CN101550348A - Processing technology for preparing biodiesel and byproducts thereof by multistage molecular distillation - Google Patents
Processing technology for preparing biodiesel and byproducts thereof by multistage molecular distillation Download PDFInfo
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- CN101550348A CN101550348A CNA200810017848XA CN200810017848A CN101550348A CN 101550348 A CN101550348 A CN 101550348A CN A200810017848X A CNA200810017848X A CN A200810017848XA CN 200810017848 A CN200810017848 A CN 200810017848A CN 101550348 A CN101550348 A CN 101550348A
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- biofuel
- molecular distillation
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- biodiesel
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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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The invention discloses a processing technology for preparing biodiesel and byproducts thereof by multistage molecular distillation with vegetable oil, animal oil or waste edible fat as a raw material; the processing technology comprise the following steps: firstly, putting the fat and solvent in a reactor for pretreating; secondly, adding alcohol solution of catalyst for ester exchange reaction, and roughly separating the esterified reaction product to obtain crude methyl ester or crude methyl ethyl oxalate; and finally, performing multistage molecular distillation treatment including desaeration, purification and decoloring to obtain the biodiesel, fatty acid direactive glyceride, derivates of the fatty acid direactive glyceride and other byproducts. The invention adopts the multistage molecular distillation technology, achieves the purification and refining process of the biodiesel (fatty acid methyl ester or methyl ethyl oxalate), ensures that the purity quotient of the purified biodiesel is higher than that of the purified biodiesel prepared by the prior method and reaches the standard of international biodiesel, separates the fatty acid direactive glyceride, derivates of the fatty acid direactive glyceride, and other byproducts, reduces the cost of the biodiesel and , is easy to realize industrial and environmental-friendly production.
Description
Technical field
The present invention relates to the technology that a kind of preparation method and byproduct comprehensive thereof utilize, a kind of preparation technology of biofuel specifically, and utilize its by product synthetic fatty acid direactive glyceride (>90%) and derivative thereof, and reduced the biofuel cost, be easy to industrialization and friendly environment production.
Background technology
The Development and Production biofuel for changing the existing fuel oil structure of China, protection urban environment and save energy resource, is further implemented the strategy of sustainable development and is of great significance.Present domestic most of biofuel producer adopts production technique ubiquity long reaction time, and esterification yield is low, and product content is low, does not reach the GB requirement, is applied in Industrial Boiler, farm machinery etc. more and requires very low industry.Though, Vegetable oil lipoprotein of China and animal grease aboundresources, but China is per capita and consumption vegetables oil and animal grease is also very low, so present stage, many biofuel enterprise was basic with not various edible vegetable oil and fats and animal grease full production, majority is in and stops production or the half-open state that partly stops; Even discarded food oils also because various factors is difficult to focus on, can not satisfies many newly-built biofuel enterprises and produce, price does not stop to go up, and has directly increased the biofuel cost.The present invention has adopted the multiple-grade molecular distillation technology, realize and finish the purification and the process for refining of biofuel (fatty acid methyl ester or ethyl ester), the biofuel purity of purifying is than existing method purity height, biofuel meets international standards, also isolate simultaneously byproducts such as glycerine monofatty ester and derivative thereof, reduce the biofuel cost, be easy to industrialization and friendly environment production.
Summary of the invention
The purpose of this invention is to provide a kind of multiple-grade molecular distillation and produce the Technology of biofuel and byproduct thereof, the present invention can obtain the biofuel of high purity performance; And can effectively utilize reaction product and isolate byproducts such as glycerine monofatty ester and derivative thereof, reduced the biofuel cost, be easy to industrialization and friendly environment production.
The present invention is achieved through the following technical solutions:
A kind of multiple-grade molecular distillation is produced the Technology of biofuel and byproduct thereof, it is characterized in that it may further comprise the steps:
1. be raw material with vegetables oil, animal oil or various discarded food oils, carry out pre-treatment: after a certain amount of 98% sulfuric acid, grease, benzene are blended in 60-80 ℃ of abundant dissolving, reflux water-dividing, standing demix, collect upper strata liquid, continue to be warming up to 65-85 ℃, slowly drip 98% sulfuric acid, after the reaction, till acid number no longer reduces.
2. the alcoholic solution that adds catalyzer carries out transesterification reaction, product of transesterification reaction is carried out roughing out obtains thick methyl esters or thick ethyl ester: add p-methyl benzenesulfonic acid, sulfuric acid, phosphorous acid, ortho-phosphoric acid, Sulphanilic Acid or wherein the composite catalyst of any one or several compositions under 65-120 ℃, react, no longer reduce until acid number, the methyl alcohol or the alcohol saturated solution that add sodium hydroxide or potassium hydroxide subsequently, feed methyl alcohol or ethanol steam down at 65-120 ℃, be lower than till 0.5 until acid number.After the roughing out of transesterification reaction thing, through adding saturated aqueous common salt, standing demix or employing supercentrifuge separate.
