CN104774694A - Method for synchronously preparing biodiesel and glycerol from high-acid-value vegetable oil - Google Patents
Method for synchronously preparing biodiesel and glycerol from high-acid-value vegetable oil Download PDFInfo
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- CN104774694A CN104774694A CN201510161201.4A CN201510161201A CN104774694A CN 104774694 A CN104774694 A CN 104774694A CN 201510161201 A CN201510161201 A CN 201510161201A CN 104774694 A CN104774694 A CN 104774694A
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- Prior art keywords
- reaction
- esterification
- methanol
- biofuel
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
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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
Abstract
The invention relates to a method for synchronously preparing biodiesel and glycerol from high-acid-value vegetable oil, which comprises the following steps: esterification reaction, distillation, ester exchange reaction, dealcoholizing, sedimentation and the like. The biodiesel product yield can reach 99%, the glycerol purity is up to 95% above, the esterification ester exchange catalyst consumption is lowered by 50%, the ester exchange time is shortened from 2 hours to 30 minutes, and the methanol obtained by ester exchange can be directly used for esterification reaction, thereby lowering the methanol recovery energy consumption.
Description
Technical field
The invention belongs to technical field of biodiesel preparation, be specifically related to a kind of high acid value vegetables oil interlock system that utilizes for the method for biofuel and glycerine.
Background technology
In the world today, the development of science and technology and the civilization of the mankind rely on mineral fuel to a great extent as main energy sources.But fossil energy is as Nonrenewable energy resources, what use along with people increases, and the total amount of the energy is fewer and feweri, and problem of energy crisis will certainly be more and more serious.One of the study hotspot in biomass liquid fuel field has been become as a kind of novel renewable energy source-biofuel.
Biofuel refers to the organic acid acetic class A fuel A made with raw materials such as oil crops, oil pressing factory's oil foot, waste cooking oils, is typical green energy resource.Due to it have that the feature of environmental protection is good, security is high, the characteristic such as flammable and oilness is good.Therefore biofuel has broad application prospects, and produces very great effect by guarantee Oil Safety, guarantee ecotope, developing rural economy, raising farmers' income etc.
Existing method for synthesizing biologic diesel oil mainly contains supercritical methanol technology and esterification ester-interchange method.Because esterification ester-interchange method has the advantages such as technique is simple, reaction conditions is gentle, enjoy everybody favor.But also there is low conversion rate, alcohol consumption is large, Methanol Recovery energy consumption large, glycerine reclaims and separately need build the problems such as device.
Summary of the invention
The object of the invention is will to provide that a kind of yield is high, energy consumption is low for high acid value preparation of biodiesel with vegetable oils, the method for catalyst levels less and simultaneously output high density glycerine.
The invention discloses a kind of high acid value vegetables oil interlock system that utilizes for the method for biofuel and glycerine, described preparation method comprises the following steps.
1, esterification
High acid value vegetables oil is added in esterifier, adds tosic acid as catalyzer, lead to methanol steam at agitation condition and carry out esterification.Esterification reaction temperature is 120 ~ 130 DEG C, reaction times 2 ~ 3h.Dewater after esterification terminates 30min at 130 DEG C.
2, distill
Underpressure distillation, obtains the biofuel generated in esterification reaction process.
3, transesterification reaction
Add in transesterification reactor by the excess that heats up in a steamer of step 2 gained, add sodium hydroxide and methyl alcohol, react 20 ~ 30mim under agitation, temperature of reaction is 50 ~ 60 DEG C.
4, dealcoholysis
After transesterify terminates, heat up unreacted methanol, and gained methyl alcohol can be directly used in esterification.
5, distill
Reactant after methanol removal distills, and obtains light phase biofuel and heavy phase glycerine after cut condensation through sedimentation, and heating up in a steamer excess is Biological asphalt.
Acid number 10 ~ the 180mgKOH/g of high acid value vegetables oil of the present invention.
In esterification of the present invention, tosic acid addition is 1 ‰ ~ 2 ‰ of vegetables oil.
The biofuel that esterification of the present invention generates first steams, and no longer enters transesterification reaction.
1 ‰ ~ 2 ‰ of described transesterification reaction addition amount of sodium hydroxide vegetables oil of the present invention.
Beneficial effect of the present invention is as follows.
1, biofuel relative raw material active principle yield of the present invention can reach 99%, and glycerine purity can reach more than 95%.
