CN101362958A - Method for quickly preparing biodiesel at low pressure by alkali catalyst-enhanced supercritical methanol method - Google Patents
Method for quickly preparing biodiesel at low pressure by alkali catalyst-enhanced supercritical methanol method Download PDFInfo
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- CN101362958A CN101362958A CNA2008100132965A CN200810013296A CN101362958A CN 101362958 A CN101362958 A CN 101362958A CN A2008100132965 A CNA2008100132965 A CN A2008100132965A CN 200810013296 A CN200810013296 A CN 200810013296A CN 101362958 A CN101362958 A CN 101362958A
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- Prior art keywords
- methyl alcohol
- oil
- low pressure
- alkaline catalysts
- methanol
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 title claims abstract description 22
- 239000003225 biodiesel Substances 0.000 title claims description 8
- 239000003513 alkali Substances 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 150000004702 methyl esters Chemical class 0.000 claims abstract description 11
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims description 29
- 235000019198 oils Nutrition 0.000 claims description 29
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000002551 biofuel Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 235000012424 soybean oil Nutrition 0.000 claims description 11
- 239000003549 soybean oil Substances 0.000 claims description 11
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 238000004587 chromatography analysis Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 235000013311 vegetables Nutrition 0.000 claims description 7
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 abstract 1
- 238000012805 post-processing Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 238000001816 cooling Methods 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000031018 biological processes and functions Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 235000019626 lipase activity Nutrition 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 150000002646 long chain fatty acid esters Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Liquid Carbonaceous Fuels (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention provides a method which is used for quickly preparing biological diesel under a condition of low pressure by an alkali catalyst reinforced ultra-critical methanol method, belonging to the field of clean energy technique. The method is characterized in that the biological diesel is prepared by using a trace alkali catalyst reinforced ultra-critical methanol method, thus achieving the object of quickly preparing the biological diesel under the condition of low pressure. Transesterification is carried out for 10-30 minutes under the conditions of 160-260 DEG C of temperature, 1-6MPa of pressure, 0.01-0.25wt% of dosage of catalyst and 8:1-24:1 of molar ratio of methanol to oil; the conversion rate of methyl ester ranges from 90.1-99.8%. The method has the effects and benefits of retaining the outstanding advantages that the ultra-critical methanol method has short reaction time and high efficiency, the product requires no neutralization and water washing and the post-processing is simple, and overcoming the shortages that the ultra-critical methanol method has high reaction temperature and pressure, large dosage of methanol, etc. The dosage of the catalyst is only 1-25% of an alkali catalyst method, the reaction time can be greatly shorted, and the energy dissipation of production and requirement on the equipment are reduced.
Description
Technical field
The invention belongs to the clean energy technology field, relating to a kind of is the production method of biofuel with vegetables oil and methyl alcohol prepared in reaction fatty acid methyl ester.
Background technology
Biofuel is the long chain fatty acid ester class material (methyl esters) that obtains after natural fats and oils and low-carbon alcohol (methyl alcohol) transesterification reaction, and its performance is similar to petrifaction diesel, is a kind of eco-friendly clean fuel that can substitute the petrifaction diesel use.
The suitability for industrialized production biofuel mainly adopts chemical method and biological process at present.Biological process has advantages such as mild condition, less energy consumption, pure consumption are few, but lipase activity is subject to the inhibition of low-carbon alcohol and inactivation, and there are shortcomings such as speed of reaction is slow, cost height, still are in technical study and improve the stage, the successful example that does not have heavy industrialization to use so far.Chemical method comprises acid system, alkaline process and the two bonded two-step approach.Acid system can solve the problem that high-acid-value material is difficult to utilize, and prepares biofuel as selecting the high acid value Oleum Gossypii semen in the CN200610044926.6 application for patent for use, but whole process needs more than 10 hours, equipment anticorrosion requirement height; Alkaline process requires harsh to glyceride stock, by the alkali lye catalysis grease of potassium and the transesterification reaction of methyl alcohol, the reaction process complexity contains small-amount free lipid acid and water and will cause saponification reaction as ZL98811443.7.Although chemical method is in industrial widespread use, the difficult recovery of catalyzer, by-product glycerin are made with extra care difficulty, subsequent disposal produces problems such as a large amount of waste water but still exist.Cao Weiliang adopts solid acid-base to carry out the preparation of biofuel as catalyzer in the CN200410038292.4 application for patent, to solve the difficult recovery of catalyzer, product aftertreatment complicated problems, but because methyl alcohol is insoluble with grease, and the employing heterogeneous catalyst caused the longest needs of reaction times 15 hours.
In order to improve production of biodiesel efficient, propositions such as Japanese scholar Saka are equipped with method of bio-diesel oil with the supercritical methanol legal system.In this process, supercritical methanol can dissolve each other with grease, forms homogeneous phase, has significantly improved speed of reaction; And need not catalyzer, the product aftertreatment is simple.Saka etc. have carried out the overcritical transesterification reaction of rapeseed oil and methyl alcohol, react that methyl ester conversion rate is 95% after 4 minutes, but temperature and pressure is higher, is respectively 350 ℃ and 45MPa[Fuel, 80 (2001): 225～231].Wang Cunwen has also mentioned similar experimental result in the CN200410013430.3 application for patent, carry out but be reflected under 220～400 ℃, 8～25MPa, and to having relatively high expectations of equipment, industrialization has difficulties.
