201310732030A CN 103725423 A CN103725423 A CN 103725423A
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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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Abstract
The invention belongs to the technical field of biodiesel production and in particular relates to a method for producing biodiesel by utilizing swill-cooked dirty oil. The method for producing biodiesel by utilizing swill-cooked dirty oil comprises the following steps: (1) physical refining; (2) pre-esterifying swill-cooked dirty oil fat; (3) performing ester exchange on the swill-cooked dirty oil fat; and (4) refining the product. The method is simple and nontoxic in operation, high in reaction activity, mild in reaction conditions and high in yield and is hardly influenced by water, and the biodiesel prepared by utilizing the method is high in quality, light in color and high in purity.
Description
Technical field
The invention belongs to the technical field of production of biodiesel, be specifically related to a kind of method of utilizing sewer oil production biofuel.
Background technology
At present, diesel oil used, all with refining of petroleum, extract, but because the consumption of oil increases year by year, the underground storage of oil reduces increasingly on the market, and for solving the energy and environmental issue, countries in the world are all in research alternative fuel.
Sewer oil, the various poor quality oils that general reference exists in life, main source is food and drink, food-processing industry, the edible oil, the frying oil of Reusability, the swill wet goods that for example reclaim, when common edible oil (main component is triglyceride level) is through repeatedly decocting, explode after use, can react and generate a large amount of free fatty acidies and polycyclic aromatic hydrocarbons, very large to harm.Up to the present, often approximately there are ten thousand tons of sewer oils of 400-500 in the whole nation, but these sewer oils mostly process as refuse, easy contaminate environment not only, and cause very large waste.
In processing numerous measures of sewer oil, the most reasonable and the most economic method is exactly rationally to utilize, and turns waste into wealth, and take it as raw material production biofuel.It is ester-interchange method that current biofuel is prepared common method, uses methyl alcohol and sewer oil (triglyceride level) that transesterification reaction occurs under different condition and generates fatty acid methyl ester, and various fatty acid methyl esters can be used as biofuel and use.Mainly two kinds of minute acid catalysis and base catalysiss of ester-interchange method: carrying out base catalysis with NaOH, KOH etc. as catalyzer is mainly because its cheap being easy to get, but in raw material triglyceride level, exist certain free fatty acids and water can affect speed of response and esterification yield, increase the difficulty of product separation simultaneously, not only aftertreatment is complicated but also easy contaminate environment, and use acid catalyzed esterification to need higher temperature, consume energy higher, easily produce sour water.In addition, use in a large number the methyl alcohol also can be to environment.
Summary of the invention
The object of the invention is to for the defect of above-mentioned existence and a kind of method of utilizing sewer oil production biofuel is provided, this simple to operate nontoxic, reactive behavior is high, reaction conditions is gentle, productive rate is high and be not subject to water impact, the biofuel quality of utilizing the method to prepare is good, of light color, purity is high.
Technical scheme of the present invention is: a kind of method of utilizing sewer oil production biofuel, comprises the following steps:
(1) physics sorting: first trench grease is processed with the phosphoric acid that mass percentage concentration is 1~5%, sloughed phosphatide, cutin in trench grease, then trench grease is preheated to 100~150 ℃; Dehydration, enter extracting tower after degassed, 180 ℃ and-carry out underpressure distillation under 0.05MPa condition, free acid and steam are steamed simultaneously, free acid is removed through condensation;
(2) the pre-esterification of trench grease: the trench grease after physics sorting is transferred in No. 1 agitator, add again excessive ethanol, under 50~80 ℃ and 0.1~0.5MPa condition, carry out the pre-esterification of trench grease, after catalyzed reaction 2~4h, stratification, first separates the water layer that contains catalyzer, ethanol and partial reaction water, then in oil reservoir, add extraction agent to extract, be extracted phase; By extraction phase 100 ℃ and-carry out underpressure distillation under 0.05MPa condition, remove extraction agent, obtain the trench grease of pre-esterification;
(3) transesterify of sewer oil: the trench grease in the pre-esterification of step (2) gained goes in No. 2 agitators, then add ethanol, under 80~100 ℃ and 0.5~1MPa condition, continue after reaction 2~3h, 60 ℃ and-distill under 0.1MPa condition, ethanol cut is transferred to ethanol tundish through pump, finally obtains biodiesel coarse cut;
(4) product is refining: the biodiesel coarse cut of step (3) gained, through separated, washing, dry, is finally obtained to biofuel product.
