CN1916113A - Method for producing biological diesel oil in use for internal-combustion engine by using centrifugal type technique of molecular distillation - Google Patents
Method for producing biological diesel oil in use for internal-combustion engine by using centrifugal type technique of molecular distillation Download PDFInfo
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- CN1916113A CN1916113A CNA2006100368644A CN200610036864A CN1916113A CN 1916113 A CN1916113 A CN 1916113A CN A2006100368644 A CNA2006100368644 A CN A2006100368644A CN 200610036864 A CN200610036864 A CN 200610036864A CN 1916113 A CN1916113 A CN 1916113A
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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
This invention discloses a centrifuge molecular distillation method for producing biodiesel oil for internal combustion engines. The method comprises: (1) esterifying plant oil or animal oil or their mixture; (2) performing coarse-separation on the esterification products to obtain crude methyl ester or crude ethyl ester; (3) degassing and separating methanol or ethanol at 50-150 deg.C, 100-5000 Pa and 300-1000 rpm, and then separating methyl ester or ethyl ester at 100-250 deg.C, 1-50 Pa and 600-1400 rpm. The obtained biodiesel oil has purity higher than 98%, and can be used in internal combustion engines. The method has such advantages as simple process, no wastewater pollution and saved water treatment cost.
Description
Technical field
The refining purification that the present invention relates to biochemical industry separation field, particularly a kind of biofuel with separate.
Background technology
Along with the overexploitation of petroleum resources, oil engine has huge commercial promise with the development of biofuel.At present, the domestic technology of taking usually with the technology of biofuel (methyl esters) at the production oil engine is:
Esterification obtains intermediate product → static layering → get upper strata liquid → washing → drying tower → product (biofuel).
Use this production technique and mainly have following problem: 1. adopt washing process, be difficult to impurity is thoroughly removed, the content of product fatty acid methyl ester etc. is relatively low, generally do not reach 95%, thereby the fatty acid methyl ester that does not reach standard biological diesel oil such as Europe discharging III is greater than 98% requirement, therefore make biofuel be difficult to apply, can not in high-grade automobile, use, require lower industry relatively and can only be applied in Industrial Boiler, farm machinery etc.; 2. produce a large amount of waste water in washing is handled, both environment was caused severe contamination, waste water resource does not meet environmental requirement now again; 3. adopt washing back product needed to carry out drying, increase equipment cost and processing cost by drying tower; 4. washing process removes and takes away most impurity (methyl alcohol, glycerine etc.), also takes away the methyl esters of part simultaneously, makes output capacity reduce.
The foreign biomolecule diesel production except that reaction (esterification) process, all needs the rapid separation and purification of multistep can finish the requirement of using purity.
Summary of the invention
Problem for the existence that overcomes above-mentioned prior art, of the present inventionly provide a kind of centrifugal type technique of molecular distillation that utilizes to produce the oil engine method of bio-diesel oil, it can be produced purity and reach more than 98%, the oil engine biofuel that meets Europe discharging III standard, omit washing process simultaneously, solved industrial wastewater problem.
The object of the invention is achieved through the following technical solutions:
A kind of centrifugal type technique of molecular distillation that utilizes is produced the oil engine method of bio-diesel oil, may further comprise the steps: be raw material with one of vegetables oil or animal oil or mixture 1., carry out esterification; 2. esterification reaction product is carried out roughing out and get thick methyl esters or thick ethyl ester; 3. thick methyl esters or thick ethyl ester are carried out the centrifugal molecular distillating processing, make the biofuel product; The centrifugal molecular distillating of described thick methyl esters or thick ethyl ester is handled and comprised two-stage at least: the prime treatment temp is 50-150 ℃, and vacuum tightness is 5000-100Pa, and rotary speed is 300～1000rpm, outgases and isolates methyl alcohol or ethanol; Back level treatment temp is 100-250 ℃, and vacuum tightness is 50-1Pa, and rotary speed is 600～1400rpm, isolates methyl esters or ethyl ester.
