CN1896182A - Production of biological diesel oil with solid alkali - Google Patents
Production of biological diesel oil with solid alkali Download PDFInfo
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- CN1896182A CN1896182A CNA2005100121948A CN200510012194A CN1896182A CN 1896182 A CN1896182 A CN 1896182A CN A2005100121948 A CNA2005100121948 A CN A2005100121948A CN 200510012194 A CN200510012194 A CN 200510012194A CN 1896182 A CN1896182 A CN 1896182A
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- solid base
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- 239000007787 solid Substances 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 239000002283 diesel fuel Substances 0.000 title abstract description 4
- 239000003513 alkali Substances 0.000 title description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 239000012535 impurity Substances 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 84
- 238000003756 stirring Methods 0.000 claims description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000003921 oil Substances 0.000 claims description 44
- 235000019198 oils Nutrition 0.000 claims description 44
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 41
- 238000005119 centrifugation Methods 0.000 claims description 36
- 239000002551 biofuel Substances 0.000 claims description 34
- 239000003225 biodiesel Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 24
- 238000001556 precipitation Methods 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 235000011187 glycerol Nutrition 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 13
- 235000013311 vegetables Nutrition 0.000 claims description 12
- 238000005189 flocculation Methods 0.000 claims description 11
- 230000016615 flocculation Effects 0.000 claims description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 235000012424 soybean oil Nutrition 0.000 claims description 7
- 239000003549 soybean oil Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052728 basic metal Inorganic materials 0.000 claims description 6
- 150000003818 basic metals Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 206010024229 Leprosy Diseases 0.000 claims description 5
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 5
- 235000013399 edible fruits Nutrition 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 210000000582 semen Anatomy 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 3
- 244000247747 Coptis groenlandica Species 0.000 claims description 3
- 235000002991 Coptis groenlandica Nutrition 0.000 claims description 3
- 244000248162 Xanthoceras sorbifolium Species 0.000 claims description 3
- 235000009240 Xanthoceras sorbifolium Nutrition 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 235000020238 sunflower seed Nutrition 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- 241000218196 Persea Species 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229920000591 gum Polymers 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 125000003473 lipid group Chemical group 0.000 abstract 1
- 235000015112 vegetable and seed oil Nutrition 0.000 abstract 1
- 239000008158 vegetable oil Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 39
- 239000006228 supernatant Substances 0.000 description 24
- 238000001035 drying Methods 0.000 description 17
- 238000010792 warming Methods 0.000 description 17
- 239000002585 base Substances 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 12
- 235000015165 citric acid Nutrition 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- -1 fatty acid ester Chemical class 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical class O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 description 3
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical class O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910001864 baryta Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical class [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000004032 superbase Substances 0.000 description 1
- 150000007525 superbases Chemical class 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
- Fats And Perfumes (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
Production of biological diesel oil by solid base is carried out by taking solid base as catalyst, and lipid exchange reacting for short-chain aliphatic alcohol and vegetable oil at suitable temperature and removing impurities of crude biological diesel oil to obtain the final product. The catalyst is re-useable and combined precipitant with flocculant It is simple and efficient, has gentle reactive condition and no environmental pollution.
Description
Technical field
The present invention relates to a kind of technology of utilizing solid alkali to prepare biofuel, relate in particular to a kind of a kind of heterogeneous catalyst technology of in the transesterification reaction of preparation biofuel, using.
Background technology
Biofuel mainly is to adopt chemical reaction method at present, produce by transesterification reaction, promptly under acidity or basic catalyst and certain temperature, carry out transesterification reaction, generate corresponding Fatty acid methyl ester or second fat with animal-plant oil and methyl alcohol or ethanol, through washing drying, promptly get biofuel again; Simultaneously, obtain by-product glycerin, the Technology of chemical method production biofuel reaches its maturity.
The acid-catalyzed transesterification process is general uses bronsted acid to carry out catalysis.Catalyzer commonly used has the vitriol oil, Phenylsulfonic acid and phosphoric acid etc.Vitriol oil low price, aboundresources, its main problem is: speed of reaction is too slow, long reaction time, the temperature height, and follow side reactions such as sulfonation, sulfation; To the serious corrosion of equipment, and use a large amount of methyl alcohol, make the recovery difficulty of glycerine, thereby this catalyzer is eliminated progressively.
