CN101402875A - Process for producing biological diesel oil - Google Patents
Process for producing biological diesel oil Download PDFInfo
- Publication number
- CN101402875A CN101402875A CNA2008101945506A CN200810194550A CN101402875A CN 101402875 A CN101402875 A CN 101402875A CN A2008101945506 A CNA2008101945506 A CN A2008101945506A CN 200810194550 A CN200810194550 A CN 200810194550A CN 101402875 A CN101402875 A CN 101402875A
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- CN
- China
- Prior art keywords
- molecular sieve
- mcm
- oil
- mesoporous molecular
- 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
-
- 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 invention discloses a preparation method of biodiesel, pertaining to the technical field of chemical synthesis of biodiesel. Soybean oil or rap oil or wild plant oil or animal oil is used as a material, an MCM-41 type mesoporous molecular sieve is doped as a catalyst and sodium hydroxide or potassium hydroxide is used as a co-catalyst for preparing the biodiesel; metal Co or Cu or Fe or Ni is doped into the MCM-41 type mesoporous molecular sieve. The method has the advantages of high MCM-41 specific surface and uniform pore diameter; moreover, the pore diameter is larger than that of a pure silicon molecular sieve, thus being beneficial to the dispersion of organic matters. The doped MCM-41 type mesoporous molecular sieve can also effectively prevent the fasculation of glycerin; the mesoporous molecular sieve can be used as the catalyst for preparing the biodiesel by using an ester exchange method; the mesoporous molecular sieve can be used together with sodium hydroxide or potassium hydroxide as the catalyst; the dosage of the sodium hydroxide or potassium hydroxide is less; the conversion rate of the biodiesel is high; and the pH value of the obtained product approaches the neutral.
Description
Technical field
The present invention relates to a kind of technical field of chemosynthetic organism diesel oil.
Background technology
Along with the global energy demand constantly increases, the rising of crude oil price and petroleum resources exhausted day by day, developing the new diesel oil energy becomes the subject matter that various countries face at present.Biofuel is because its superior environmental-protecting performance has received the concern of countries in the world.The preparation method of biofuel has multiple, mainly be to produce at present with chemical method, promptly under acidity or basic catalyst effect, carry out transesterification reaction, generate corresponding lipid acid short chain alcohol ester, through alkali or pickling, under water, can obtain biofuel after the drying with vegetable and animals oils and short chain alcohol.Produce a large amount of sewage in the production process, product per ton produces about 20 tons of sewage.
The doping type mesopore molecular sieve had both kept MCM-41 mesopore molecular sieve high-specific surface area, the uniform characteristics in aperture, had improved activity of such catalysts again, thereby had obtained widespread use.Chinese patent CN1821195A utilizes CTAB to be template, and tetraethoxy is the silicon source, and Xiao Suangu is doping precursor synthetic Co-MCM-41 under alkaline condition, with its catalyzer as synthetic verbenol of α-Pai Xi and verbenone.Chinese patent CN 101148396A mixes stirring with tetraethoxy with CTAB, water, sodium hydroxide and Cobaltous diacetate, through 90 ℃ of hydro-thermal reaction 168h, and 100 dry 12h, roasting gets Co-MCM-41, is used for the preparation of cycloalkanol and naphthenone.U.S. Pat 7357983B2 with organosilicon source and rose vitriol respectively with the alkyl ammonia effect of different chain length, be about at pH that synthetic Co-MCM-41 is used to prepare Single Walled Carbon Nanotube under 11 the condition.High chemical journal, 2000,21 (9), 1451～1454 have described organosilicon source, CTAB and CuCl
2Under the ammoniacal liquor existence condition, be mixed with the process of Cu-MCM-41.Catalysis Today with organosilicon source and palmityl trimethyl ammonium chloride effect, makes Cu-MCM-41 to the spirituous solution that wherein adds cupric nitrate and neutralized verdigris in 2002 (75), 189～195.Above-mentioned Cu-MCM-41 all is used for the hydroxylating of phenol.The catalysis journal, 2006,27 (5), 372～374 is template with CTAB, water glass is the silicon source, [Cu (NH
3)
4] Cl
2Be the doping precursor, under the environment of sulfuric acid adjusting pH to 11, synthesized Cu-MCM-41, be used as the catalyzer of diesel oil adsorption desulfurizing.Chinese patent CN 10113873A loads on alkali-metal weakly alkaline or neutral compound (among Li, Na, K or the Rb a kind of) on the MCM-41 mesopore molecular sieve, and this kind molecular sieve type solid alkali catalyst is used to prepare biofuel.