Described step 3. in, the prime of thick methyl esters or thick ethyl ester is handled and comprised: the degassing is handled, and treatment temp is 50-100 ℃, and vacuum tightness is 5000-1000Pa; Separation of methanol or alcoholic acid are handled, and controlled temperature is 50-120 ℃, and vacuum tightness is 1000-100Pa, and rotary speed is 500～1000rpm.
Described step 2. in, roughing out is static layering or separates with high speed centrifugation.
Described step 1. in, vegetables oil or animal oil raw material and methyl alcohol or ethanol carry out esterification, its reaction product mainly comprises methyl esters or ethyl ester, glycerine, methyl alcohol or ethanol and impurity.
Roughing out of the present invention is meant that simple layering or supercentrifuge separate.Thick methyl esters is meant that the purity that obtains by roughing out is lower than 95% methyl esters.Thick ethyl ester is meant that the purity that obtains by roughing out is lower than 95% ethyl ester.
With respect to prior art, the present invention has following advantage:
(1) the present invention has adopted centrifugal type technique of molecular distillation, compares with the falling film type molecular distillation with the scraped film type molecular distillation, and centrifugal molecular distillating is owing to the rotating disk high speed rotating, and the liquid film and the liquid film that can obtain as thin as a wafer are more evenly distributed, and vaporator rate and separation efficiency are better; The heated time of material on generating surface is shorter, has reduced the danger of heat-sensitive materials pyrolysated; The treatment capacity of material is bigger, is more suitable for industrial continuous production.
(2) the present invention carries out roughing out to esterification reaction product and gets thick methyl esters or thick ethyl ester; Can reduce the first-stage centrifugal fractionation by distillation, simplify flow process, reduce equipment cost and running cost, and, can improve centrifugal molecular distillating efficient significantly by isolating bigger thick methyl esters of treatment capacity or thick ethyl ester.
(3) the present invention realizes and finishes purification and the process for refining of oil engine with biofuel (methyl esters or ethyl ester), and the biofuel purity of purification can reach more than 98%, thereby produces the biofuel up to standard that meets international standard.
(4) method of the present invention has been omitted the washing and the drying process of traditional method, and technical process is simple, does not have contaminated wastewater, saves the water treatment expense.
Description of drawings
Fig. 1 is a process flow diagram of the present invention;
Fig. 2 is a production synoptic diagram of the present invention.
Embodiment
As shown in Figure 1, the present invention is that a kind of centrifugal type technique of molecular distillation that utilizes is produced the oil engine method of bio-diesel oil, and the main technique step is: raw material → reaction back intermediate product → roughing out → centrifugal molecular distillating → finished product (oil engine biofuel) and byproduct (glycerine).
At first, be to be the feedstock production coarse biodiesel with one of vegetables oil or animal oil or mixture.Vegetables oil can adopt Oleum Cocois, plam oil, rapeseed oil, Jatropha curcas oil (numb maple), soybean oil or peanut oil or the like, and animal oil can adopt lard, butter, fowl poultry oil or fish oil etc., does not enumerate one by one at this.
The preparation biofuel mainly comprises following four kinds of methods at present: enzymolysis, pyrolysis, supercritical esterification and transesterify and esterification.Transesterify and esterification are the main method of producing fatty acid methyl ester at present.Transesterify is to utilize methyl alcohol or ethanol, and the glyceryl in the triglyceride is replaced to get off, and forms the longer chain fatty acid methyl esters, increases mobile and reduction viscosity, makes it to be suitable as fuel and uses.This reaction can be very low in temperature, carry out under the normal pressure, and the reaction conditions gentleness is easy to control, can add catalyzer simultaneously and shorten reaction time, improves productive rate.Vegetables oil or animal oil and methyl alcohol (or ethanol) are carried out esterification (or transesterification reaction), and its reaction back intermediate product contains methyl esters (or ethyl ester), glycerine (glycerol), excessive methyl alcohol (or ethanol) and a small amount of impurity.Its reaction equation is as follows:
After carrying out above-mentioned esterification, esterification reaction product is carried out roughing out by static layering or with high speed centrifugation, then thick methyl esters being carried out centrifugal molecular distillating handles, the fractionation by distillation temperature is at 50 ℃-250 ℃, fractionation by distillation vacuum tightness is at 5000Pa---and 1Pa, distilling kettle base solution at last is nonesterified dimension E, plant sterol, lipid, impurity etc.