2, catalyst for esterification reaction addition of the present invention is 1 ‰ ~ 2 ‰ of vegetables oil.
3, the present invention first steams the biofuel that esterification process produces, and decreases the consumption of Exchange Ester Process catalyzer and methyl alcohol, shortens the transesterification reaction time, improves transesterify plant factor.
4, the methyl alcohol that step 4 dealcoholysis of the present invention obtains directly can be used in esterification.
5, biofuel and glycerine directly steam by step 5 of the present invention simultaneously, exempt purification of glycerin process.
Accompanying drawing explanation
Fig. 1 and 2 is that a kind of high acid value vegetables oil interlock system that utilizes is for the method technical process of biofuel and glycerine.
Embodiment
embodiment 1.
1, esterification
Be the impure 160g of 96mgKOH/g vegetables oil 800g(by acid number) add in esterifier, start and stir, add 0.8g tosic acid, be heated to 120 DEG C of logical methanol steams and carry out esterification.Esterification temperature controls at 130 DEG C, reaction times 2h.Dewater after esterification terminates 30min at 130 DEG C.
2, distill
Carry out underpressure distillation, obtain the biofuel 413g generated in esterification reaction process.
3, transesterification reaction
Add in transesterification reactor by the excess that heats up in a steamer of step 2 gained, add 0.8g sodium hydroxide and 77.4g methyl alcohol, react 30mim under agitation, temperature of reaction controls at 60 DEG C.
4, dealcoholysis
After transesterify terminates, heat up unreacted methanol, and gravity settling layering, lower floor obtains purity 60% glycerine 9.5g.
5, distill
Upper strata underpressure distillation, obtains biofuel 221g.
embodiment 2.
1, esterification
Be the impure 160g of 96mgKOH/g vegetables oil 800g(by acid number) add in esterifier, start and stir, add 1.6g tosic acid, be heated to 120 DEG C, is passed in esterifier after the methanol gasifying that dealcoholysis layering is obtained and carry out esterification.Esterification temperature controls at 130 DEG C, reaction times 2h.Dewater after esterification terminates 30min at 130 DEG C.
2, distill
Carry out underpressure distillation, obtain the biofuel 402g generated in esterification reaction process.
3, transesterification reaction
Add in transesterification reactor by the excess that heats up in a steamer of step 2 gained, add sodium hydroxide methyl alcohol and the 80.1g methyl alcohol of 1.6g sodium hydroxide, react 30mim under agitation, temperature of reaction controls at 60 DEG C.
4, dealcoholysis
After transesterify terminates, heat up unreacted methanol.
5, distill
Liquid after methanol removal carries out underpressure distillation, and heating up in a steamer excess is Biological asphalt.Cut condensation is obtained purity 96% glycerine 5.8g, biofuel 232g.
Claims (6)
1. utilize high acid value vegetables oil interlock system for a method for biofuel and glycerine, it is characterized in that, step is as follows:
1) add in esterifier by high acid value vegetables oil, add tosic acid, pass into methanol steam under agitation and carry out esterification, reaction terminates rear dehydration;
2) underpressure distillation, cut obtains biofuel through condensation;
3) heating up in a steamer excess adds in transesterification reactor, adds sodium hydroxide, carries out transesterification reaction under agitation;
4) intensification removes unreacted methanol, and gained methyl alcohol direct reuse is to esterification;
5) reaction solution after methanol removal carries out Biological asphalt, biofuel and sweet oil separating.
2. the method for claim 1, is characterized in that: step 2) in esterification generate biofuel first steam, no longer enter transesterification reaction.
3. the method for claim 1, is characterized in that: in esterification reaction process, catalyzer tosic acid addition is 1 ‰ ~ 2 ‰ of vegetables oil.
4. the method for claim 1, is characterized in that: in ester-exchange reaction, catalyzer sodium hydroxide addition is 1 ‰ ~ 2 ‰ of vegetables oil.
5. the method for claim 1, is characterized in that, step is as follows:
1) add in esterifier by high acid value vegetables oil, add tosic acid, pass into methanol steam under agitation and carry out esterification, temperature is 120 ~ 130 DEG C, reaction times 2 ~ 3h, and dewater after reaction terminates 20 ~ 30min at 130 DEG C;
2) carry out underpressure distillation, cut obtains biofuel and raw glycerine through separation;
3) heating up in a steamer excess adds in transesterification reactor, adds sodium hydroxide, reacts 20 ~ 30min under agitation, temperature of reaction 50 ~ 60 DEG C;
4) after transesterification reaction terminates, heat up remove unreacted methanol, gained methyl alcohol can direct reuse to esterification;
5) reaction solution after methanol removal carries out multi_layer extraction and goes out raw glycerine, and residuum goes out bio oil production by fractionation by distillation, and heating up in a steamer excess is Biological asphalt.