3. thick methyl esters or thick ethyl ester carry out multiple-grade molecular distillation to be handled: thick methyl esters or thick ethyl ester through the multiple-grade molecular distillation degassing, purify, make biofuel after the decolouring and byproducts such as glycerine monofatty ester and derivative thereof are minimum comprises three grades: the one-level treatment temp is 100-120 ℃, vacuum tightness is 5000-10Pa, methyl alcohol or ethanol are isolated in the degassing, and methyl alcohol or ethanol can be applied mechanically after recycling; The second-stage treatment temperature is 120-300 ℃, and vacuum tightness is 100-50Pa, the biofuel of the fatty acids of purifying out methyl esters or ethyl ester; The tertiary treatment temperature is 200-300 ℃, and vacuum tightness is 50-1Pa, and glycerine monofatty ester byproducts such as (>90%) is isolated in decolouring.
Described step 3. in, one-level degassing treatment temp is 60-100 ℃, vacuum tightness is 5000-100Pa; Separation of methanol or ethanol, controlled temperature are 100-120 ℃, vacuum tightness 2000-100Pa; Isolate glycerine monofatty ester byproducts such as (>90%) for three grades, degassing treatment temp is 110-120 ℃, vacuum tightness 50-1Pa.
The present invention has adopted the multiple-grade molecular distillation technology, realize and finish the purification and the process for refining of biofuel (fatty acid methyl ester or ethyl ester), the biofuel purity of purifying is than existing method purity height, biofuel meets international standards, also isolate simultaneously glycerine monofatty ester and derivative byproduct thereof, reduce the biofuel cost, be easy to industrialization and friendly environment production.
Description of drawings
Accompanying drawing is a process flow diagram of the present invention.
Embodiment
Embodiment 1
The sewer oil that reclaims and benzene are heated to 60-80 ℃ fully after the dissolving, isolate foreign material, press the grease weight ratio and 6% 98% sulfuric acid is added reflux water-dividing 2h, standing demix, collect upper strata liquid, continue to be warming up to 65-80 ℃, slowly drip and press the grease weight ratio, reacted 2.5 hours 6% 98% sulfuric acid, measure acid number, till no longer reducing.(account for 6% of oil product gross weight toward its adding p-methyl benzenesulfonic acid and 98% sulfuric acid, acid weight ratio 1: 1), under 70-80 ℃, react, till acid number no longer reduces, the methyl alcohol saturated solution that adds sodium hydroxide (account for oil product gross weight 1.3%) subsequently, after dropwising, feed methyl alcohol or ethanol steam down at 70-105 ℃, be lower than till 0.5 until acid number, after the roughing out of transesterification reaction thing, through adding saturated aqueous common salt, standing demix, it is 80-100 ℃ that thick methyl esters or thick ethyl ester enter multiple-grade molecular distillation one-level stripper column degassing treatment temp, and vacuum tightness is 100Pa; Separation of methanol or ethanol, methyl alcohol or ethanol can be applied mechanically after recycling; Entering secondary molecular distillation tower treatment temp is 300 ℃, and vacuum tightness is 50Pa, the biofuel of the fatty acids of purifying out methyl esters or ethyl ester; Entering three grades of molecule distillation plant generating surface temperature at last is 280 ℃, and degassing treatment temp is 120 ℃, and vacuum tightness is 1Pa, and glycerine monofatty ester byproducts such as (>90%) is isolated in decolouring, and residual impurity is discharged.
Embodiment 2
Will height acidifying Fructus Zanthoxyli oil under water-bath after intensification 65-75 ℃, slowly dropping is 0.4% 98% sulfuric acid by the grease weight ratio, added in about 30 minutes, measure acid number, standing demix, collect upper strata liquid, continue to be warmed up to 60-80 ℃, slowly add and press 98% sulfuric acid of grease weight ratio 0.3%, reacted 1.5 hours, till the mensuration acid number no longer reduces, continue to be warming up to 60-80 ℃, add sodium hydroxide and press the methyl alcohol saturated solution of grease weight ratio 1.1%, after dropwising, feed methyl alcohol or ethanol steam down at 95-105 ℃, be lower than till 0.5 until acid number, after the roughing out of transesterification reaction thing, through adding saturated aqueous common salt, standing demix, it is 60-70 ℃ that thick methyl esters or thick ethyl ester enter multiple-grade molecular distillation one-level stripper column degassing treatment temp, vacuum tightness is 5000Pa; Separation of methanol or ethanol, methyl alcohol or ethanol can be applied mechanically after recycling; Entering secondary molecular distillation tower treatment temp is 180 ℃, and vacuum tightness is 50Pa, the biofuel of the fatty acids of purifying out methyl esters or ethyl ester; Entering three grades of molecule distillation plant generating surface temperature at last is 200 ℃, and degassing treatment temp is 110 ℃, and vacuum tightness is 50Pa, and glycerine monofatty ester byproducts such as (>90%) is isolated in decolouring, and residual impurity is discharged.