Owing to carried out roughing out, contain in a small amount methyl alcohol (or ethanol) of a large amount of methyl esters, glycerine (glycerol) etc. in the therefore thick methyl esters (or thick ethyl ester).Molecular distillation is handled and comprised two-stage: the prime treatment temp is 50-100 ℃, and vacuum tightness is 5000-1000Pa, and (temperature is 50-100 ℃ to be divided into the degassing, vacuum tightness is 5000-1000Pa), separation of methanol or ethanol (temperature is 50-120 ℃, and vacuum tightness is 5000-100Pa, rotating speed 300-1400rpm); Back level treatment temp is 100-250 ℃, and vacuum tightness is 50-1Pa, isolates methyl esters or ethyl ester.
Embodiment 1
Adopt Oleum Cocois and methyl alcohol to carry out esterification, the mol ratio of Oleum Cocois and methyl alcohol is 1: 6.Esterification reaction product is got upper strata liquid (thick methyl esters) 900ml and is entered surge tank 1 by static layering, and as shown in Figure 2, entering stripper column 2 degassing treatment temps then is 60 ℃, and vacuum tightness is 5000Pa; Degassing after product enters first step centrifugal molecular distillating post 3 and separates the remaining methyl alcohol of esterification, and temperature is 80 ℃, and vacuum tightness is 1000Pa, rotary speed 600rpm; Enter second stage centrifugal molecular distillator 4 at last 825 gram methyl esters are separated, temperature is 180 ℃, and vacuum tightness is 50Pa, and rotary speed 1000rpm residual impurity is discharged.After testing, prepared methyl esters purity is 99%.
Adopt butter and ethanol to carry out esterification, butter and alcoholic acid mol ratio are 1: 6.5.Esterification reaction product is got upper strata liquid (thick ethyl ester) 750ml and is entered surge tank 1 by static layering, and as shown in Figure 2, entering stripper column 2 degassing treatment temps then is 100 ℃, and vacuum tightness is 1000Pa; Degassing after product enters first step centrifugal molecular distillating post 3 and separates the remaining ethanol of esterification, and temperature is 150 ℃, and vacuum tightness is 100Pa, rotary speed 300rpm; Enter second stage centrifugal molecular distillator 4 at last ethyl ester 635 grams are separated, temperature is 280 ℃, and vacuum tightness is 1Pa, and rotary speed 1400rpm residual impurity is discharged.After testing, prepared ethyl ester purity is 98.6%.
Adopt rapeseed oil and methyl alcohol to carry out esterification, the mol ratio of rapeseed oil and methyl alcohol is 1: 7.Esterification reaction product carries out roughing out by high speed centrifugation, gets thick methyl esters 700ml and enters surge tank 1, and as shown in Figure 2, entering stripper column 2 degassing treatment temps then is 80 ℃, and vacuum tightness is 3000Pa; Degassing after product enters first step molecular distillation post 3 and separates the remaining methyl alcohol of esterification, and temperature is 110 ℃, and vacuum tightness is 500Pa, rotary speed 1000rpm; Enter second stage centrifugal molecular distillator 4 at last methyl esters 638 grams are separated, temperature is 230 ℃, and vacuum tightness is 25Pa, and rotary speed 1200rpm residual impurity is discharged.After testing, prepared methyl esters purity is 98.3%.
Embodiment 4
Adopt fish oil and methyl alcohol to carry out esterification, the mol ratio of fish oil and methyl alcohol is 1: 7.5.Esterification reaction product carries out roughing out by high speed centrifugation, gets thick methyl esters 800ml and enters surge tank, enters first step molecular distillation post then, outgases and separation of methanol, and temperature is 50 ℃, and vacuum tightness is 1000Pa, rotary speed 800rpm; Enter second stage centrifugal molecular distillator at last methyl esters 762 grams are separated, temperature is 250 ℃, and vacuum tightness is 10Pa, and rotary speed 1100rpm residual impurity is discharged.After testing, prepared methyl esters purity is 99%.