The contriver mixes to MCM-41 respectively with transition metal such as Co, Cu, Fe, Ni, has prepared the adulterated mesopore molecular sieve of different metal.
Summary of the invention
The purpose of this invention is to provide the employing doping MCM-41 type mesoporous molecular sieve is catalyzer, a kind of method of preparation biofuel.
The present invention is a raw material with soybean oil or rapeseed oil or wild plant oil or animal oil, is catalyzer with the doping MCM-41 type mesoporous molecular sieve, is synergistic catalyst with sodium hydroxide or potassium hydroxide, the preparation biofuel; Adulterated metal Co or Cu or Fe or Ni in the described doping MCM-41 type mesoporous molecular sieve.
Wherein, the doping MCM-41 type mesoporous molecular sieve consumption is 0.2～1.0wt% of oil plant, and sodium hydroxide or potassium hydroxide consumption are 0.05～0.3wt% of oil plant.
Among the present invention, the doping MCM-41 type mesoporous molecular sieve that provides is the skeleton that enters mesopore molecular sieve with metal-doped, can not destroy the structure of mesopore molecular sieve, advantage with MCM-41 high-specific surface area, uniform pore size, and the aperture is big than the pure silicon molecular sieve, helps the characteristics of organic diffusion.Doping MCM-41 type mesoporous molecular sieve can also effectively prevent the polycondensation of glycerine, the catalyzer that this mesopore molecular sieve be can be used as preparing biodiesel by ester interchange, with sodium hydroxide or potassium hydroxide jointly as catalyzer, sodium hydroxide or potassium hydroxide consumption are few, the transformation efficiency height of biofuel, the pH value of products obtained therefrom is near neutral.
Embodiment
One, preparation doping MCM-41 type mesoporous molecular sieve processing step:
1, with Na
2SiO
39H
2The aqueous solution of O mixes stirring 5～120min at ambient temperature with the aqueous solution of CTAB; Wherein, silicon source and CTAB mol ratio are 0.5～8: 1.
2, use 1molL
-1H
2SO
4Regulating step 1) mixing solutions of gained is to neutrality, stirring at room 5～60min.
3, to step 2) the adulterated metallic compound aqueous solution of gained mixed solution dropping desire, stirring at room 5～60min.
Metallic compound is nitrate or the chlorate of Co or Cu or Fe or Ni.
The mol ratio of silicon and doping metals is 2～100: 1.
4, with volumetric molar concentration be 25%～28% ammoniacal liquor regulating step 3 gained mixed solutions to pH=8～11, continue stirring at room 30～120min;
5, with step 4 products therefrom as for 80～160 ℃ of crystallization 24～96h in the autoclave of inner liner polytetrafluoroethylene.
6, with step 5 products therefrom after filtration, washing, alcohol wash, as for drying naturally under the room temperature condition.
7, with step 6 products therefrom temperature programming to 550 ℃ insulation 5h, get doping MCM-41 type mesoporous molecular sieve.
Two, specific embodiment:
Embodiment 1:
The preparation of doping type mesopore molecular sieve:
The 5.7g water glass is dissolved in the 34g water, to the CTAB aqueous solution that wherein adds 8g 23.5wt%, stirring at room 30min; Use 1molL
-1H
2SO
4Regulate pH value to 7, stirring at room 15min; Co (the NO that in this mixed solution, adds 15g 1.2wt%
3)
26H
2The O aqueous solution, stirring at room 15min; Ammoniacal liquor with 25～28% is regulated pH value to 9.5, continues stirring at room 2h; Reaction solution is placed the autoclave of teflon lined, and 120 ℃ of crystallization 72h, product wash 3 times, room temperature through suction filtration, washing 10 times, alcohol and dry temperature programming to 550 ℃ insulation 5h.Get the Co-MCM-41 of Si: Co=20.
The preparation of biofuel:
80g soybean oil and 20g methyl alcohol are put into the reactor of 500ml, stir,, be heated to 85 ℃, behind the reaction 2h, stop to stir and heating to wherein adding 0.5g Co-MCM-41 and 0.2g NaOH.Reaction solution is standing demix after filtering, and lower floor is a glycerine, and the upper strata obtains biofuel by distillation for removing methanol.Reaction conversion ratio reaches 95.0%.
80g rapeseed oil and 20g methyl alcohol are put into the reactor of 500ml, stir,, be heated to 85 ℃, behind the reaction 2h, stop to stir and heating to wherein adding 0.4g Co-MCM-41 and 0.1g KOH.Reaction solution is standing demix after filtering, and lower floor is a glycerine, and the upper strata obtains biofuel by distillation for removing methanol.Reaction conversion ratio reaches 96.4%.
