CN1915948A - Method for refining glycerol being as byproduct of biology diesel oil - Google Patents
Method for refining glycerol being as byproduct of biology diesel oil Download PDFInfo
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- CN1915948A CN1915948A CNA2006100372936A CN200610037293A CN1915948A CN 1915948 A CN1915948 A CN 1915948A CN A2006100372936 A CNA2006100372936 A CN A2006100372936A CN 200610037293 A CN200610037293 A CN 200610037293A CN 1915948 A CN1915948 A CN 1915948A
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- glycerine
- glycerol
- purification according
- phosphoric acid
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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
Abstract
This invention discloses a method for refining glycerol byproduct of biodiesel oil manufacture. The method comprises: (1) evaporating crude glycerol to recover methanol, and neutralizing alkaline catalyst with phosphoric acid to acidity; (2) centrifuging to obtain three layers (crude fatty acids as the upper layer, glycerol semi-final product as the middle layer, and phosphates as the bottom layer); (3) evaporating to remove water from glycerol semi-final product, and adding ethanol to crystallize and remove phosphates; (4) molecular-distilling to obtain medical grade glycerol. The method has advantages as simple process, low energy consumption, high glycerol purity and good glycerol quality.
Description
Technical field
The present invention relates to the process for purification of the byproduct-glycerine in the production biofuel process.
Background technology
Biofuel be a kind of renewable, biodegradable, nontoxic, sulphur content is low, the little clean energy of discharge of poisonous waste amount in the waste gas, it can be used as, and important new forms of energy replace or part substitutes petroleum diesel.Produce a large amount of by-product glycerins in the production of biodiesel process, 1 ton of biofuel of about every production just will produce 100kg glycerine.Surging along with the international petroleum oil price, the biofuel of the type energy is with the extremely extensive favor of countries in the world as an alternative, and the glycerin by-products of generation can get more and more.Glycerine is broad-spectrum food, chemical industry and medical material, in the pharmaceutical grade glycerine partial dependency import always of China's high purity (99.5%).In the mass production biofuel, make full use of its by product, production pharmaceutical grade glycerine has tangible economic implications and social benefit.
With base catalysis technology, be the raw material production biofuel with refined vegetable oil, after the transesterification reaction, can obtain raw glycerine through separating, main component is glycerine (40-50%), methyl alcohol (25-30%), basic catalyst and soap (20-25%).Present stage, refining purification pharmaceutical grade glycerine mainly contains rectification under vacuum method, ion exchange method etc. from raw glycerine.Because the glycerine boiling point is very high, rectification under vacuum needs higher temperature (180 ℃), and energy consumption is big.Ion exchange method, owing to need dilution glycerine to remove metal ion in the raw glycerine by ion exchange resin, energy consumption is also bigger when evaporation concentration, needs simultaneously the purified product processing of further decolouring.
Summary of the invention
The process for purification that the purpose of this invention is to provide a kind of biodiesel byproduct product glycerine, operational path is short, and equipment requirements is simple, and energy consumption is low, the products obtained therefrom quality better.
For reaching above-mentioned purpose, the process for purification of biodiesel byproduct product glycerine of the present invention is as follows: raw glycerine at first evaporates recovery methyl alcohol, use again in the phosphoric acid and basic catalyst to slant acidity; The gained neutralizer obtains three layers through centrifugation, and the upper strata is a croude fatty acids, and the middle level is a glycerol semi-final product, and lower floor is a phosphoric acid salt; After steaming the moisture in the glycerol semi-final product, interpolation ethanol carries out crystallization and further removes phosphoric acid salt, carries out molecular distillation at last, obtains pharmaceutical grade glycerine finished product.
Described raw glycerine is with base catalysis method production biofuel, after the transesterification reaction, through separating the raw glycerine that obtains, main component glycerine, methyl alcohol, basic catalyst and soap.
The condition of the phosphoric acid neutralization reaction of described raw glycerine is: per 20 grams remove the phosphoric acid solution of 3～10 milliliter 40% of methyl alcohol raw glycerine adding, 50～70 ℃ of temperature of reaction, reaction times 20～60min; Gained neutralizer centrifuge speeds is 3000～3500r/min.
Described alcoholic acid volumetric concentration is 95%, adds to 1: 1～2 volume ratio in the glycerol semi-final product steamed behind the moisture.The temperature of described alcohol crystal is 10～20 ℃, and crystallization time is 20～40 minutes.As preferred version, to add 95% ethanol in the glycerol semi-final product of 1: 1 volume ratio after moisture is fallen in steaming, the temperature of alcohol crystal is 20 ℃, and crystallization time is 20 minutes.
