CN101402876A - Method for producing biological diesel oil with seed oil of Chinese pine - Google Patents
Method for producing biological diesel oil with seed oil of Chinese pine Download PDFInfo
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- CN101402876A CN101402876A CNA2008102323083A CN200810232308A CN101402876A CN 101402876 A CN101402876 A CN 101402876A CN A2008102323083 A CNA2008102323083 A CN A2008102323083A CN 200810232308 A CN200810232308 A CN 200810232308A CN 101402876 A CN101402876 A CN 101402876A
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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 preparation method for biodiesel by using Chinese pine seed oil which includes the following steps: step I, the Chinese pine seed oil, methanol and a catalyst of sodium hydroxide or potassium hydroxide are added into a three-neck flask for reaction; the reaction temperature is controlled between 20 to 75 DEG C; the reaction time is 5 to 120 minutes; step II, distillation is carried out on the mixed system under a normal pressure for recycling excessive methanol; step III, the temperature is reduced to the room temperature and the mixed system is stood and layered for 6 to 24 hours; the lower layer is coarse glycerin and the upper layer is the coarse product of the biodiesel; the coarse product of the biodiesel is separated and dilute sulphuric acid is added into the coarse product for adjusting the pH of a layer system; warm water is used for washing the coarse product for obtaining the biodiesel; and step IV, an anhydrous sodium sulfate drier is added into the biodiesel for carrying out drying treatment for preparing pure biodiesel. The preparation method is characterized by energy saving, environment protection and improving the operating factor of the Chinese pine seeds.
Description
Technical field
The invention belongs to technical field of biodiesel preparation, particularly a kind of method with producing biological diesel oil with seed oil of Chinese pine.
Background technology
Energy security is one of national strategy safety control basis.In China because populous, efficiency of energy utilization is low, energy structure is unreasonable and Energy production invisible cost height, energy problem's its sternness to the utmost.Since China in 1993 becomes oil importers, annual petroleum import amount is with 4% speed increase, this makes the external interdependency of CNPC be increased to grandson 33.8%[Yongming in 2000 from 7.6% of nineteen ninety-five, Yuan Zhenhong, Sun Zhenjun. Chinese biological mass-energy source and biomass are utilized status and prospects [J]. renewable energy source, 2006, (2): 78-82].Estimate that the crude runs of China in 2010 will reach 2.7 hundred million tons, but crude oil yield be no more than 1.7 hundred million tons [Meng Fanqing, Wang Demin magnify year etc. the preparation research of biofuel [J]. chemistry world, 2004,45 (7): 359-362].To this, it is to seek saving type and substituted type oil fuel that China has formulated the major measure that solves national petroleum resources shortage, alleviation contradiction between oil supply and demand, well selects and utilize reproducible biomass resource production biofuel to be one.Therefore China's edible oil shortage can not prepare biofuel with soybean oil, rapeseed oil, peanut oil or cottonseed wet goods edible oil with external the same, can only select for use animals and plants waste grease and woody oleiferous plants to prepare biofuel.
Chinese pine (Pinus tabulaeformis) belongs to the Pinaceae arbor, it is the woody oil tree species of China's special product, strong to environmental compatibility, impoverishment tolerant, wind resistance, anti-dry and cold weather, be suitable for the growth of mountain region and knob, can be in the deserted mountain, the wasteland cultivation, it is the good forest of checking winds and fixing drifting sand, mainly be distributed in ground such as Liaoning, Jilin, the Inner Mongol, Hebei, Henan, Shanxi, Shaanxi, Shandong, Gansu, Ningxia, Qinghai, the north, Sichuan in China, become one of topmost reproducting tree species of northern China wide geographic area.Chinese pine seed oil length is a kind of inexhaustible renewable oil sources up to more than 30%.
