CN100400621C - Novel chinaberry biologic diesel oil and method for preparing the same - Google Patents
Novel chinaberry biologic diesel oil and method for preparing the same Download PDFInfo
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- CN100400621C CN100400621C CNB2006100413940A CN200610041394A CN100400621C CN 100400621 C CN100400621 C CN 100400621C CN B2006100413940 A CNB2006100413940 A CN B2006100413940A CN 200610041394 A CN200610041394 A CN 200610041394A CN 100400621 C CN100400621 C CN 100400621C
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- chinaberry
- diesel oil
- highly effective
- organic solvent
- grease
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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 new-typed chinaberry biological diesel and preparing method, which comprises the following steps: 1) removing impurity in the chinaberry fat; stirring to emulsify; 2) adding carbinol and chinaberry fat in the sealed container according to 1: 2-1:8; placing high-effective biological enzyme and relative hydrophilic organic solvent to react for 4-26 h on the organic solvent-water boundary; 3) separating; filtering; stewing to obtain rough glycerin; distilling upper liquid; recycling the organic solvent to obtain the product.
Description
Technical field
The present invention relates to a kind of novel chinaberry biologic diesel oil and preparation method thereof.
Background technology
At present, the energy more than 80% and organic raw material come from fossil energy in the world.Along with the exhaustion of fossil energy, the mankind will face serious energy dilemma.Energy dilemma also just becomes the huge challenge that the middle of this century is about to face.According to statistics, if by the present explored energy in the horizon mining world, coal resources still can be exploited 100 years, oil 30~40 years, Sweet natural gas 50~60 years.
Diesel oil occupies critical role as a kind of important power fuel in the fuel structure of countries in the world.Along with development of global economy, comprise that the energy-output ratio of diesel oil increases day by day.Because the traditional energy reserves are limited, the global energy shortage problem is serious day by day.Simultaneously, the problem of environmental pollution that uses traditional petroleum diesel to cause is also outstanding day by day, many ecological problems such as the Greenhouse effect of Yin Faing, the reduction of living species diversity have thus had a strong impact on the energy security and the sustainable development of social economy of various countries, are threatening environment for human survival.For satisfying the demand of social development to the energy, realize the continuous utilization of resource, various cleanings, reproducible petroleum diesel substitute energy are all being tried to explore to develop from the angle of environment protection and resource strategy in countries in the world.Under such background, biodiesel technology is arisen at the historic moment, and environment friendly and recyclability that it is outstanding have caused world developed country, especially the great attention of natural resources shortage country.
Compare with petroleum diesel, biofuel is nontoxic, biodegradable, and is few to the pollution of soil and water, belongs to environmentally friendly green fuel; Substantially not sulfur-bearing and aromatic hydrocarbon etc. can effectively reduce CO in the motor-vehicle tail-gas, CO after the burning
2, SO
x, hydrocarbon polymer and total particle material discharging, can satisfy European II number and the III emission standard; Cetane value and oxygen level height help the trouble-free burning in diesel motor, and the combustionproperty and the capability of antidetonance are good; Have engine cold-starting performance preferably, condensation point can reach-20 ℃ when additive-free; Have good lubricating property, can reduce the wear rate of oil injection pump, engine cylinder and connecting rod, prolong its work-ing life; The flash-point height has good safety performance.More of paramount importancely be, biofuel has recyclability, and resource can be exhausted, and raw material sources is extensive, and diesel motor need not made any change or renewal part when using as the oil as substitute of diesel product.
Because at present biofuel mostly adopts chemical method synthetic, its complicated process of preparation, alcohol must use in a large number, and subsequent technique must have corresponding pure retrieving arrangement, and energy consumption height, color and luster are dark.Because unsaturated fatty acids is at high temperature apt to deteriorate in the fat; Esterification products is difficult to reclaim the cost height; And production process has waste lye discharging, and raw material supply instability, raw materials cost are too high.Therefore, though technological development of many national biofuel in recent years and commercial operations have all obtained significant progress.But, restricted the large-scale production of biofuel owing to many reasons such as production technology, raw material supply, raw materials cost.
Summary of the invention
What the present invention will solve is exactly the problem that above-mentioned biological oily raw material of system and prior art exist, and a kind of novel chinaberry biologic diesel oil and preparation method thereof is provided.