Embodiment 3
Become sour useless butter and the benzene of sending here from the slaughterhouse is heated to 70-80 ℃ fully after the dissolving, separate foreign material, press the grease weight ratio and 3% 98% sulfuric acid is added reflux water-dividing 1h, standing demix, collect upper strata liquid, continue to be warming up to 65-80 ℃, slowly drip and press the grease weight ratio, reacted 0.5 hour 2% 98% sulfuric acid, measure acid number, till no longer reducing.Continue to be warmed up to 75-80 ℃, slowly add and press 98% sulfuric acid and the p-methyl benzenesulfonic acid (weight ratio 1: 1) of grease weight ratio 0.3%, reacted 1.5 hours, till the mensuration acid number no longer reduces, continue to be warming up to 60-80 ℃, add sodium hydroxide and press the methyl alcohol saturated solution of grease weight ratio 1.0%, after dropwising, feed methyl alcohol or ethanol steam down at 65-70 ℃, be lower than till 0.5 until acid number, after the roughing out of transesterification reaction thing, through adding saturated aqueous common salt, standing demix, it is 100 ℃ that thick methyl esters or thick ethyl ester enter multiple-grade molecular distillation one-level stripper column degassing treatment temp, vacuum tightness is 500Pa; Separation of methanol or ethanol, methyl alcohol or ethanol can be applied mechanically after recycling; Entering secondary molecular distillation tower treatment temp is 300 ℃, and vacuum tightness is 1000Pa, the biofuel of the fatty acids of purifying out methyl esters or ethyl ester; Entering three grades of molecule distillation plant generating surface temperature at last is 280 ℃, and degassing treatment temp is 120 ℃, and vacuum tightness is 25Pa, and glycerine monofatty ester byproducts such as (>90%) is isolated in decolouring, and residual impurity is discharged.
Claims (6)
1. a multiple-grade molecular distillation is produced the Technology of biofuel and byproduct thereof, it is characterized in that it may further comprise the steps: be raw material with vegetables oil, animal oil or various discarded food oils 1., carry out pre-treatment; 2. the alcoholic solution that adds catalyzer carries out transesterification reaction, product of transesterification reaction is carried out roughing out obtain thick methyl esters or thick ethyl ester; 3. thick methyl esters or thick ethyl ester carry out multiple-grade molecular distillation to be handled: make biofuel and byproducts such as glycerine monofatty ester and derivative thereof after the degassing, purification, the decolouring.
2. produce the Technology of biofuel and byproduct thereof according to claims 1 described a kind of multiple-grade molecular distillation, it is characterized in that: described step 3. in, thick methyl esters or thick ethyl ester carry out multiple-grade molecular distillation to be handled: the degassing, purify, make biofuel after the decolouring and byproducts such as glycerine monofatty ester and derivative thereof are minimum comprises three grades: the one-level treatment temp is 100-120 ℃, vacuum tightness is 5000-10Pa, methyl alcohol or ethanol are isolated in the degassing, and methyl alcohol or ethanol can be applied mechanically after recycling; The second-stage treatment temperature is 120-300 ℃, and vacuum tightness is 100-50Pa, the biofuel of the fatty acids of purifying out methyl esters or ethyl ester; The tertiary treatment temperature is 200-300 ℃, and vacuum tightness is 50-1Pa, and glycerine monofatty ester byproducts such as (>90%) is isolated in decolouring.
3. produce the Technology of biofuel and byproduct thereof according to claims 2 described a kind of multiple-grade molecular distillations, it is characterized in that: described step 3. in, one-level degassing treatment temp is 60-100 ℃, vacuum tightness is 5000-100Pa; Separation of methanol or ethanol, controlled temperature are 100-120 ℃, vacuum tightness 2000-100Pa; Isolate glycerine monofatty ester byproducts such as (>90%) for three grades, degassing treatment temp is 110-120 ℃, vacuum tightness 50-1Pa.
4. produce the Technology of biofuel and byproduct thereof according to claims 1 described a kind of multiple-grade molecular distillation, it is characterized in that: described step 2. in, add p-methyl benzenesulfonic acid, sulfuric acid, phosphorous acid, ortho-phosphoric acid, Sulphanilic Acid or wherein the composite catalyst of any one or several compositions under 65-120 ℃, react, no longer reduce until acid number, the methyl alcohol or the alcohol saturated solution that add sodium hydroxide or potassium hydroxide subsequently feed methyl alcohol or ethanol steam down at 65-120 ℃, are lower than till 0.5 until acid number.After the roughing out of transesterification reaction thing, through adding saturated aqueous common salt, static layering or employing supercentrifuge separate.