The preparation method of biofuel mainly comprises hybrid system, mini-emulsion process, pyrolysis method.Hybrid system prepares biofuel viscosity height, the difficult incomplete combustion that atomizes, and cetane value is low, complex process, expense is higher; The biofuel calorific value and the cetane value of mini-emulsion process preparation have reduced, and also have problems such as carbon distribution, coking and lubricating oil dilution; Pyrolysis method has reduced the viscosity of biofuel effectively and has improved cetane value, but apparatus expensive, reactant are difficult to control, help clean-burning oxygen after the pyrolysis in the vegetables oil and lose with the form of carbonic acid gas, the product property instability, Chinese pine seeds of trees utilization ratio is low.
Summary of the invention
In order to overcome above-mentioned production biofuel the deficiencies in the prior art, the invention provides the high method of a kind of cetane value with producing biological diesel oil with seed oil of Chinese pine, have the characteristics of save energy, protection environment, raising Chinese pine seeds of trees utilization ratio.
For achieving the above object, the preparation method that the present invention adopts is: a kind of method with producing biological diesel oil with seed oil of Chinese pine may further comprise the steps:
The first step is put into there-necked flask with oily pine nut oil, methyl alcohol and potassium hydroxide or sodium hydroxide catalyst three and is reacted, and temperature of reaction is controlled between 20 ℃～75 ℃, and the reaction times is 5～120 minutes; Wherein, methyl alcohol and greasy mol ratio are 3: 1～8: 1, and catalyzer is 0.5%～2.0% of a Chinese pine seed weight of oil.
Second step, after reaction finishes mixed system is distilled under normal pressure, 65～75 ℃, reclaim excessive methyl alcohol.
The 3rd step, reduce to room temperature, with mixed system standing demix 6～24 hours, the upper strata was the thick product of biofuel, lower floor is a raw glycerine; The thick product of biofuel is separated with raw glycerine; Add the methyl alcohol dilution that accounts for raw glycerine quality 20%～30% in raw glycerine, the adjusting pH value carries out the acid neutralization 4.0～7.0, centrifugal rotational speed is that 1800～2200rpm carries out centrifugation, and the time is 8 minutes～15 minutes and underpressure distillation, obtains byproduct glycerine; In the thick product of biofuel, add mass percent and be 10% dilute sulphuric acid regulating course system pH to 7.0, with 65～75 ℃ warm water it is washed again, clarify, obtain biofuel until lower floor's liquid.
The 4th step obtained adding in the biofuel anhydrous sodium sulfate drying agent that accounts for biofuel mass percent 3%～4% in the 3rd step and carries out drying treatment, finally prepared purified biofuel.
Because utilization of the present invention is the raw material of woody oleiferous plants plant seed grease as the preparation biofuel, the biofuel cetane value height of preparing, excellent property technology is simple, and expense is lower.In addition, the utilization ratio of Chinese pine seed own is low especially, except that being used as seeds grow seedlings, great majority are in the state that runs its course, so the present invention not only finds a kind of reproducible new oil sources for biofuel,, and can increase local forest zone farmers' income for oily pine nut oil provides new prospect; Characteristics with save energy, protection environment, raising Chinese pine seeds of trees utilization ratio.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail.
Embodiment one
A kind of method with producing biological diesel oil with seed oil of Chinese pine may further comprise the steps:
The first step is put into there-necked flask with 10g oil pine nut oil, methyl alcohol and potassium hydroxide catalyst three and is reacted, and temperature of reaction is controlled at 45 ℃, and the reaction times is 15 minutes; Wherein, methyl alcohol and greasy mol ratio are 5: 1, and potassium hydroxide catalyst is 0.7% of a Chinese pine seed weight of oil.
Second step, after reaction finishes mixed system is distilled under normal pressure, 70 ℃, reclaim excessive methyl alcohol.