Chinaberry is the evergreen or deciduous tree of Meliaceae Melia, is that a kind of speed is given birth to multi-functional economic tree, and it is very wide to distribute in China, and principal item has seal chinaberry, China tree, melia toosendan, Melia dubia Cav. etc.The nimbin of separation and Extraction, Toosendanin, Kuliansu are the wide spectrum of generally acknowledging in the world at present, efficient, low toxicity, the easy sterilant of degraded, noresidue from the chinaberry fruit, nearly all plant insect is all had repelling and killing efficacy, is the core material of producing plant toosedarin (chinaberry element) soft pesticide.Simultaneously, the chinaberry fruit contains abundant Vegetable oil lipoprotein (about 45%).Discover through the applicant, chinaberry vegetables oil molecule generally is made up of 14-18 carbochain, and diesel oil molecules is made up of about 15 carbochain, because carbon number is close in chinaberry vegetables oil molecule and the diesel oil molecules, so the grease that directly squeezes of chinaberry fruit and extract the cheap raw material that the remaining chinaberry fruit fatty wastes in plant toosedarin (chinaberry element) back can become refinement, production chinaberry biologic diesel oil.
The present invention produces refinement, the production technology that principle, technology apply to chinaberry biologic diesel oil with the biology of bioenergy hydrogen (H2), utilizes the grease that the chinaberry fruit directly squeezes and extracts the remaining fatty wastes in plant toosedarin (chinaberry element) back and produce novel chinaberry biologic diesel oil.According to chemical composition analyze, chinaberry biologic diesel oil fuel nucleus is a high palmitic acid methane, and it is to decompose by the glyceride that is main component with unsaturated oleic acid C18 to obtain.
Concrete technical scheme of the present invention is as follows:
1) stock oil pre-treatment: the chinaberry grease is removed by filter impurity, then stirring and emulsifying;
2) pre-reaction, transesterify: the chinaberry grease of handling with methyl alcohol with through step 1) joins in the encloses container by 1: 2~1: 8 mol ratio, and add highly effective biological zyme and hydrophilic relatively organic solvent, with the highly effective biological zyme catalyzer catalyzed transesterification 4~26 hours on organic solvent-water termination;
3) separate, filter: after reaction finishes, highly effective biological zyme separated from reaction product again reaction product is carried out centrifugal layering, leave standstill the raw glycerine that lower floor is separated in the back, organic solvent is reclaimed in liquid distillation in upper strata, promptly obtains finished product.
Above-mentioned steps 1) the chinaberry grease described in comprises with the chinaberry fruit and directly squeezes grease and extract the remaining chinaberry fruit fatty wastes in plant toosedarin (chinaberry element) back, and they can use separately also can arbitrary proportion to mix and use; When the chinaberry grease emulsifying during to the homogeneous phase oily liquids emulsification finish.
Above-mentioned steps 2) in, highly effective biological zyme is made up of nitrogenase, hydrogenase or lipase, and they mix use with 1: 1: 3 mass ratio, and itself and the greasy mass ratio of chinaberry are 1: 800~1: 1600.Aforementioned nitrogenase, hydrogenase come from cyanobacteria, green alga, and lipase comes from South Pole candiyeast, the female thread fungus of garden alcohol.
Described hydrophilic relatively organic solvent is selected from ethanol, butanols, acetone or methyl alcohol, and itself and the greasy mass ratio of chinaberry are 1: 0.8~1: 2.4.The purpose that adds organic solvent is to reduce the solubleness of solute, and its precipitation is separated out.
Above-mentioned steps 3) adopt whizzer that highly effective biological zyme is separated from reactant in.
The present invention has following advantage:
1) whole process of preparation is under normal temperature, condition of normal pressure, and highly effective biological zyme can follow bad the use in process of production;
2) production unit that is adopted is approximate with the oily equipment of general system, need not specific equipment;
3) production process does not have " three wastes " discharging, is process for cleanly preparing;
4) Vegetable oil lipoprotein is abundant especially in the raw material, and cost is low;
5) low to the raw materials quality requirement, available crude oil (not needing to make with extra care), various oil can singly be used, and also can use with;
6) yield can reach more than 95%;
7) energy-efficient, less investment.
8) can make byproduct glycerine simultaneously.
Embodiment
The employing of embodiment 1 stock oil is directly squeezed grease with the chinaberry fruit and is prepared chinaberry biologic diesel oil:
1, the pre-treatment of stock oil: the chinaberry grease is removed by filter impurity, carry out stirring and emulsifying then to the homogeneous phase oily liquids.