Sodium hydroxide and potassium hydroxide are the catalyzer that adopts in the traditional ester exchange process.The loss of simple employing base-catalyzed transesterification method production fatty acid methyl ester is big, yield is low, and general elder generation adding an acidic catalyst carries out pre-esterification to raw material, adds basic catalyst then and carries out transesterify; Selected not at that time in condition, may take place how much or the secondary reflection of position isomerism, caused yield; Reaction product must be washed, and produces alkali waste in the washing process, if any residual alkali, then generates soap in the diesel oil, easy blocking pipe, and problems such as the generation three wastes cause environmental pollution.
Alkali, alkaline-earth metal alkylate adopt sodium methylate, magnesium ethylate etc. usually, and bibliographical information is all arranged both at home and abroad.Its biggest advantage is the catalytic activity height, but fast reaction speed under the low temperature, and the reaction of need not reducing pressure, catalyzer is soluble in fatty acid ester, but has the shortcoming of homogeneous catalytic reaction equally.
Adopt the homogeneous catalysis method, be difficult to obtain the high-quality methyl esters of high yield, often need neutralize to remove catalyzer the not easily separated purification of by-product glycerol simultaneously.The disadvantage of homogeneous reaction is that aftertreatment is complicated, causes cost to rise, and raw material availability descends, and produces problems such as the three wastes.Therefore, demand the biodiesel manufacture technology of development of new urgently.
Solid super basic catalyst more and more is subjected to numerous investigators' attention with its particular performances.The major advantage of solid super base has: 1. catalytic activity height, reaction conditions gentleness; 2. target product selectivity is good, the product purity height; 3. catalyzer easily separates with product, and technology is simple; 4. catalyzer is reusable, also can use continuously; 5. little to conversion unit corrodibility.
The solid base catalyst that this patent discloses a kind of utilization prepares the technology of biofuel,
Summary of the invention
The object of the present invention is to provide a kind of technology of utilizing solid base catalyst to prepare biofuel; this reaction conditions gentleness, technological process be simple and easy to control, can guarantee to obtain the fine biofuel; catalyzer can be recycled, and has good economic benefits, and environment is not polluted.
Technical scheme of the present invention is as follows:
A kind of preparation method of bio-diesel oil is characterized in that this method carries out as follows:
1) 0.4～9% the solid base catalyst that takes by weighing the vegetables oil weight that intend to drop into is packed in the reaction vessel; This solid base catalyst is made up of alkaline-earth metal and alkali-metal oxide compound, described alkaline-earth metal is one or more among Mg, Ca, Sr and the Ba, described basic metal is one or more among Li, Na, K and the Rb, and wherein the mol ratio of basic metal and alkaline-earth metal is not more than 2/3; Described solid base catalyst is full particle or porous grain type, and wherein porous grain type comprises particle itself that have the porous pattern and with the porous complex body of solid base catalyst attached to the surperficial gained of porous material; This solid base catalyst is a raw material with one or more of alkaline-earth metal and alkali-metal oxyhydroxide, oxide compound, oxysalt and non-oxysalt, by the precipitator method, sol-gel method, support method or the auxiliary synthesis method preparation of template;
2) take by weighing the pure and mild vegetables oil of short-chain fat, join in the reaction vessel, wherein the mol ratio of the pure and mild vegetables oil of short-chain fat is 3.5～12: 1;
3) under whipped state, be heated to 40～90 ℃, after reaction in 0.8～20 hour, stopped reaction;
When 4) treating that temperature is reduced to 30～60 ℃, stir and vacuum state under underpressure distillation recovery short chain fatty alcohol, till vacuum tightness no longer included variation, described vacuum tightness was-0.08～-0.1MPa;
5) product obtains coarse biodiesel and glycerine after solid particulate is removed in centrifugation;
6) impurity in the resulting coarse biodiesel of removing makes biofuel.