The 3rd step, reduce to room temperature, with mixed system standing demix 6 hours, the upper strata was the thick product of biofuel, lower floor is a raw glycerine; The thick product of biofuel is separated with raw glycerine; Adding accounts for raw glycerine and weighs 20% methyl alcohol dilution in raw glycerine, and the adjusting pH value carries out the acid neutralization 4.0, centrifugal rotational speed is that 1800rpm carries out centrifugation, and the time is 8 minutes and underpressure distillation, obtains byproduct glycerine; Adding mass percent in the thick product of biofuel is 10% dilute sulphuric acid regulating course system pH to 7.0, with 65 ℃ warm water it is washed again, clarifies until lower floor's liquid, obtains biofuel.
The 4th step obtained in the biofuel adding accounting for biofuel and weigh 4% anhydrous sodium sulfate drying agent and carry out drying treatment in the 3rd step, finally prepare purified biofuel.
Under this technology, the productive rate of biofuel is 88.4%.
Embodiment two
A kind of method with producing biological diesel oil with seed oil of Chinese pine may further comprise the steps:
The first step is put into there-necked flask with 10g oil pine nut oil, methyl alcohol and potassium hydroxide catalyst three and is reacted, and temperature of reaction is controlled at 60 ℃, and the reaction times is 15 minutes; Wherein, methyl alcohol and greasy mol ratio are 7: 1, and potassium hydroxide catalyst is 1.1% of a Chinese pine seed weight of oil.
Second step, after reaction finishes mixed system is distilled under normal pressure, 67 ℃, reclaim excessive methyl alcohol.
The 3rd step, reduce to room temperature, with mixed system standing demix 16 hours, the upper strata was the thick product of biofuel, lower floor is a raw glycerine; The thick product of biofuel is separated with raw glycerine; Add the methyl alcohol dilution that accounts for raw glycerine quality 25% in raw glycerine, the adjusting pH value carries out the acid neutralization 5.0, centrifugal rotational speed is that 2000rpm carries out centrifugation, and the time is 10 minutes and underpressure distillation, obtains byproduct glycerine; In the thick product of biofuel, add mass percent and be 10% dilute sulphuric acid regulating course system pH to 7.0, with 70 ℃ warm water it is washed again, clarify, obtain biofuel until lower floor's liquid.
The 4th step obtained in the biofuel adding accounting for the 3.5% anhydrous sodium sulfate drying agent of biofuel mass percent and carry out drying treatment in the 3rd step, finally prepare purified biofuel.
Under this technology, the productive rate of biofuel is 93.9%.
Embodiment three
A kind of method with producing biological diesel oil with seed oil of Chinese pine may further comprise the steps:
The first step is put into there-necked flask with 10g oil pine nut oil, methyl alcohol and sodium hydroxide catalyst three and is reacted, and temperature of reaction is controlled at 75 ℃, and the reaction times is 120 minutes; Wherein, methyl alcohol and greasy mol ratio are 12: 1, and sodium hydroxide catalyst is 0.9% of a Chinese pine seed weight of oil.
Second step, after reaction finishes mixed system is distilled under normal pressure, 75 ℃, reclaim excessive methyl alcohol.
The 3rd step, reduce to room temperature, with mixed system standing demix 24 hours, the upper strata was the thick product of biofuel, lower floor is a raw glycerine; The thick product of biofuel is separated with raw glycerine; Add the methyl alcohol dilution that accounts for raw glycerine quality 30% in raw glycerine, the adjusting pH value carries out the acid neutralization 7.0, centrifugal rotational speed is that 2200rpm carries out centrifugation, and the time is 15 minutes and underpressure distillation, obtains byproduct glycerine; In the thick product of biofuel, add mass percent and be 10% dilute sulphuric acid regulating course system pH to 7.0, with 75 ℃ warm water it is washed again, clarify, obtain biofuel until lower floor's liquid.
The 4th step obtained in the biofuel adding accounting for the 3% anhydrous sodium sulfate drying agent of biofuel mass percent and carry out drying treatment in the 3rd step, finally prepare purified biofuel.
Under this technology, the productive rate of biofuel is 92.35%.