Catalyst levels in described step (2) is 0.05~1% of trench grease weight.
Catalyzer in described step (2) is organic titanate catalyzer.
Described organic titanate catalyzer is at least one in titanium tetraethoxide, titanium tetraisopropylate, four n-butyl titaniums.
Described No. 1 agitator and No. 2 agitators are vertical stirrer.
Extraction agent in described step (2) is the mixture of glycerine and ethanol, and wherein the weight part ratio of glycerine and ethanol is 5:1.
Beneficial effect of the present invention is: the present invention utilizes organic titanate as esterifying catalyst, utilize it to replace respectively the vitriol oil and sodium hydroxide to come catalysis sewer oil to prepare derv fuel oil, overcome the purification difficult of traditional acid-base catalysis method product, produce a large amount of waste liquids, the shortcoming such as larger to the destruction of environment.Utilize organic titanate simultaneously catalytic esterification and transesterification reaction, simple to operate nontoxic, reactive behavior is high, reaction conditions is gentle, productive rate is high and be not subject to water impact.In addition, when pre-esterification and transesterification reaction, adopt ethanol to replace traditional methyl alcohol, and again in production technique, ethanol can recycle, more energy-conserving and environment-protective.Concrete advantage is as follows:
(1) in the present invention, organic titanate, as catalyzer, has good catalytic activity to the esterification of sewer oil free fatty acid and transesterification reaction.Under above preferred condition, the diesel oil goods of high yield and purity have been obtained.It is simple that the method is prepared biodiesel processes, and equipment investment is low, do not produce sour water, and environmental pollution is little, has good environmental protection characteristic, and product purity is high, and transformation efficiency can reach more than 95%, and industrial prospect is good;
(2) to use the object of methyl alcohol be that the solvability of basic catalyst in methyl alcohol is better to traditional method, and solvability in ethanol is poor, and selecting of alcohol of the present invention do not affected by catalyst solubility, so more energy-conserving and environment-protective of preparation process;
(3) preparation technology is simple to operate, pollution-free, and cost of investment is lower, and level of automation is high, is suitable for large-scale production;
(4) gained biofuel good product quality, of light color, purity is high.
Gained biofuel product performance index of the present invention is as follows:
From These parameters, biofuel color and luster of the present invention is close with ordinary diesel oil, and fuel value is higher than ordinary diesel oil and common biofuel, and cetane value is higher than ordinary diesel oil and common biofuel, and free glycerol content and 10% steams excess all lower than common biofuel.
Embodiment
Below by specific embodiment, the present invention will be described in detail.
Embodiment 1
A method of utilizing sewer oil production biofuel, comprises the following steps:
(1) physics sorting: first trench grease is processed with the phosphoric acid that mass percentage concentration is 2%, sloughed phosphatide, cutin in trench grease, then trench grease is preheated to 100 ℃; Dehydration, enter extracting tower after degassed, 180 ℃ and-carry out underpressure distillation under 0.05MPa condition, free acid and steam are steamed simultaneously, free acid is removed through condensation;
(2) the pre-esterification of trench grease: the trench grease after physics sorting is transferred in No. 1 vertical stirrer, add again excessive ethanol, under 80 ℃ and 0.1MPa condition, carry out the pre-esterification of trench grease, after catalyzed reaction 2h, stratification, first separates the water layer that contains catalyzer, ethanol and partial reaction water, then in oil reservoir, add extraction agent to extract, be extracted phase; By extraction phase 100 ℃ and-carry out underpressure distillation under 0.05MPa condition, remove extraction agent, obtain the trench grease of pre-esterification;
(3) transesterify of sewer oil: the trench grease in the pre-esterification of step (2) gained goes in No. 2 vertical stirrers, then add ethanol, under 100 ℃ and 1MPa condition, continue after reaction 3h, 60 ℃ and-distill under 0.1MPa condition, ethanol cut is transferred to ethanol tundish through pump, finally obtains biodiesel coarse cut;
(4) product is refining: the biodiesel coarse cut of step (3) gained, through separated, washing, dry, is finally obtained to biofuel product.
