CN1858160A - Method for preparing biological diesel oil using nano solid acid or alkali catalyst - Google Patents

Method for preparing biological diesel oil using nano solid acid or alkali catalyst Download PDF

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CN1858160A
CN1858160A CNA2006100192454A CN200610019245A CN1858160A CN 1858160 A CN1858160 A CN 1858160A CN A2006100192454 A CNA2006100192454 A CN A2006100192454A CN 200610019245 A CN200610019245 A CN 200610019245A CN 1858160 A CN1858160 A CN 1858160A
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nano
solid acid
diesel oil
nano solid
bio
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CN100503786C (en
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黄凤洪
郭萍梅
黄庆德
李文林
黄沁洁
杨湄
夏伏建
王江薇
钮琰星
刘昌盛
程小英
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Oil Crops Research Institute of Chinese Academy of Agriculture Sciences
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Oil Crops Research Institute of Chinese Academy of Agriculture Sciences
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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
    • 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

The present invention relates to process of preparing low carbon alkyl ester and biological diesel oil by means of nanometer solid acid or alkali catalyst. Under the action of catalyst in the amount of 1-20 wt% of animal and vegetable oil, low carbon alcohol and animal and vegetable oil in the molar ratio of 3.5-40 to 1 are reacted at the pressure from normal to 25 MPa and temperature of 40-100 deg.c to produce coarse methyl ester and glycerin, which are centrifugally separated and distilled to obtain low carbon alcohol, or neutral biological diesel oil and glycerin, separately. The present invention has biological diesel oil converting rate up to 96% and yield up to 99%, and the product meets the ASTM D 6751-02 standard. The nanometer solid acid or alkali catalyst may be used repeatedly for 3-100 times in producing biological diesel oil, and the product needs no neutralization and washing.

Description

Adopt nano solid acid or base catalysis to prepare method of bio-diesel oil
Technical field
The present invention relates to a kind ofly prepare lipid acid low-carbon alkyl---method of bio-diesel oil, belong to oil chemistry and Application in Chemical Engineering field with nanoscale solids acid or base catalysis.
Background technology
Biofuel is a kind of green regenerative energy sources, can be used as fine petrifaction diesel substitute.It is to be raw material with animal oil, vegetables oil, discarded edible wet goods, and (carbonatoms 1-4) carries out transesterification reaction under certain condition with low-carbon alcohol, and the product that obtains is biofuel (lipid acid low-carbon alkyl), and byproduct is a glycerine.What traditional homogeneous catalyst adopted usually is the liquid soda acid, mainly contain the vitriol oil, NaOH, KOH etc., the remarkable defective that these liquid catalysts exist is in the product needed of reaction back and washing, cause environmental pollution, byproduct glycerine is mutually impure more, is difficult for purifying, and catalyzer can not reclaim repeatedly and use.
Therefore, the research report of solid catalysis conversion biodiesel is more and more, at Chinese oil [.2004,29 (12) 68～70] in " tin tetrachloride is to high-acid value grease catalyzing esterification experimental study of effect " literary composition that Guo Ping plum etc. is delivered in, the esterification yield of tin tetrachloride that uses reaches more than 97%, but use properties is relatively poor repeatedly.In disclosed patented technology, as described in CN1580190A, CN1664072A, adopt common solid acid, base catalysis to prepare method of bio-diesel oil, can simplify technology, avoid pollution, but use properties is the problem that needs consideration repeatedly environment.Therefore, press for exploitation catalytic activity height, use properties is good repeatedly solid catalyst prepares biofuel.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that exists at above-mentioned prior art and provide a kind of and prepare method of bio-diesel oil with nano solid acid or base catalysis, and it has active high, the good characteristics of use properties repeatedly of catalyst.