Behind alcohol crystal, the temperature of molecular distillation is 105～120 ℃, and distillation pressure is 25～35Pa.As preferred version, behind alcohol crystal, the temperature of molecular distillation is 110 ℃, and distillation pressure is 30Pa.
Technology of the present invention is simple, and energy consumption is low, prepared glycerine finished product purity height, quality better.
Description of drawings
Fig. 1 is a purification of glycerin process flow sheet of the present invention.
Embodiment
Embodiment one
1, the preparation of raw glycerine:
In round-bottomed flask, add 1000 gram plam oils, add the KOH of 250 gram methyl alcohol and 12 grams, under 60 ℃ temperature, carried out stirring reaction 1 hour with the speed of 300r/min.Reacted the back and left standstill in pear shape separatory funnel 1-2 hour, be divided into two-layerly after leaving standstill, the upper strata is a biofuel, and lower floor's reaction solution is the raw glycerine layer, emits subnatant, i.e. the raw material raw glycerine.
2, raw glycerine neutralization:
In absolute pressure 1.0 * 10
4Pa, 45 ℃ of following rotary evaporations of temperature reclaim the methyl alcohol in the raw glycerine, obtain the methyl alcohol raw glycerine.Take by weighing the raw glycerine that removes methyl alcohol of 20 grams, 40% the phosphoric acid solution that adds 5ml, stir with glass stick, be placed on then in 60 ℃ of water-baths of constant temperature and carried out neutralization reaction 20 minutes, react the back and under the rotating speed of 3500r/min, carried out centrifugation, obtained three layers: upper strata croude fatty acids, middle level G ﹠ W, lower floor's phosphoric acid salt.Topple over earlier and upper strata lipid acid, pour out the glycerine in middle level again, the glycerine of getting the middle level is in absolute pressure 5 * 10
3Be rotated under 80 ℃ of the Pa, temperature and steam the moisture that produces in the reaction, glycerol semi-final product.
3, alcohol crystal:
In 50 milliliters of centrifuge tubes, add 10 gram glycerol semi-final product, add 95% ethanol of 10ml again, stir evenly with glass stick, 20 ℃ of following crystallizations of low temperature 20 minutes.Carry out suction filtration then, remove and to decrystallize, ethanol is removed in the filtered solution evaporation, can obtain thickness, transparent glycerine.
4, molecular distillation:
The glycerine 100g that takes by weighing behind the alcohol crystal adds in the molecular distillation charging stock tank, earlier 60 ℃, raw material outgased, dewaters to raw material during absolute pressure 50Pa and no longer end during bubbling.After the degassing, manually control feed valve, 1 droplet/second of feeding rate control is carried out molecular distillation under 105 ℃ of distillation temperatures, pressure 25Pa, obtains purity and be 99.6% pharmaceutical grade glycerine finished product, wherein K
+Content be 1.00mg/kg, the content of Na+ is 0.24mg/kg, the content of As+ is 0.05mg/kg, the content of Pb+ is 0.05mg/kg.Yield is 95.2%.
Embodiment two:
1, the preparation of raw glycerine:
With embodiment one.
2, raw glycerine neutralization:
In absolute pressure 1.0 * 10
4Pa, 45 ℃ of following rotary evaporations of temperature reclaim and get methyl alcohol in the raw glycerine, obtain the methyl alcohol raw glycerine.Take by weighing the raw glycerine that removes methyl alcohol of 20 grams, 40% the phosphoric acid solution that adds 7ml, stir with glass stick, be placed on then in 50 ℃ of water-baths of constant temperature and carried out neutralization reaction 60 minutes, react the back and under the rotating speed of 3500r/min, carried out centrifugation, obtained three layers: upper strata croude fatty acids, middle level G ﹠ W, lower floor's phosphoric acid salt.Topple over earlier and upper strata lipid acid, pour out the glycerine in middle level again, the glycerine of getting the middle level is in absolute pressure 5 * 10
3Pa, temperature are rotated for 80 ℃ and steam the moisture that produces in the reaction, get glycerol semi-final product.
3, alcohol crystal:
In 50 milliliters of centrifuge tubes, add 10 gram glycerol semi-final product, add 95% ethanol of a certain amount of 15ml again, stir evenly with glass stick, 10 ℃ of following crystallizations of low temperature 20 minutes.Carry out suction filtration then, remove and to decrystallize, ethanol is removed in the filtered solution evaporation, can obtain thickness, transparent glycerine.
4, molecular distillation:
The glycerine 100g that takes by weighing behind the alcohol crystal adds in the molecular distillation charging stock tank, earlier 60 ℃, raw material outgased, dewaters to raw material during absolute pressure 50Pa and no longer end during bubbling.After the degassing, manually control feed valve, 1 droplet/second of feeding rate control is carried out molecular distillation under 110 ℃ of distillation temperatures, pressure 30Pa, purity is 99.6% pharmaceutical grade glycerine finished product, the glycerine yield is 97.3%.