Catalyst levels in described step (2) is 0.05% of trench grease weight.
Catalyzer in described step (2) is organic titanate catalyzer.
Described organic titanate catalyzer is at least one in titanium tetraethoxide, titanium tetraisopropylate, four n-butyl titaniums.
Extraction agent in described step (2) is the mixture of glycerine and ethanol, and wherein the weight part ratio of glycerine and ethanol is 5:1.
Embodiment 2
A method of utilizing sewer oil production biofuel, comprises the following steps:
(1) physics sorting: first trench grease is processed with the phosphoric acid that mass percentage concentration is 1%, sloughed phosphatide, cutin in trench grease, then trench grease is preheated to 150 ℃; Dehydration, enter extracting tower after degassed, 180 ℃ and-carry out underpressure distillation under 0.05MPa condition, free acid and steam are steamed simultaneously, free acid is removed through condensation;
(2) the pre-esterification of trench grease: the trench grease after physics sorting is transferred in No. 1 vertical stirrer, add again excessive ethanol, under 50 ℃ and 0.5MPa condition, carry out the pre-esterification of trench grease, after catalyzed reaction 4h, stratification, first separates the water layer that contains catalyzer, ethanol and partial reaction water, then in oil reservoir, add extraction agent to extract, be extracted phase; By extraction phase 100 ℃ and-carry out underpressure distillation under 0.05MPa condition, remove extraction agent, obtain the trench grease of pre-esterification;
(3) transesterify of sewer oil: the trench grease in the pre-esterification of step (2) gained goes in No. 2 vertical stirrers, then add ethanol, under 80 ℃ and 0.5MPa condition, continue after reaction 2h, 60 ℃ and-distill under 0.1MPa condition, ethanol cut is transferred to ethanol tundish through pump, finally obtains biodiesel coarse cut;
(4) product is refining: the biodiesel coarse cut of step (3) gained, through separated, washing, dry, is finally obtained to biofuel product.
Catalyst levels in described step (2) is 1% of trench grease weight.
Catalyzer in described step (2) is organic titanate catalyzer.
Described organic titanate catalyzer is at least one in titanium tetraethoxide, titanium tetraisopropylate, four n-butyl titaniums.
Extraction agent in described step (2) is the mixture of glycerine and ethanol, and wherein the weight part ratio of glycerine and ethanol is 5:1.
Embodiment 3
A method of utilizing sewer oil production biofuel, comprises the following steps:
(1) physics sorting: first trench grease is processed with the phosphoric acid that mass percentage concentration is 5%, sloughed phosphatide, cutin in trench grease, then trench grease is preheated to 120 ℃; Dehydration, enter extracting tower after degassed, 180 ℃ and-carry out underpressure distillation under 0.05MPa condition, free acid and steam are steamed simultaneously, free acid is removed through condensation;
(2) the pre-esterification of trench grease: the trench grease after physics sorting is transferred in No. 1 vertical stirrer, add again excessive ethanol, under 60 ℃ and 0.3MPa condition, carry out the pre-esterification of trench grease, after catalyzed reaction 3h, stratification, first separates the water layer that contains catalyzer, ethanol and partial reaction water, then in oil reservoir, add extraction agent to extract, be extracted phase; By extraction phase 100 ℃ and-carry out underpressure distillation under 0.05MPa condition, remove extraction agent, obtain the trench grease of pre-esterification;
(3) transesterify of sewer oil: the trench grease in the pre-esterification of step (2) gained goes in No. 2 vertical stirrers, then add ethanol, under 90 ℃ and 0.8MPa condition, continue after reaction 2.5h, 60 ℃ and-distill under 0.1MPa condition, ethanol cut is transferred to ethanol tundish through pump, finally obtains biodiesel coarse cut;
(4) product is refining: the biodiesel coarse cut of step (3) gained, through separated, washing, dry, is finally obtained to biofuel product.