5. produce the Technology of biofuel and byproduct thereof according to claims 1 described a kind of multiple-grade molecular distillation, it is characterized in that: described step 1. in, with vegetables oil, animal oil or discarded food oils is raw material, carries out pre-treatment: after a certain amount of 98% sulfuric acid, grease, benzene are blended in 60-80 ℃ of abundant dissolving, and reflux water-dividing, standing demix, collect upper strata liquid, continue to be warming up to 65-85 ℃, slowly drip 98% sulfuric acid, after the reaction, till acid number no longer reduces.
6. a multiple-grade molecular distillation is produced the Technology of biofuel and byproduct thereof, and it is characterized in that: described byproduct is byproducts such as glycerine monofatty ester (>90%) and derivative thereof.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102516056A (en) * | 2011-12-08 | 2012-06-27 | 河北欣奇典生物科技有限公司 | Method for reproduction of fatty acid with molecular distillation distillate of unsaturated fatty acid |
CN102776067A (en) * | 2012-05-31 | 2012-11-14 | 源华能源科技(福建)有限公司 | Process for purifying crude fatty acidmethyl ester through molecular distillation |
CN102041177B (en) * | 2009-10-18 | 2013-01-16 | 陕西春光生物能源开发有限公司 | Method for preparing biodiesel |
CN110172377A (en) * | 2019-06-20 | 2019-08-27 | 成都恒润高新科技股份有限公司 | A method of biodiesel is continuously prepared using waste animal and vegetable oil |
CN111265904A (en) * | 2020-03-30 | 2020-06-12 | 龙岩卓越新能源股份有限公司 | Method for continuously dealcoholizing biodiesel byproduct crude glycerol |
CN112625805A (en) * | 2020-09-23 | 2021-04-09 | 武汉科技大学 | Method for synthesizing biodiesel under catalysis of solid acid catalyst |
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CN1869162A (en) * | 2006-06-29 | 2006-11-29 | 华南理工大学 | Method of producing biological diesel oil directly using molecular distillation technology |
CN1935945A (en) * | 2006-09-28 | 2007-03-28 | 南京大学 | Biodiesel preparing method and its byproduct recovering and utilizing method |
KR100787495B1 (en) * | 2006-04-18 | 2008-01-16 | 조화현 | Process for preparing biodiesel |
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2008
- 2008-03-31 CN CNA200810017848XA patent/CN101550348A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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KR100787495B1 (en) * | 2006-04-18 | 2008-01-16 | 조화현 | Process for preparing biodiesel |
CN1869162A (en) * | 2006-06-29 | 2006-11-29 | 华南理工大学 | Method of producing biological diesel oil directly using molecular distillation technology |
CN1935945A (en) * | 2006-09-28 | 2007-03-28 | 南京大学 | Biodiesel preparing method and its byproduct recovering and utilizing method |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102041177B (en) * | 2009-10-18 | 2013-01-16 | 陕西春光生物能源开发有限公司 | Method for preparing biodiesel |
CN102516056A (en) * | 2011-12-08 | 2012-06-27 | 河北欣奇典生物科技有限公司 | Method for reproduction of fatty acid with molecular distillation distillate of unsaturated fatty acid |
CN102516056B (en) * | 2011-12-08 | 2015-07-01 | 河北欣奇典生物科技有限公司 | Method for reproduction of fatty acid with molecular distillation distillate of unsaturated fatty acid |
CN102776067A (en) * | 2012-05-31 | 2012-11-14 | 源华能源科技(福建)有限公司 | Process for purifying crude fatty acidmethyl ester through molecular distillation |
CN110172377A (en) * | 2019-06-20 | 2019-08-27 | 成都恒润高新科技股份有限公司 | A method of biodiesel is continuously prepared using waste animal and vegetable oil |
CN111265904A (en) * | 2020-03-30 | 2020-06-12 | 龙岩卓越新能源股份有限公司 | Method for continuously dealcoholizing biodiesel byproduct crude glycerol |
CN112625805A (en) * | 2020-09-23 | 2021-04-09 | 武汉科技大学 | Method for synthesizing biodiesel under catalysis of solid acid catalyst |
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Address after: Western International Plaza No. 2 710075 Shaanxi city of Xi'an province high road 10 Applicant after: Xi'an Baorun Industrial Development Co., Ltd. Address before: 710043 Torch Road 7, Dong hi tech, Shaanxi, Xi'an Applicant before: Xi'an Baorun Industrial Development Co., Ltd. |
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Application publication date: 20091007 |