Embodiment three
1, the preparation of raw glycerine:
With embodiment one.
2, raw glycerine neutralization:
In absolute pressure 1.0 * 10
4Pa, 45 ℃ of following rotary evaporations of temperature reclaim and get methyl alcohol in the raw glycerine, obtain the methyl alcohol raw glycerine.Take by weighing the raw glycerine that removes methyl alcohol of 20 grams, 40% the phosphoric acid solution that adds 10ml, stir with glass stick, be placed on then in 70 ℃ of water-baths of constant temperature and carried out neutralization reaction 40 minutes, react the back and under the rotating speed of 3000r/min, carried out centrifugation, obtained three layers: upper strata croude fatty acids, middle level G ﹠ W, lower floor's phosphoric acid salt.Topple over earlier and upper strata lipid acid, pour out the glycerine in middle level again, get the glycerine absolute pressure 5 * 10 in middle level
3Be rotated under 80 ℃ of the Pa, temperature and steam the moisture that produces in the reaction, glycerol semi-final product.
3, alcohol crystal:
In 50 milliliters of centrifuge tubes, add 10 gram glycerol semi-final product, add 95% ethanol of a certain amount of 20ml again, stir evenly with glass stick, 20 ℃ of following crystallizations of low temperature 20 minutes.Carry out suction filtration then, remove and to decrystallize, ethanol is removed in the filtered solution evaporation, can obtain thickness, transparent glycerine.
4, molecular distillation:
The glycerine 100g that takes by weighing behind the alcohol crystal adds in the molecular distillation charging stock tank, earlier 60 ℃, raw material outgased, dewaters to raw material during absolute pressure 50Pa and no longer end during bubbling.After the degassing, manually control feed valve, 1 droplet/second of feeding rate control is at 120 ℃ of distillation temperatures, pressure 35Pa molecular distillation.Obtain purity and be 99.6% pharmaceutical grade glycerine finished product, the glycerine yield is 98.2%.
Claims (9)
1, a kind of process for purification of biodiesel byproduct product glycerine, it is characterized in that: raw glycerine at first evaporates recovery methyl alcohol, use again in the phosphoric acid and basic catalyst to slant acidity; The gained neutralizer obtains three layers through centrifugation, and the upper strata is a croude fatty acids, the middle level glycerol semi-final product, and lower floor is a phosphoric acid salt; After steaming the moisture in the glycerol semi-final product, interpolation ethanol carries out crystallization and further removes phosphoric acid salt, carries out molecular distillation at last, obtains pharmaceutical grade glycerine finished product.
2, process for purification according to claim 1 is characterized in that: described raw glycerine is with base catalysis method production biofuel, after the transesterification reaction, through separating the raw glycerine that obtains, main component glycerine, methyl alcohol, basic catalyst and soap.
3, process for purification according to claim 1 is characterized in that: the condition of the phosphoric acid neutralization reaction of raw glycerine is: per 20 grams remove the phosphoric acid solution of 3～10 milliliter 40% of methyl alcohol raw glycerine adding, 50～70 ℃ of temperature of reaction, reaction times 20～60min; Gained neutralizer centrifuge speeds is 3000～3500r/min.
4, process for purification according to claim 1 is characterized in that: described alcoholic acid volumetric concentration is 95%, adds to 1: 1～2 volume ratio in the glycerol semi-final product steamed behind the moisture.
5, process for purification according to claim 4 is characterized in that: to be 95% ethanol add in the glycerol semi-final product of steaming behind the moisture with 1: 1 volume ratio described concentration.
6, process for purification according to claim 4 is characterized in that: the temperature of described alcohol crystal is 10～20 ℃, and crystallization time is 20～40 minutes.
7, process for purification according to claim 6 is characterized in that: the temperature of described alcohol crystal is 20 ℃, and crystallization time is 20 minutes.
8, process for purification according to claim 1 is characterized in that: behind alcohol crystal, the temperature of molecular distillation is 105～120 ℃, and distillation pressure is 25～35Pa.