The present invention is that to address the above problem the technical scheme that is adopted as follows: adopt nano solid acid or alkaline catalysts, the catalyzer add-on is 1～20% of a vegetable and animals oils weight, low-carbon alcohol and vegetable and animals oils mol ratio are 3.5～40: 1, the heated and stirred reaction, the pressure of retort: normal pressure～25Mp, temperature: 40-100 ℃, the centrifugation of reaction back goes out thick methyl esters and glycerine mutually, thick methyl esters is distilled out low-carbon alcohol respectively mutually with glycerine, promptly obtain neutral biofuel and glycerine.
Press such scheme, described nano solid acid or alkaline catalysts are to adopt preparation method of nano material such as vacuum condensation method, mechanical ball milling method, sol-gel method, original position method of formation, chemical precipitation method, hydrothermal synthesis method to be prepared from.Recyclable recirculation is again used after the centrifugation.
Described nano solid acid catalyst comprises: nano level oxide compound and composite oxides Al 2O 3, SiO 2, TiO 2, Al 2O 3-SiO 2, TiO 2-SiO 2Deng; Nano solid supper corrosive acid: ZrSO 4, ZrO 2/ SiO 2, SO 4 2-/ TiO 2, SO 4 2-/ Al 2O 3, SO 4 2-/ ZrO 2, SO 4 2-/ Fe 2O 3, SO 4 2-(S 2O 8 2-)/CoFe 2O 4, SO 4 2-/ ZrO 2-Fe 3O 4, SO 4 2-/ ZnFe 2O 4Deng; Nano-scale rare earth solid super-strong acid: SO 4 2-/ ZrO 2/ Ce 4+, SO 4 2-/ ZrO 2-CeO 2, SO 4 2-/ TiO 2/ La 3+, SO 4 2-/ Ti-La-O, SO 4 2-/ Fe 2O 3-Dy 2O 3Deng.Wherein, SO particularly 4 2-/ TiO 2, SO 4 2-/ Al 2O 3, ZrO 2/ SiO 2, TiO 2-SiO 2Show fabulous catalytic activity.
Described nano solid base catalyst is: nano level inorganic chemical ZnO, MgO, CaO, SrO and BaO, nano hydrotalcite (MgAl (O)/MgFe 2O 4) and houghite; Nano level mixture Mg-Al, MgO-NaOH, MgO-Na etc.; Nanometer level RE oxide La 2O 3, Y 2O 3, Nd 2O 3, Ce 2O 3Carrier or loaded article (metal oxide) are the loaded nano solid alkali of nanoparticle, as at nano level Al 2O 3, SiO 2, TiO 2Deng flooding K on the carrier 2CO 3Or KHCO 3, NaOH, KOH etc., perhaps metal oxide supported on various carriers with above-mentioned nanoparticle.Wherein, nano hydrotalcite (MgAl (O)/MgFe particularly 2O 4), K +/ Al 2O 3, K +/ SiO 2, K +/ gac shows fabulous catalytic activity.
Described vegetable and animals oils is animal oil and/or vegetables oil, comprises lard, butter, sheep oil, rapeseed oil, soybean oil, sesame oil, peanut oil, plam oil, discarded edible oil; Described low-carbon alcohol is methyl alcohol, ethanol, propyl alcohol, butanols, or both mixing arbitrarily, and the recyclable recirculation of the unnecessary low-carbon alcohol that distills out after the reaction is used.
Press such scheme, the transesterification reaction catalysis time after adding catalyzer and the low-carbon alcohol is 0.1～10 hour.
The invention has the beneficial effects as follows:
1, adopt nano solid acid or alkaline catalysts catalysis animal-plant oil transesterification reaction, the biofuel transformation efficiency reaches more than 96%, and yield is more than 99%, and technical target of the product meets ASTM D 6751-02 standard.
2, compare with common solid catalyst, adopt the usability repeatedly of nano solid acid or alkaline catalysts to be greatly enhanced,, can use 3～100 artifact diesel oil transformation efficiencys repeatedly still about 96% without any activation treatment.
3, adopt nano solid acid or the alkali catalyst for ester exchange reaction as vegetable and animals oils and low-carbon alcohol, the product that obtains does not need the neutralization washing to wait aftertreatment, without sewage discharge.Solved traditional liquid phase acid or liquid phase alkaline catalysts and prepared in the biofuel, problems such as the corrodibility to equipment, the aftertreatment of existence is loaded down with trivial details, the difficult purification of byproduct glycerine.