Claims (4)
1, a kind of method with producing biological diesel oil with seed oil of Chinese pine is characterized in that, may further comprise the steps:
The first step is put into there-necked flask with oily pine nut oil, methyl alcohol and potassium hydroxide or sodium hydroxide catalyst three and is reacted, and temperature of reaction is controlled between 20 ℃～75 ℃, and the reaction times is 5～120 minutes; Wherein, methyl alcohol and greasy mol ratio are 3: 1～8: 1, and catalyzer is 0.5%～2.0% of a Chinese pine seed weight of oil.
Second step, after reaction finishes mixed system is distilled under normal pressure, 65～75 ℃, reclaim excessive methyl alcohol.
The 3rd step, reduce to room temperature, with mixed system standing demix 6～24 hours, the upper strata was the thick product of biofuel, lower floor is a raw glycerine; The thick product of biofuel is separated with raw glycerine; Add the methyl alcohol dilution that accounts for raw glycerine quality 20%～30% at raw glycerine, the adjusting pH value carries out the acid neutralization 4.0～7.0, centrifugal rotational speed is that 1800～2200rpm carries out centrifugation, and the time is 8 minutes～15 minutes and underpressure distillation, obtains byproduct glycerine; In the thick product of biofuel, add mass percent and be 10% dilute sulphuric acid regulating course system pH to 7.0, with 65～75 ℃ warm water it is washed again, clarify, obtain biofuel until lower floor's liquid.
The 4th step obtained adding in the biofuel anhydrous sodium sulfate drying agent that accounts for biofuel mass percent 3%～4% in the 3rd step and carries out drying treatment, finally prepared purified biofuel.
2, a kind of method with producing biological diesel oil with seed oil of Chinese pine according to claim 1 is characterized in that, may further comprise the steps:
The first step is put into there-necked flask with 10g oil pine nut oil, methyl alcohol and potassium hydroxide catalyst three and is reacted, and temperature of reaction is controlled at 45 ℃, and the reaction times is 15 minutes; Wherein, methyl alcohol and greasy mol ratio are 5: 1, and potassium hydroxide catalyst is 0.7% of a Chinese pine seed weight of oil.
Second step, after reaction finishes mixed system is distilled under normal pressure, 70 ℃, reclaim excessive methyl alcohol.
The 3rd step, reduce to room temperature, with mixed system standing demix 6 hours, the upper strata was the thick product of biofuel, lower floor is a raw glycerine; The thick product of biofuel is separated with raw glycerine; Adding accounts for raw glycerine and weighs 20% methyl alcohol dilution in raw glycerine, and the adjusting pH value carries out the acid neutralization 4.0, centrifugal rotational speed is that 1800 rpm carry out centrifugation, and the time is 8 minutes and underpressure distillation, obtains byproduct glycerine; Adding mass percent in the thick product of biofuel is 10% dilute sulphuric acid regulating course system pH to 7.0, with 65 ℃ warm water it is washed again, clarifies until lower floor's liquid, obtains biofuel.
The 4th step obtained in the biofuel adding accounting for biofuel and weigh 4% anhydrous sodium sulfate drying agent and carry out drying treatment in the 3rd step, finally prepare purified biofuel.
3, a kind of method with producing biological diesel oil with seed oil of Chinese pine according to claim 1 is characterized in that, may further comprise the steps:
The first step is put into there-necked flask with 10g oil pine nut oil, methyl alcohol and potassium hydroxide catalyst three and is reacted, and temperature of reaction is controlled at 60 ℃, and the reaction times is 15 minutes; Wherein, methyl alcohol and greasy mol ratio are 7: 1, and potassium hydroxide catalyst is 1.1% of a Chinese pine seed weight of oil.
Second step, after reaction finishes mixed system is distilled under normal pressure, 67 ℃, reclaim excessive methyl alcohol.