2, batching: with mol ratio is that 1: 4~1: 6 methyl alcohol and chinaberry grease joins in the encloses container, and adds highly effective biological zyme and hydrophilic relatively organic solvent ethanol, and wherein: the mass ratio of highly effective biological zyme and stock oil is 1: 1200~1400; The mass ratio of organic solvent and stock oil is 1: 1.2~1: 1.4.
3, pre-reaction, transesterify: under 25~55 ℃ temperature condition, be catalyzer, in encloses container, utilize highly effective biological zyme catalyzed transesterification on the organic solvent oil-water interface, hybrid reaction 10~16 hours with the highly effective biological zyme; Separate, filter: after reaction finishes, highly effective biological zyme is separated from reaction product, again reaction product is carried out centrifugal layering, isolate the raw glycerine of lower floor after leaving standstill, upper strata liquid distillation, reclaim organic solvent, obtain the finished product chinaberry biologic diesel oil simultaneously, the chinaberry biologic diesel oil yield reaches more than 95%.
Remaining chinaberry fruit fatty wastes prepared chinaberry biologic diesel oil after embodiment 2 adopted and extracts plant toosedarin (chinaberry rope):
1, the pre-treatment of stock oil: chinaberry fruit fatty wastes is removed by filter impurity, carry out stirring and emulsifying then to the homogeneous phase oily liquids.
2, batching: with mol ratio is that 1: 2~1: 4 methyl alcohol and chinaberry grease joins in the container, and adds highly effective biological zyme and hydrophilic relatively organic solvent methyl alcohol, and wherein: the mass ratio of highly effective biological zyme and stock oil is 1: 800~1000; The mass ratio of organic solvent and stock oil is 1: 0.8~1: 1.2.
3, pre-reaction, transesterify: under 25~55 ℃ temperature condition, be catalyzer, in encloses container, utilize highly effective biological zyme catalyzed transesterification on the organic solvent oil-water interface, hybrid reaction 16~24 hours with the highly effective biological zyme; Separate, filter: reaction is separated highly effective biological zyme after finishing from reaction product, again reaction product is carried out centrifugal layering, isolates the raw glycerine of lower floor after leaving standstill, and organic solvent is reclaimed in liquid distillation in upper strata, obtains the finished product chinaberry biologic diesel oil simultaneously.The chinaberry biologic diesel oil yield reaches more than 85%.
Embodiment 3 employings are directly squeezed grease with the chinaberry fruit and are extracted the remaining chinaberry fruit fatty wastes mixture in plant toosedarin (chinaberry element) back and prepare chinaberry biologic diesel oil:
1, the pre-treatment of stock oil: the chinaberry fruit directly squeezed grease and extract the remaining chinaberry fruit fatty wastes mixture in plant toosedarin (chinaberry element) back by mass ratio mixing in 1: 1 and remove by filter impurity, carry out stirring and emulsifying then to the homogeneous phase oily liquids.
2, batching: with mol ratio is that 1: 3~1: 5 methyl alcohol and chinaberry grease joins in the container, and adds highly effective biological zyme and hydrophilic relatively organic solvent butanols, and wherein: the mass ratio of highly effective biological zyme and stock oil is 1: 1000~1200; The mass ratio of organic solvent and stock oil is 1: 1.0~1: 1.4.
3, pre-reaction, transesterify: under 25~55 ℃ temperature condition, be catalyzer, in encloses container, utilize highly effective biological zyme catalyzed transesterification on the organic solvent oil-water interface, hybrid reaction 12~18 hours with the highly effective biological zyme; Separate, filter: reaction is separated highly effective biological zyme after finishing from reaction product, again reaction product is carried out centrifugal layering, isolates the raw glycerine of lower floor after leaving standstill, and organic solvent is reclaimed in liquid distillation in upper strata, obtains the finished product chinaberry biologic diesel oil simultaneously.The chinaberry biologic diesel oil yield reaches more than 90%.
Claims (10)
1. novel chinaberry biologic diesel oil is characterized in that it is prepared from by the following step:
1) stock oil pre-treatment: the chinaberry grease is removed by filter impurity, then stirring and emulsifying;
2) pre-reaction, transesterify: the chinaberry grease of handling with methyl alcohol with through step 1) joins in the encloses container by 1: 2~1: 8 mol ratio, and add highly effective biological zyme and hydrophilic relatively organic solvent, with the highly effective biological zyme catalyzer catalyzed transesterification 4~26 hours on organic solvent-water termination; Aforementioned highly effective biological zyme is mixed by 1: 1: 3 mass ratio by nitrogenase, hydrogenase and lipase;
3) separate, filter: after reaction finishes, highly effective biological zyme separated from reaction product again reaction product is carried out centrifugal layering, leave standstill the raw glycerine that lower floor is separated in the back, organic solvent is reclaimed in liquid distillation in upper strata, promptly obtains finished product.