At catalytic field, nano catalytic material presents fabulous catalytic activity, and nano material is meant that microstructures such as crystal grain and crystal boundary can both reach the material of nano level yardstick, and the nanoparticle particle diameter is generally between 1～100nm.Its surface atom number increases considerably along with the minimizing of nano-particles size with the ratio of total atom number, particle surface energy and surface tension are also along with increase, the serious mismatch of huge specific surface area and key attitude, many active centre occur, thereby show much better than chemical catalysis activity than common catalytic material.
Description of drawings
Fig. 1 is the workflow block diagram of one embodiment of the invention.
Embodiment
Further specify embodiments of the invention below in conjunction with accompanying drawing.
Embodiment 1:
Raw material: cold rolling vegetable seed crude oil, methyl alcohol, nano hydrotalcite (MgAl (O)/MgFe 2O 4);
By weight cold rolling vegetable seed crude oil of 200g and 60g methyl alcohol are added in three mouthfuls of round-bottomed flasks of 500ml, place the electrically heated constant temperature sleeve, stir, add 5g nano hydrotalcite (MgAl (O)/MgFe again 2O 4), being heated to 70 ℃, the methanol eddy stirring reaction stopped heated and stirred after 5 hours.Then reactant is poured in the Centrifuge Cup, centrifugal thick methyl esters and the raw glycerine told, the decompression rotary distillation removes methyl alcohol and obtains the 198.67g biofuel, yield 99.34%, obtain glycerine 19.87g, adopt GB/T 13216.6-91 to record glycerol content 98%, theoretical glycerine output is 20g, and promptly the biofuel transformation efficiency is more than 97.36%.Fatty acid methyl ester absolute content in the biofuel product that the employing gas Chromatographic Determination obtains, measurement result is approaching with the biofuel transformation efficiency that obtains with the glycerol content evaluation, is 97.11%.
According to technical process in the accompanying drawing nano hydrotalcite is used 8 times repeatedly without any activation treatment, estimate the biofuel transformation efficiency with the glycerine yield, its catalytic activity is still more than 96% after 8 times.The result is as follows.
The number of occurrence 1 time 2 times 3 times 4 times 5 times 6 times 7 times 8 times
Transformation efficiency (%) 97.36 96.41 96.21 96.33 96.15 96.12 96.15 96.08
Compare with USS ASTM D 6751-02, measuring method is all measured according to the requirement on the ASTM D 6751.
Sequence number Index name U.S. ASTM6751 standard ※ The product measured value
1 Flash-point (method of remaining silent), ℃ 130(Min) 176
2 Moisture and impurity, % 0.05(Max) 0.042
3 Kinetic viscosity (40 ℃), mm 2/s 1.9~6.0 4.1
4 Sulphated ash (weight), % 0.02(Max) /
5 Sulphur content (weight), % 0.05(Max) 0.01
6 Cetane value 47(Min) 48
7 Acid value, mmKOH/g 0.8(Max) 0.75
8 Free glycerol, % 0.02(Max) 0.015
9 Total glycerine, % 0.24(Max) 0.234
10 Phosphorus content, % 0.001(Max) 0.001
11 90% steams temperature, ℃ 360(Max) 351
From measurement result as can be seen, the biofuel product index that obtains all reaches ASTM D 6751-02 standard.