Summary of the invention
The objective of the invention is to be equipped with biofuel long reaction time, product aftertreatment complexity at the traditional chemical legal system, enzyme catalysis method cost height, the easy inactivation of enzyme, and shortcoming such as supercritical methanol method severe reaction conditions, provide a kind of and realize that with alkaline catalysts enhanced supercritical methyl alcohol method low pressure prepares the novel method of biofuel fast.
Preparation method of the present invention comprises the steps:
(1) mol ratio by methyl alcohol and vegetables oil is that 8:1～24:1 carries out weighing, the alkaline catalysts of 0.01～0.25wt% (in oil) is dissolved in the methyl alcohol, again methyl alcohol and vegetables oil are joined in the autoclave, controlled temperature is at 160～260 ℃, reaction pressure 1～6MPa, stirring reaction 10～30 minutes;
(2) product that after the reaction end (1) is obtained carries out underpressure distillation, removes excessive methyl alcohol; With the product standing demix, the upper strata is the biofuel phase again, and lower floor is the glycerine phase.Product is carried out gas chromatographic analysis, and methyl ester conversion rate is 90.1～99.8%.
Aforesaid vegetables oil is soybean oil, rapeseed oil, Oleum Helianthi;
Aforesaid alkaline catalysts is potassium hydroxide, sodium hydroxide, potassium methylate, sodium methylate.
It is short, less demanding to stock oil that effect of the inventive method and benefit are to have kept the supercritical methanol method reaction times, product aftertreatment characteristic of simple; Owing to introduce a spot of alkaline catalysts, improved the processing condition of supercritical methanol technology, make temperature of reaction and pressure significantly reduce, greatly reduce production energy consumption and to the requirement of equipment.
Embodiment
Be described in detail the specific embodiment of the present invention below in conjunction with technical scheme.
Embodiment 1
Take by weighing soybean oil 60g and methyl alcohol 52.4g, molar ratio of methanol to oil is about 24:1, alkaline catalysts KOH consumption 0.15g, i.e. 0.25wt% (in oil).After catalyzer is dissolved in methyl alcohol, mix with soybean oil again and add in the autoclave, be heated with stirring to 240 ℃, pick up counting, stopped reaction behind the reaction 20min, ice-water bath cooling reactor is to room temperature, excessive methanol is removed in underpressure distillation, with the product standing demix, the upper strata is the biofuel phase then, and lower floor is the glycerine phase.The upper strata product is carried out gas chromatographic analysis, and methyl ester conversion rate is 92.4%.
Embodiment 2
Take by weighing soybean oil 60g and methyl alcohol 52.4g, molar ratio of methanol to oil is about 24:1, alkaline catalysts KOH consumption 0.06g, i.e. 0.1wt% (in oil).After catalyzer is dissolved in methyl alcohol, mix with soybean oil again and add in the autoclave, be heated with stirring to 160 ℃, pick up counting, stopped reaction behind the reaction 20min, ice-water bath cooling reactor is to room temperature, excessive methanol is removed in underpressure distillation, with the product standing demix, the upper strata is the biofuel phase then, and lower floor is the glycerine phase.The upper strata product is carried out gas chromatographic analysis, and methyl ester conversion rate is 98.5%.
Embodiment 3
Take by weighing soybean oil 100g and methyl alcohol 43.6g, molar ratio of methanol to oil is about 12:1, alkaline catalysts KOH consumption 0.25g, i.e. 0.25wt% (in oil).After catalyzer is dissolved in methyl alcohol, mix with soybean oil again and add in the autoclave, be heated with stirring to 260 ℃, pick up counting, stopped reaction behind the reaction 30min, ice-water bath cooling reactor is to room temperature, excessive methanol is removed in underpressure distillation, with the product standing demix, the upper strata is the biofuel phase then, and lower floor is the glycerine phase.The upper strata product is carried out gas chromatographic analysis, and methyl ester conversion rate is 91.1%.
Embodiment 4
Take by weighing soybean oil 60g and methyl alcohol 52.4g, molar ratio of methanol to oil is about 24:1, alkaline catalysts NaOH consumption 0.03g, i.e. 0.05wt% (in oil).After catalyzer is dissolved in methyl alcohol, mix with soybean oil again and add in the autoclave, be heated with stirring to 260 ℃, pick up counting, stopped reaction behind the reaction 30min, ice-water bath cooling reactor is to room temperature, excessive methanol is removed in underpressure distillation, with the product standing demix, the upper strata is the biofuel phase then, and lower floor is the glycerine phase.The upper strata product is carried out gas chromatographic analysis, and methyl ester conversion rate is 90.1%.