The 3rd step, reduce to room temperature, with mixed system standing demix 16 hours, the upper strata was the thick product of biofuel, lower floor is a raw glycerine; The thick product of biofuel is separated with raw glycerine; Add the methyl alcohol dilution that accounts for raw glycerine quality 25% in raw glycerine, the adjusting pH value carries out the acid neutralization 5.0, centrifugal rotational speed is that 2000rpm carries out centrifugation, and the time is 10 minutes and underpressure distillation, obtains byproduct glycerine; In the thick product of biofuel, add mass percent and be 10% dilute sulphuric acid regulating course system pH to 7.0, with 70 ℃ warm water it is washed again, clarify, obtain biofuel until lower floor's liquid.
The 4th step obtained in the biofuel adding accounting for the 3.5% anhydrous sodium sulfate drying agent of biofuel mass percent and carry out drying treatment in the 3rd step, finally prepare purified biofuel.
4, a kind of method with producing biological diesel oil with seed oil of Chinese pine according to claim 1 is characterized in that, may further comprise the steps:
The first step is put into there-necked flask with 10g oil pine nut oil, methyl alcohol and sodium hydroxide catalyst three and is reacted, and temperature of reaction is controlled at 75 ℃, and the reaction times is 120 minutes; Wherein, methyl alcohol and greasy mol ratio are 12: 1, and sodium hydroxide catalyst is 0.9% of a Chinese pine seed weight of oil.
Second step, after reaction finishes mixed system is distilled under normal pressure, 75 ℃, reclaim excessive methyl alcohol.
The 3rd step, reduce to room temperature, with mixed system standing demix 24 hours, the upper strata was the thick product of biofuel, lower floor is a raw glycerine; The thick product of biofuel is separated with raw glycerine; Add the methyl alcohol dilution that accounts for raw glycerine quality 30% in raw glycerine, the adjusting pH value carries out the acid neutralization 7.0, centrifugal rotational speed is that 2200rpm carries out centrifugation, and the time is 15 minutes and underpressure distillation, obtains byproduct glycerine; In the thick product of biofuel, add mass percent and be 10% dilute sulphuric acid regulating course system pH to 7.0, with 75 ℃ warm water it is washed again, clarify, obtain biofuel until lower floor's liquid.
The 4th step obtained in the biofuel adding accounting for the 3% anhydrous sodium sulfate drying agent of biofuel mass percent and carry out drying treatment in the 3rd step, finally prepare purified biofuel.
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| CN2008102323083A CN101402876B (en) | 2008-11-18 | 2008-11-18 | Method for producing biological diesel oil with seed oil of Chinese pine |
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| CN2008102323083A CN101402876B (en) | 2008-11-18 | 2008-11-18 | Method for producing biological diesel oil with seed oil of Chinese pine |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831358A (en) * | 2010-05-27 | 2010-09-15 | 江春德 | Method for producing biodiesel by using waste oil and fat |
| CN101717694B (en) * | 2009-10-20 | 2012-04-18 | 安徽工业大学 | Method for separating decanted product oil out from oil foot of pressed teal oil |
| CN105268456A (en) * | 2015-11-10 | 2016-01-27 | 陕西科技大学 | Solid acid catalyst, preparing method of solid acid catalyst and acid reducing method based on catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100590177C (en) * | 2006-12-20 | 2010-02-17 | 西北农林科技大学 | Process of preparing biodiesel oil with pricklyash seed oil in high acid value |
| CN101289630A (en) * | 2008-06-06 | 2008-10-22 | 西北农林科技大学 | Process for preparing biodiesel from chinaberry seed oil |
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- 2008-11-18 CN CN2008102323083A patent/CN101402876B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717694B (en) * | 2009-10-20 | 2012-04-18 | 安徽工业大学 | Method for separating decanted product oil out from oil foot of pressed teal oil |
| CN101831358A (en) * | 2010-05-27 | 2010-09-15 | 江春德 | Method for producing biodiesel by using waste oil and fat |
| CN105268456A (en) * | 2015-11-10 | 2016-01-27 | 陕西科技大学 | Solid acid catalyst, preparing method of solid acid catalyst and acid reducing method based on catalyst |
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| CN101402876B (en) | 2012-06-27 |
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