Embodiment 2:
Raw material: the soybean oil of coming unstuck, methyl alcohol, K +/ nanometer Al 2O 3, K +/ common Al 2O 3
By weight 200g is come unstuck in three mouthfuls of round-bottomed flasks of soybean oil and 60g methyl alcohol adding 500ml, place the electrically heated constant temperature sleeve, stir, add 5g nano-solid catalyzer: K again +/ nanometer Al2O3 is heated to 70 ℃, and the methanol eddy stirring reaction stopped heated and stirred after 5 hours.Then reactant is poured in the Centrifuge Cup, centrifugal thick methyl esters and the raw glycerine told, the decompression rotary distillation removes methyl alcohol and obtains the 199.50g biofuel, yield 99.75%, obtain glycerine 19.69g, adopt GB/T 13216.6-91 to record glycerol content 97.98%, theoretical glycerine output is 20g, and promptly the biofuel transformation efficiency 96.46%.Adopt fatty acid methyl ester absolute content in the gas Chromatographic Determination biofuel product, measurement result is approaching with the biofuel transformation efficiency that obtains with the glycerol content evaluation, is 96.05%.
Catalyzer K +/ nanometer Al 2O 3After using 10 times repeatedly, obtain the biofuel conversion rate of products still about 96%.
Every determination of quality index reaches ASTM D 6751-02 standard after measured with embodiment 1.
Under identical reaction conditions, with K +/ common Al 2O 3Be catalyzer, one time transformation efficiency reaches 96.68%, but obviously descending appears in transformation efficiency after using 2 times repeatedly, is about 89%.
Embodiment 3:
The discarded edible oil of raw material: acid value 24mgKOH/g, methyl alcohol, nano solid supper corrosive acid: ZrO 2/ SiO 2, common solid super-strong acid: ZrO 2/ SiO 2
The discarded edible oil that to collect by weight earlier through sedimentation, filter and obtain foreign matter content less than 0.1% raw oil material, measure its acid value, be 24mgKOH/g.In three mouthfuls of round-bottomed flasks of 500ml, add discarded edible oil and the 60g methyl alcohol that 200g handles well, stir, add 5g nano solid supper corrosive acid: ZrO again 2/ SiO 2Be heated to the methanol eddy temperature, stirring reaction stopped heated and stirred after 5 hours, pour out the reactant centrifugation, the thick methyl esters and the raw glycerine that obtain are removed methyl alcohol, obtain biofuel product 199.86g, yield 99.93%, byproduct glycerine 19.81g, glycerol content 97.08%, biofuel transformation efficiency 96.16%.Methyl esters absolute content 96.09% in the gas Chromatographic Determination biofuel product.
Nano solid supper corrosive acid ZrO 2/ SiO 2After using 9 times repeatedly, the biofuel conversion rate of products is still about 96%.Every quality index evaluation all reaches ASTM D 6751 standards with embodiment 1.
Under the same terms typical catalyst is tested repeatedly, the result shows and is using the 3rd artifact diesel oil transformation efficiency to drop to 90% repeatedly.
Embodiment 4:
Raw material: lard, methyl alcohol, nanometer K +/ gac, common K +/ gac
By weight 200g lard and 60g methyl alcohol are added in three mouthfuls of round-bottomed flasks of 500ml, add 5g nanometer K while stirring +/ gac, being heated to the methanol eddy temperature picks up counting, react and stop heated and stirred after 5 hours, pour out the reactant centrifugation, the thick methyl esters and the raw glycerine that obtain are removed methyl alcohol, obtain biofuel product 198.95g, yield 99.48%, byproduct glycerine 19.79g, glycerol content 97.19%, biofuel transformation efficiency 96.17%.Methyl esters absolute content 96.04% in the gas Chromatographic Determination biofuel product.
Nanometer K +After/gac used 8 times repeatedly, the biofuel conversion rate of products was still about 96%.Every quality index evaluation all reaches ASTM D 6751 standards with embodiment 1.
Under the same terms to common K +/ gac is tested repeatedly, and the result shows and using the 3rd artifact diesel oil transformation efficiency to drop to 89% repeatedly.

Claims (9)

1. one kind is adopted nano solid acid or base catalysis to prepare method of bio-diesel oil, it is characterized in that adopting nano solid acid or alkaline catalysts, the catalyzer add-on is 1～20% of a vegetable and animals oils weight, low-carbon alcohol and vegetable and animals oils mol ratio are 3.5～40: 1, heated and stirred reaction, the pressure of retort: normal pressure～25Mp, temperature: 40-100 ℃, the centrifugation of reaction back goes out thick methyl esters and glycerine mutually, and thick methyl esters is distilled out low-carbon alcohol respectively mutually with glycerine, promptly obtains neutral biofuel and glycerine.