2. novel chinaberry biologic diesel oil according to claim 1, it is characterized in that the chinaberry grease described in the step 1) comprise directly squeeze grease and extract the plant toosedarin with the chinaberry fruit after remaining chinaberry fruit fatty wastes, they use separately or mix with arbitrary proportion and use.
3. novel chinaberry biologic diesel oil according to claim 1, the chinaberry grease emulsifying that it is characterized in that step 1) during to the homogeneous phase oily liquids emulsification finish.
4. novel chinaberry biologic diesel oil according to claim 1 is characterized in that step 2) described in highly effective biological zyme and the greasy mass ratio of chinaberry be 1: 800~1: 1600.
5. novel chinaberry biologic diesel oil according to claim 1 is characterized in that the described hydrophilic relatively organic solvent of step 1) is selected from ethanol, butanols, acetone or methyl alcohol, and itself and the greasy mass ratio of chinaberry are 1: 0.8~1: 2.4.
6. the preparation method of the described novel chinaberry biologic diesel oil of claim 1 is characterized in that comprising the steps:
1) stock oil pre-treatment: the chinaberry grease is removed by filter impurity, then stirring and emulsifying;
2) pre-reaction, transesterify: the chinaberry grease of handling with methyl alcohol with through step 1) joins in the encloses container by 1: 2~1: 8 mol ratio, and add highly effective biological zyme and hydrophilic relatively organic solvent, with the highly effective biological zyme catalyzer catalyzed transesterification 4~26 hours on organic solvent-water termination; Aforementioned highly effective biological zyme is mixed by 1: 1: 3 mass ratio by nitrogenase, hydrogenase and lipase;
3) separate, filter: after reaction finishes, highly effective biological zyme separated from reaction product again reaction product is carried out centrifugal layering, leave standstill the raw glycerine that lower floor is separated in the back, organic solvent is reclaimed in liquid distillation in upper strata, promptly obtains finished product.
7. as the preparation method of novel chinaberry biologic diesel oil as described in the claim 6, it is characterized in that the chinaberry grease described in the step 1) comprise directly squeeze grease and extract the plant toosedarin with the chinaberry fruit after remaining chinaberry fruit fatty wastes, they use separately or mix with arbitrary proportion and use.
8. the preparation method of chinaberry biologic diesel oil as claimed in claim 6, the chinaberry grease emulsifying that it is characterized in that step 1) during to the homogeneous phase oily liquids emulsification finish.
9. the preparation method of chinaberry biologic diesel oil as claimed in claim 6 is characterized in that step 2) described in highly effective biological zyme and the greasy mass ratio of chinaberry be 1: 800~1: 1600.
10. the preparation method of chinaberry biologic diesel oil as claimed in claim 6 is characterized in that the described hydrophilic relatively organic solvent of step 1) is selected from ethanol, butanols, acetone or methyl alcohol, and itself and the greasy mass ratio of chinaberry are 1: 0.8~1: 2.4.
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CNB2006100413940A CN100400621C (en) | 2006-08-22 | 2006-08-22 | Novel chinaberry biologic diesel oil and method for preparing the same |
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CNB2006100413940A CN100400621C (en) | 2006-08-22 | 2006-08-22 | Novel chinaberry biologic diesel oil and method for preparing the same |
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CN100400621C true CN100400621C (en) | 2008-07-09 |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6156946A (en) * | 1996-04-12 | 2000-12-05 | Exxon Research And Engineering Company | Biological activation of aromatics for chemical processing and/or upgrading of aromatic compounds, petroleum, coal, resid, bitumen and other petrochemical streams |
CN1640991A (en) * | 2004-12-06 | 2005-07-20 | 华中科技大学 | Method for producing biological diesel using lipase |
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- 2006-08-22 CN CNB2006100413940A patent/CN100400621C/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6156946A (en) * | 1996-04-12 | 2000-12-05 | Exxon Research And Engineering Company | Biological activation of aromatics for chemical processing and/or upgrading of aromatic compounds, petroleum, coal, resid, bitumen and other petrochemical streams |
CN1640991A (en) * | 2004-12-06 | 2005-07-20 | 华中科技大学 | Method for producing biological diesel using lipase |
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