Short chain fatty alcohol of the present invention is methyl alcohol, ethanol or their mixture; Described vegetables oil adopts leprosy fruit oil, Oleum Gossypii semen, rapeseed oil, transgenosis rapeseed oil, Viscotrol C, soybean oil, genetically engineered soybean oil, coptis wood oil, shinyleaf yellowhorn oil, Persea cubeba kernel oil, plam oil, sunflower seed oil or peanut oil; The solid particulate that product is removed through centrifugation in the described step 5) uses as catalyst recirculation.
Technical characterictic of the present invention also is: the impurity of removing in the above-mentioned step 6) in the coarse biodiesel adopts settling process and centrifugal separation, or elder generation adds the mixture of precipitation agent, flocculation agent or precipitation agent and flocculation agent, the deionized water that adds oil phase volume 2～50% then mixes the back centrifugation and removes impurity; Described precipitation agent adopts ammoniacal liquor, volatile salt, oxalic acid, citric acid or phosphoric acid, the amount of adding be vegetables oil heavy 0.02～5%; Described flocculation agent adopts contract methylcellulose gum, polyvinyl alcohol, polyacrylamide or polyacrylic acid, the amount of adding be vegetables oil heavy 0.02～5%.
In the process of the impurity in removing coarse biodiesel, when adopting the method for the mixture that adds precipitation agent, flocculation agent or precipitation agent and flocculation agent, the water of adding recycles after centrifugation.
The present invention compared with prior art, have the following advantages and the high-lighting effect: this technology goes for plurality of raw materials, the preparation biofuel productive rate can reach more than 85%.The even phase catalyst that solid alkali can solve available technology adopting as catalyzer is difficult to and the problem of product separation, and the solid alkali of recovery can be used as catalyst recirculation and uses.Adopt precipitation agent and flocculation agent way of combining, simply remove the impurity in the coarse biodiesel efficiently, obtain the fine biofuel.The deionized water that uses when removing the impurity in the coarse biodiesel can recycle.This technology has advantages such as reaction conditions gentleness, technological process be simple and easy to control, environmentally friendly, has good economic benefits.
Embodiment
Solid base catalyst used in the present invention is to be called " a kind of solid base catalyst and preparation method and application " by the applicant in the name of in January, 2005 application (application number: specification sheets 200510011269.0) is described, this solid base catalyst is made up of alkaline-earth metal and alkali-metal oxide compound, described alkaline-earth metal is one or more among Mg, Ca, Sr and the Ba, described basic metal is one or more among Li, Na, K and the Rb, and wherein the mol ratio of basic metal and alkaline-earth metal is not more than 2/3; Described solid base catalyst is full particle or porous grain type, and wherein porous grain type comprises particle itself that have the porous pattern and with the porous complex body of solid base catalyst attached to the surperficial gained of porous material; This solid base catalyst is a raw material with one or more of alkaline-earth metal and alkali-metal oxyhydroxide, oxide compound, oxysalt and non-oxysalt, by the precipitator method, sol-gel method, support method or the auxiliary synthesis method preparation of template (concrete preparation method sees embodiment).
Convenient for the narration of back, represent full particle type solid base catalyst with SX, DK represents the multi-hole type solid base catalyst, and FH represents the porous complex body.When containing a metal ion species, but aperture and specific surface area can add an integer in the back as (1,2,3 when a great difference is arranged ...) etc., to show difference.
The following examples are used to further specify the present invention rather than are used for limiting the present invention.
Embodiment 1:
Under agitation, 7.86 gram calcium nitrate tetrahydrates are dissolved in 400 milliliters of ethanol, continue to stir 30 minutes.200 milliliters of deionization solution that are dissolved with 3.51 gram yellow soda ash are added drop-wise in the above-mentioned solution lentamente, and centrifugation precipitation with deionized water wash precipitation 4 times, places 110 ℃ dry 24 hours of baking oven then.The gained sample promptly obtains full particle type solid alkali SX1 in 1200 ℃ of calcinings 0.5 hour.