Catalyst levels in described step (2) is 0.08% of trench grease weight.
Catalyzer in described step (2) is organic titanate catalyzer.
Described organic titanate catalyzer is at least one in titanium tetraethoxide, titanium tetraisopropylate, four n-butyl titaniums.
Extraction agent in described step (2) is the mixture of glycerine and ethanol, and wherein the weight part ratio of glycerine and ethanol is 5:1.
The performance of product described in embodiment 1~3 is as follows respectively:
Claims (6)
1. a method of utilizing sewer oil production biofuel, comprises the following steps:
(1) physics sorting: first trench grease is processed with the phosphoric acid that mass percentage concentration is 1~5%, sloughed phosphatide, cutin in trench grease, then trench grease is preheated to 100~150 ℃; Dehydration, enter extracting tower after degassed, 180 ℃ and-carry out underpressure distillation under 0.05MPa condition, free acid and steam are steamed simultaneously, free acid is removed through condensation;
(2) the pre-esterification of trench grease: the trench grease after physics sorting is transferred in No. 1 agitator, add again excessive ethanol, under 50~80 ℃ and 0.1~0.5MPa condition, carry out the pre-esterification of trench grease, after catalyzed reaction 2~4h, stratification, first separates the water layer that contains catalyzer, ethanol and partial reaction water, then in oil reservoir, add extraction agent to extract, be extracted phase; By extraction phase 100 ℃ and-carry out underpressure distillation under 0.05MPa condition, remove extraction agent, obtain the trench grease of pre-esterification;
(3) transesterify of sewer oil: the trench grease in the pre-esterification of step (2) gained goes in No. 2 agitators, then add ethanol, under 80~100 ℃ and 0.5~1MPa condition, continue after reaction 2~3h, 60 ℃ and-distill under 0.1MPa condition, ethanol cut is transferred to ethanol tundish through pump, finally obtains biodiesel coarse cut;
(4) product is refining: the biodiesel coarse cut of step (3) gained, through separated, washing, dry, is finally obtained to biofuel product.
2. utilize according to claim 1 the method for sewer oil production biofuel, it is characterized in that, the catalyst levels in described step (2) is 0.05~1% of trench grease weight.
3. utilize according to claim 1 the method for sewer oil production biofuel, it is characterized in that, the catalyzer in described step (2) is organic titanate catalyzer.
4. utilize according to claim 3 the method for sewer oil production biofuel, it is characterized in that, described organic titanate catalyzer is at least one in titanium tetraethoxide, titanium tetraisopropylate, four n-butyl titaniums.
5. utilize according to claim 1 the method for sewer oil production biofuel, it is characterized in that, described No. 1 agitator and No. 2 agitators are vertical stirrer.
6. utilize according to claim 1 the method for sewer oil production biofuel, it is characterized in that, the extraction agent in described step (2) is the mixture of glycerine and ethanol, and wherein the weight part ratio of glycerine and ethanol is 5:1.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101113358A (en) * | 2006-07-27 | 2008-01-30 | 上海中油企业集团有限公司 | Method for reclaiming and utilizing trench oil |
CN101805672A (en) * | 2010-03-08 | 2010-08-18 | 中山大学 | Biodiesel and preparation method thereof |
CN103421615A (en) * | 2013-05-20 | 2013-12-04 | 西安市宝润实业发展有限公司 | Technology for producing biodiesel through illegal cooking oil or waste cooking oil |
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- 2013-12-25 CN CN201310732030.7A patent/CN103725423A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101113358A (en) * | 2006-07-27 | 2008-01-30 | 上海中油企业集团有限公司 | Method for reclaiming and utilizing trench oil |
CN101805672A (en) * | 2010-03-08 | 2010-08-18 | 中山大学 | Biodiesel and preparation method thereof |
CN103421615A (en) * | 2013-05-20 | 2013-12-04 | 西安市宝润实业发展有限公司 | Technology for producing biodiesel through illegal cooking oil or waste cooking oil |
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Application publication date: 20140416 |