Embodiment 2:
The preparation of doping type mesopore molecular sieve
The 5.7g water glass is dissolved in the 34g water, to the CTAB aqueous solution that wherein adds 8g 23.5wt%, stirring at room 30min; Use 1molL
-1H
2SO
4Regulate pH value to 7, stirring at room 15min; Cu (the NO that in this mixed solution, adds 15g 1.25wt%
3)
23H
2The O aqueous solution, stirring at room 15min; Ammoniacal liquor with 25～28% is regulated pH value to 9.5, continues stirring at room 2h; Reaction solution is placed the autoclave of teflon lined, and 120 ℃ of crystallization 72h, product wash 3 times, room temperature through suction filtration, washing 10 times, alcohol and dry temperature programming to 550 ℃ insulation 5h.Get the Cu-MCM-41 of Si: Cu=20.
The preparation of biofuel
80g soybean oil and 20g methyl alcohol are put into the reactor of 500ml, stir,, be heated to 85 ℃, behind the reaction 2h, stop to stir and heating to wherein adding 0.3g Cu-MCM-41 and 0.2gKOH.Reaction solution is standing demix after filtering, and lower floor is a glycerine, and the upper strata obtains biofuel by distillation for removing methanol.Reaction conversion ratio reaches 82.5%.
Embodiment 3:
The preparation of doping type mesopore molecular sieve
The 5.7g water glass is dissolved in the 34g water, to the CTAB aqueous solution that wherein adds 8g 23.5wt%, stirring at room 30min; Use 1molL
-1H
2SO
4Regulate pH value to 7, stirring at room 15min; The FeCl that in this mixed solution, adds 15g 1.1wt%
36H
2The O aqueous solution, stirring at room 15min; Ammoniacal liquor with 25～28% is regulated pH value to 9.5, continues stirring at room 2h; Reaction solution is placed the autoclave of teflon lined, and 120 ℃ of crystallization 72h, product wash 3 times, room temperature through suction filtration, washing 10 times, alcohol and dry temperature programming to 550 ℃ insulation 5h.Get the Fe-MCM-41 of Si: Fe=20.
The preparation of biofuel
80g soybean oil and 20g methyl alcohol are put into the reactor of 500ml, stir,, be heated to 85 ℃, behind the reaction 2h, stop to stir and heating to wherein adding 0.5g Fe-MCM-41 and 0.2gNaOH.Reaction solution is standing demix after filtering, and lower floor is a glycerine, and the upper strata obtains biofuel by distillation for removing methanol.Reaction conversion ratio reaches 94.6%.
In above preparation biofuel, soybean oil can use rapeseed oil, wild plant oil or animal oil to substitute.
Claims (2)
1, a kind of preparation method of biofuel is characterized in that with soybean oil or rapeseed oil or wild plant oil or animal oil be raw material, is catalyzer with the doping MCM-41 type mesoporous molecular sieve, is synergistic catalyst with sodium hydroxide or potassium hydroxide, the preparation biofuel; Adulterated metal Co or Cu or Fe or Ni in the described doping MCM-41 type mesoporous molecular sieve.
2, according to the preparation method of the described biofuel of claim 1, it is characterized in that the doping MCM-41 type mesoporous molecular sieve consumption is 0.2～1.0wt% of oil plant, sodium hydroxide or potassium hydroxide consumption are 0.05～0.3wt% of oil plant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101945506A CN101402875A (en) | 2008-10-29 | 2008-10-29 | Process for producing biological diesel oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101945506A CN101402875A (en) | 2008-10-29 | 2008-10-29 | Process for producing biological diesel oil |
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| Publication Number | Publication Date |
|---|---|
| CN101402875A true CN101402875A (en) | 2009-04-08 |
Family
ID=40537045
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|---|---|---|---|
| CNA2008101945506A Pending CN101402875A (en) | 2008-10-29 | 2008-10-29 | Process for producing biological diesel oil |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112403464A (en) * | 2020-11-20 | 2021-02-26 | 王立鹏 | Modified gasified slag biodiesel catalyst and preparation method and application thereof |
-
2008
- 2008-10-29 CN CNA2008101945506A patent/CN101402875A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112403464A (en) * | 2020-11-20 | 2021-02-26 | 王立鹏 | Modified gasified slag biodiesel catalyst and preparation method and application thereof |
| CN112403464B (en) * | 2020-11-20 | 2023-08-11 | 江苏海洋大学 | Modified gasification slag biodiesel catalyst and preparation method and application thereof |
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Open date: 20090408 |