Claims (7)
1. one kind is utilized centrifugal type technique of molecular distillation to produce the oil engine method of bio-diesel oil, it is characterized in that may further comprise the steps: be raw material with one of vegetables oil or animal oil or mixture 1., carry out esterification; 2. esterification reaction product is carried out roughing out and get thick methyl esters or thick ethyl ester; 3. thick methyl esters or thick ethyl ester are carried out the centrifugal molecular distillating processing, make the biofuel product; The centrifugal molecular distillating of described thick methyl esters or thick ethyl ester is handled and comprised two-stage at least: the prime treatment temp is 50-150 ℃, and vacuum tightness is 5000-100Pa, and rotary speed is 300～1000rpm, outgases and isolates methyl alcohol or ethanol; Back level treatment temp is 100-250 ℃, and vacuum tightness is 50-1Pa, and rotary speed is 600～1400rpm, isolates methyl esters or ethyl ester.
2. the centrifugal type technique of molecular distillation that utilizes according to claim 1 is produced the oil engine method of bio-diesel oil, it is characterized in that: described step 3. in, the prime of thick methyl esters or thick ethyl ester is handled and comprised: the degassing is handled, and treatment temp is 50-100 ℃, and vacuum tightness is 5000-1000Pa; Separation of methanol or alcoholic acid are handled, and controlled temperature is 50-120 ℃, and vacuum tightness is 1000-100Pa, and rotary speed is 500～1000rpm.
3. the centrifugal type technique of molecular distillation that utilizes according to claim 1 is produced the oil engine method of bio-diesel oil, it is characterized in that: described step 2. in, roughing out is static layering or separates with high speed centrifugation.
4. the centrifugal type technique of molecular distillation that utilizes according to claim 1 is produced the oil engine method of bio-diesel oil, it is characterized in that: described step 1. in, vegetables oil or animal oil raw material and methyl alcohol or ethanol carry out esterification, and its reaction product mainly comprises methyl esters or ethyl ester, glycerine, methyl alcohol or ethanol and impurity.
5. the centrifugal type technique of molecular distillation that utilizes according to claim 1 is produced the oil engine method of bio-diesel oil, and it is characterized in that: described vegetables oil is Oleum Cocois, plam oil, numb maple oil, rapeseed oil, Jatropha curcas oil, soybean oil or peanut oil.
6. the centrifugal type technique of molecular distillation that utilizes according to claim 1 is produced the oil engine method of bio-diesel oil, it is characterized in that: described animal oil is lard, butter, fowl poultry oil or fish oil.
7. the centrifugal type technique of molecular distillation that utilizes according to claim 1 is produced the oil engine method of bio-diesel oil, it is characterized in that: the esterification of described step in 1. replaces with enzymolysis, pyrolysis or supercritical esterification.
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| CNB2006100368644A CN100424153C (en) | 2006-08-01 | 2006-08-01 | Method for producing biological diesel oil in use for internal-combustion engine by using centrifugal type technique of molecular distillation |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906348A (en) * | 2010-08-18 | 2010-12-08 | 黄卫红 | Method for reducing waste engine oil into base oil |
| CN102432459A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Purifying method of dihydroxy alcohol ester compound |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257253C (en) * | 2004-05-14 | 2006-05-24 | 中国林业科学研究院林产化学工业研究所 | Biological diesel fuel preparing method from natural grease |
| CN100375779C (en) * | 2005-06-24 | 2008-03-19 | 清华大学 | Technical method for preparing biodiesel using reactive separation process coupling technique |
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2006
- 2006-08-01 CN CNB2006100368644A patent/CN100424153C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906348A (en) * | 2010-08-18 | 2010-12-08 | 黄卫红 | Method for reducing waste engine oil into base oil |
| CN102432459A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Purifying method of dihydroxy alcohol ester compound |
| CN102432459B (en) * | 2010-09-29 | 2014-12-03 | 中国石油化工股份有限公司 | Purifying method of dihydroxy alcohol ester compound |
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