6. the method for claim 1, is characterized in that, step is as follows:
1) add in esterifier by high acid value vegetables oil, add tosic acid methanol solution, pass into methanol steam under agitation and carry out esterification, temperature is 120 ~ 130 DEG C, reaction times 2 ~ 3h, and dewater after reaction terminates 20 ~ 30min at 130 DEG C;
2) carry out underpressure distillation, cut obtains biofuel and raw glycerine through separation;
3) heating up in a steamer excess adds in transesterification reactor, adds sodium hydrate methanol solution, reacts 20 ~ 30min under agitation, temperature of reaction 50 ~ 60 DEG C;
4), after transesterification reaction terminates, heat up and remove unreacted methanol, gained methyl alcohol direct reuse is to esterification;
5) reaction solution after methanol removal carries out fractionation by distillation, and heating up in a steamer excess is Biological asphalt, and cut can obtain biofuel and smart glycerol product through gravity settling after condensation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510161201.4A CN104774694A (en) | 2015-04-08 | 2015-04-08 | Method for synchronously preparing biodiesel and glycerol from high-acid-value vegetable oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510161201.4A CN104774694A (en) | 2015-04-08 | 2015-04-08 | Method for synchronously preparing biodiesel and glycerol from high-acid-value vegetable oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104774694A true CN104774694A (en) | 2015-07-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201510161201.4A Pending CN104774694A (en) | 2015-04-08 | 2015-04-08 | Method for synchronously preparing biodiesel and glycerol from high-acid-value vegetable oil |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995288A (en) * | 2006-12-25 | 2007-07-11 | 昆明理工大学 | Process for preparing biodiesel oil |
| CN101070480A (en) * | 2006-05-12 | 2007-11-14 | 中国石油化工股份有限公司 | Process for preparing biological diesel oil |
| CN101200648A (en) * | 2006-12-13 | 2008-06-18 | 中国石油化工股份有限公司 | Preparation method of biological diesel fuel |
| CN102477357A (en) * | 2010-11-25 | 2012-05-30 | 中国石油化工股份有限公司 | Method for preparing biodiesel |
| CN102586031A (en) * | 2012-02-27 | 2012-07-18 | 华侨大学 | Ion-liquid-based method for preparing biodiesel |
| CN104312735A (en) * | 2014-11-13 | 2015-01-28 | 山东华亚环保科技有限公司 | Method for producing biodiesel by utilizing waste vegetable oil |
-
2015
- 2015-04-08 CN CN201510161201.4A patent/CN104774694A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070480A (en) * | 2006-05-12 | 2007-11-14 | 中国石油化工股份有限公司 | Process for preparing biological diesel oil |
| CN101200648A (en) * | 2006-12-13 | 2008-06-18 | 中国石油化工股份有限公司 | Preparation method of biological diesel fuel |
| CN103074123A (en) * | 2006-12-13 | 2013-05-01 | 中国石油化工股份有限公司 | Method for preparing biodiesel |
| CN1995288A (en) * | 2006-12-25 | 2007-07-11 | 昆明理工大学 | Process for preparing biodiesel oil |
| CN102477357A (en) * | 2010-11-25 | 2012-05-30 | 中国石油化工股份有限公司 | Method for preparing biodiesel |
| CN102586031A (en) * | 2012-02-27 | 2012-07-18 | 华侨大学 | Ion-liquid-based method for preparing biodiesel |
| CN104312735A (en) * | 2014-11-13 | 2015-01-28 | 山东华亚环保科技有限公司 | Method for producing biodiesel by utilizing waste vegetable oil |
Non-Patent Citations (4)
| Title |
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| 刘伟伟等: "对甲苯磺酸催化高酸值油脂甲酯化的实验", 《中国油脂》 * |
| 苏有勇等: "高酸值生物柴油原料降酸的研究", 《中国油脂》 * |
| 蔡新安等: "高酸值潲水油制取生物柴油的研究", 《景德镇高专学报》 * |
| 谢国剑: "高酸值潲水油制取生物柴油的研究", 《化工技术与开发》 * |
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Application publication date: 20150715 |
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