9, process for purification according to claim 8 is characterized in that: behind alcohol crystal, the temperature of molecular distillation is 110 ℃, and distillation pressure is 30Pa.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100372936A CN100376525C (en) | 2006-08-25 | 2006-08-25 | Method for refining glycerol being as byproduct of biology diesel oil |
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| CNB2006100372936A CN100376525C (en) | 2006-08-25 | 2006-08-25 | Method for refining glycerol being as byproduct of biology diesel oil |
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| CN1915948A true CN1915948A (en) | 2007-02-21 |
| CN100376525C CN100376525C (en) | 2008-03-26 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101633605A (en) * | 2008-07-23 | 2010-01-27 | 张伟民 | Method for preparing glycerin from byproduct in manufacture procedure of biodiesel |
| CN101392054B (en) * | 2008-10-31 | 2010-08-11 | 句容市宁武化工有限公司 | Method for preparing glyceryl polyether glycol |
| CN102154023A (en) * | 2011-03-22 | 2011-08-17 | 南昌大学 | Method for preparing hydrocarbon fuel by using microwave-assisted catalytic soap decarboxylation method |
| CN102268280A (en) * | 2011-07-08 | 2011-12-07 | 南昌大学 | Method for preparing hydrocarbon fuel by using microwave assisted catalytic saponin decarboxylation method |
| CN103274900A (en) * | 2013-06-07 | 2013-09-04 | 文建方 | Method for extracting glycerol from biodiesel wastewater |
| CN105026356A (en) * | 2013-03-06 | 2015-11-04 | 阿科玛法国公司 | Use of sulphonic acid for recovering glycerol from a triglyceride transesterification reaction |
| CN107418978A (en) * | 2017-06-24 | 2017-12-01 | 天津大学 | A kind of method that farnesene is prepared using biological diesel oil byproduct |
| CN108821945A (en) * | 2018-05-15 | 2018-11-16 | 浙江工业大学 | A kind of recovery method of by-product glycerol of biological diesel oil and base catalyst |
| CN109020785A (en) * | 2018-07-25 | 2018-12-18 | 清远市福泰甘油精制有限公司 | The glycerol generated during a kind of pair of production of biodiesel carries out refining method |
| CN111871364A (en) * | 2020-07-24 | 2020-11-03 | 武汉轻工大学 | Preparation method of solid acid and method for purifying glycerin from biodiesel byproduct |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423456B (en) * | 2008-12-02 | 2012-07-11 | 昆明理工大学 | Recovery and purification method of glycerol as by-product of biodiesel production prepared by Jatrohpa curcas seed oil |
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2006
- 2006-08-25 CN CNB2006100372936A patent/CN100376525C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101633605A (en) * | 2008-07-23 | 2010-01-27 | 张伟民 | Method for preparing glycerin from byproduct in manufacture procedure of biodiesel |
| CN101392054B (en) * | 2008-10-31 | 2010-08-11 | 句容市宁武化工有限公司 | Method for preparing glyceryl polyether glycol |
| CN102154023A (en) * | 2011-03-22 | 2011-08-17 | 南昌大学 | Method for preparing hydrocarbon fuel by using microwave-assisted catalytic soap decarboxylation method |
| CN102268280A (en) * | 2011-07-08 | 2011-12-07 | 南昌大学 | Method for preparing hydrocarbon fuel by using microwave assisted catalytic saponin decarboxylation method |
| CN105026356A (en) * | 2013-03-06 | 2015-11-04 | 阿科玛法国公司 | Use of sulphonic acid for recovering glycerol from a triglyceride transesterification reaction |
| CN103274900A (en) * | 2013-06-07 | 2013-09-04 | 文建方 | Method for extracting glycerol from biodiesel wastewater |
| CN107418978A (en) * | 2017-06-24 | 2017-12-01 | 天津大学 | A kind of method that farnesene is prepared using biological diesel oil byproduct |
| CN108821945A (en) * | 2018-05-15 | 2018-11-16 | 浙江工业大学 | A kind of recovery method of by-product glycerol of biological diesel oil and base catalyst |
| CN108821945B (en) * | 2018-05-15 | 2021-06-08 | 浙江工业大学 | Recovery method of biodiesel byproduct glycerin and alkali catalyst |
| CN109020785A (en) * | 2018-07-25 | 2018-12-18 | 清远市福泰甘油精制有限公司 | The glycerol generated during a kind of pair of production of biodiesel carries out refining method |
| CN111871364A (en) * | 2020-07-24 | 2020-11-03 | 武汉轻工大学 | Preparation method of solid acid and method for purifying glycerin from biodiesel byproduct |
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| Publication number | Publication date |
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| CN100376525C (en) | 2008-03-26 |
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Assignee: Jiangmen Hongjie Fine Chemical Industry Co., Ltd. Assignor: Jinan University Contract fulfillment period: 2008.4.21 to 2014.4.21 contract change Contract record no.: 2009440000852 Denomination of invention: Method for refining glycerol being as byproduct of biology diesel oil Granted publication date: 20080326 License type: Exclusive license Record date: 2009.7.30 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.4.21 TO 2014.4.21; CHANGE OF CONTRACT Name of requester: JIANGMEN CITY HONGJIE FINE CHEMICAL CO., LTD. Effective date: 20090730 |
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Granted publication date: 20080326 Termination date: 20110825 |