Embodiment 5 (contrast experiment)
Take by weighing soybean oil 60g and methyl alcohol 52.4g, molar ratio of methanol to oil is about 24:1, mix the back and add in the autoclave (not adding catalyzer), be heated with stirring to 260 ℃, pick up counting, stopped reaction behind the reaction 30min, ice-water bath cooling reactor is to room temperature, and excessive methanol is removed in underpressure distillation, then with the product standing demix, the upper strata is the biofuel phase, and lower floor is the glycerine phase.The upper strata product is carried out gas chromatographic analysis, methyl ester conversion rate＜25%.
Embodiment 6
Take by weighing rapeseed oil 60g and methyl alcohol 52.4g, molar ratio of methanol to oil is about 24:1, alkaline catalysts NaOH consumption 0.06g, i.e. 0.1wt% (in oil).After catalyzer is dissolved in methyl alcohol, mix with rapeseed oil again and add in the autoclave, be heated with stirring to 160 ℃, pick up counting, stopped reaction behind the reaction 20min, ice-water bath cooling reactor is to room temperature, excessive methanol is removed in underpressure distillation, with the product standing demix, the upper strata is the biofuel phase then, and lower floor is the glycerine phase.The upper strata product is carried out gas chromatographic analysis, and methyl ester conversion rate is 96.5%.
Claims (4)
1. an alkaline catalysts enhanced supercritical methyl alcohol method realizes that low pressure prepares method of bio-diesel oil fast, it is characterized in that comprising the steps:
(1) mol ratio by methyl alcohol and vegetables oil is that 8:1～24:1 carries out weighing, the alkaline catalysts of 0.01～0.25wt% is dissolved in the methyl alcohol, methyl alcohol and vegetables oil is joined in the autoclave again, controlled temperature is at 160～260 ℃, reaction pressure 1～6MPa, stirring reaction 10～30 minutes;
(2) product that after the reaction end (1) is obtained carries out underpressure distillation, removes excessive methyl alcohol; With the product standing demix, the upper strata is the biofuel phase again, and lower floor is the glycerine phase; Product is carried out gas chromatographic analysis, and methyl ester conversion rate is 90.1～99.8%.
2. a kind of alkaline catalysts enhanced supercritical methyl alcohol method according to claim 1 realizes that low pressure prepares method of bio-diesel oil fast, it is characterized in that used vegetables oil is soybean oil, rapeseed oil, Oleum Helianthi, plam oil or Cortex jatrophae oil.
3. a kind of alkaline catalysts enhanced supercritical methyl alcohol method according to claim 1 realizes that low pressure prepares method of bio-diesel oil fast, it is characterized in that used alkaline catalysts is potassium hydroxide, sodium hydroxide, potassium methylate or sodium methylate.
4. a kind of alkaline catalysts enhanced supercritical methyl alcohol method according to claim 1 realizes that low pressure prepares method of bio-diesel oil fast, it is characterized in that the used transesterification reaction time is: when reacting liquid temperature reaches 160～260 ℃, pick up counting, reacted 10～30 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100132965A CN101362958A (en) | 2008-09-17 | 2008-09-17 | Method for quickly preparing biodiesel at low pressure by alkali catalyst-enhanced supercritical methanol method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100132965A CN101362958A (en) | 2008-09-17 | 2008-09-17 | Method for quickly preparing biodiesel at low pressure by alkali catalyst-enhanced supercritical methanol method |
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| CN101362958A true CN101362958A (en) | 2009-02-11 |
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| CNA2008100132965A Pending CN101362958A (en) | 2008-09-17 | 2008-09-17 | Method for quickly preparing biodiesel at low pressure by alkali catalyst-enhanced supercritical methanol method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101818102A (en) * | 2010-04-30 | 2010-09-01 | 大连理工大学 | Method for preparing biodiesel by catalytic intensification of supercritical methanol |
| CN102492561A (en) * | 2011-12-23 | 2012-06-13 | 吉林大学 | Method for preparing bio-diesel by using fresh rice bran |
| CN108219979A (en) * | 2016-12-22 | 2018-06-29 | 内蒙古中细软技术开发有限公司 | Supercritical extraction biodiesel synthesis |
| CN111334350A (en) * | 2020-03-19 | 2020-06-26 | 宜宾中通环保科技有限公司 | High-cleanness composite biodiesel and preparation method thereof |
-
2008
- 2008-09-17 CN CNA2008100132965A patent/CN101362958A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101818102A (en) * | 2010-04-30 | 2010-09-01 | 大连理工大学 | Method for preparing biodiesel by catalytic intensification of supercritical methanol |
| CN102492561A (en) * | 2011-12-23 | 2012-06-13 | 吉林大学 | Method for preparing bio-diesel by using fresh rice bran |
| CN108219979A (en) * | 2016-12-22 | 2018-06-29 | 内蒙古中细软技术开发有限公司 | Supercritical extraction biodiesel synthesis |
| CN111334350A (en) * | 2020-03-19 | 2020-06-26 | 宜宾中通环保科技有限公司 | High-cleanness composite biodiesel and preparation method thereof |
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Application publication date: 20090211 |