2. employing nano solid acid according to claim 1 or base catalysis prepare method of bio-diesel oil, it is characterized in that described nano solid acid or alkaline catalysts are to adopt preparation method of nano material such as vacuum condensation method, mechanical ball milling method, sol-gel method, original position method of formation, chemical precipitation method, hydrothermal synthesis method to be prepared from.
3. employing nano solid acid according to claim 1 and 2 or base catalysis prepare method of bio-diesel oil, it is characterized in that described nano solid acid or alkaline catalysts are the materials that crystal grain and crystal boundary microstructure can both reach the nano level yardstick, the nanoparticle particle diameter is between 1～100nm.
4. employing nano solid acid according to claim 1 and 2 or base catalysis prepare method of bio-diesel oil, it is characterized in that described nano solid acid catalyst comprises: nano level oxide compound and composite oxides Al 2O 3, SiO 2, TiO 2, Al 2O 3-SiO 2, TiO 2-SiO 2Nano solid supper corrosive acid: ZrSO 4, ZrO 2/ SiO 2, SO 4 2-/ TiO 2, SO 4 2-/ Al 2O 3, SO 4 2-/ ZrO 2, SO 4 2-/ Fe 2O 3, SO4 2-(S 2O 8 2-)/CoFe 2O 4, SO 4 2-/ ZrO 2-Fe 3O 4, SO 4 2-/ ZnFe 2O 4Nano-scale rare earth solid super-strong acid: SO 4 2-/ ZrO 2/ Ce 4+, SO 4 2-/ ZrO 2-CeO 2, SO 4 2-/ TiO 2/ La 3+, SO 4 2-/ Ti-La-O, SO 4 2-/ Fe 2O 3-Dy 2O 3
5. employing nano solid acid according to claim 1 and 2 or base catalysis prepare method of bio-diesel oil, it is characterized in that described nano solid base catalyst is: nano level inorganic chemical ZnO, MgO, CaO, SrO and BaO, nano hydrotalcite (MgAl (O)/MgFe 2O 4) and houghite; Nano level mixture Mg-Al, MgO-NaOH, MgO-Na; Nanometer level RE oxide La 2O 3, Y 2O 3, Nd 2O 3, Ce 2O 3Carrier or loaded article (metal oxide) are the loaded nano solid alkali of nanoparticle.
6. employing nano solid acid according to claim 1 and 2 or base catalysis prepare method of bio-diesel oil, it is characterized in that described vegetable and animals oils is animal oil and/or vegetables oil.
7. employing nano solid acid according to claim 1 and 2 or base catalysis prepare method of bio-diesel oil, it is characterized in that described low-carbon alcohol is methyl alcohol, ethanol, propyl alcohol, butanols, or both mixing arbitrarily, the low-carbon alcohol that steams recycling use again.
8. employing nano solid acid according to claim 1 and 2 or base catalysis prepare method of bio-diesel oil, and the transesterification reaction catalysis time that it is characterized in that adding after catalyzer and the low-carbon alcohol is 0.1～10 hour.。
9. employing nano solid acid according to claim 1 and 2 or base catalysis prepare method of bio-diesel oil, and nano solid acid after the centrifugation or alkaline catalysts reclaim recirculation again and use.
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WO2009046636A1 (en) * 2007-09-29 2009-04-16 Huazhong Agricultural University Method for producing biodiesel using solid acid-base bifunctional catalyst
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US7897798B2 (en) 2006-08-04 2011-03-01 Mcneff Research Consultants, Inc. Methods and apparatus for producing alkyl esters from lipid feed stocks and systems including same
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US7943791B2 (en) 2007-09-28 2011-05-17 Mcneff Research Consultants, Inc. Methods and compositions for refining lipid feed stocks
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