19.2 gram methyl alcohol and 85 gram leprosy fruit oil are joined in 500 milliliters the round-bottomed flask putting 1.7 gram SX1 in advance well, install prolong and drying tube, be warming up to 90 ℃ of reactions 2.5 hours, stopped reaction under stirring.When treating that temperature is reduced to 60 ℃, under slowly stirring, methyl alcohol is reclaimed in underpressure distillation under the vacuum tightness of-0.1MPa, till vacuum tightness no longer includes variation.Solid particulate is removed in centrifugation.Liquid in the centrifuge tube is divided into two-layer, and the upper strata is a coarse biodiesel, and lower floor is a glycerine.With the supernatant liquid sucking-off, place 500 ml beakers, add 2.55 gram citric acids, to stir 10 minutes, precipitation is removed in centrifugation.Draw supernatant liquid, add the polyvinyl alcohol of 0.017 gram, stirred 2 minutes, add 1.8 ml deionized water, stirred 10 minutes, solid is removed in centrifugation, obtains biofuel.
Every detection index of the biofuel that makes is listed in subordinate list 1.
Embodiment 2:
Under agitation, 7.86 gram calcium nitrate tetrahydrates are dissolved in 15.72 ml deionized water, continue to stir 60 minutes.200 milliliters of deionization solution that are dissolved with 10.55 gram yellow soda ash are added drop-wise in the above-mentioned solution lentamente, and centrifugation precipitation with deionized water wash precipitation 4 times, places 110 ℃ dry 24 hours of baking oven then.The gained sample promptly obtains full particle type solid alkali SX2 in 700 ℃ of calcinings 10 hours.
3.2 gram methyl alcohol, 0.72 gram ethanol and 8.5 gram Viscotrol C are joined in 500 milliliters the round-bottomed flask putting 0.034 gram SX2 in advance well, install prolong and drying tube, be warming up to 40 ℃ of reactions 0.8 hour, stopped reaction under stirring.When maintaining the temperature at 40 ℃, under slowly stirring, methyl alcohol is reclaimed in underpressure distillation under the vacuum tightness of-0.08MPa, till vacuum tightness no longer includes variation.Solid particulate is removed in centrifugation.Liquid in the centrifuge tube is divided into two-layer, and the upper strata is a coarse biodiesel, and lower floor is a glycerine.With the supernatant liquid sucking-off, place 250 ml beakers, add 1.7 milligrams of oxalic acid, to stir 10 minutes, precipitation is removed in centrifugation.Draw supernatant liquid, add the polyacrylamide of 0.42 gram, stirred 2 minutes, add 5.4 ml deionized water, solid is removed in centrifugation, obtains biofuel.
Embodiment 3:
4 gram nitrate of baryta and 4.3 are restrained Magnesium dichloride hexahydrates and join in 600 milliliters of ethanol ultra-sonic dispersion 30 minutes.Under agitation, above-mentioned solution is heated to 60 ℃, adds 200 milliliters of Virahols, succsinic acid 0.8 gram adds XC-72 gac 2.75 grams, and carried out 4 hours at stirring and ultrasonic interval, slowly drip 200 milliliters of the aqueous solution that contain 0.5 gram poly(oxyethylene glycol) 400, continue to stir 4 hours.90 ℃ of following slow solvent evaporated are warming up to 850 ℃ with the speed of 1 ℃/min from 30 ℃, and at 850 ℃ of calcinings 4 hours, multi-hole type solid alkali DK1.
1.12 gram methyl alcohol and 8.5 gram Oleum Gossypii semens are joined in 500 milliliters the round-bottomed flask putting 0.77 gram DK1 in advance well, install prolong and drying tube, be warming up to 75 ℃ of reactions 20 hours, stopped reaction under stirring.When treating that temperature is reduced to 30 ℃, under slowly stirring, methyl alcohol is reclaimed in underpressure distillation under the vacuum tightness of-0.1MPa, till vacuum tightness no longer includes variation.Solid particulate is removed in centrifugation.Liquid in the centrifuge tube is divided into two-layer, and the upper strata is a coarse biodiesel, and lower floor is a glycerine.With the supernatant liquid sucking-off, place 250 ml beakers, add 0.42 gram citric acid, to stir 10 minutes, precipitation is removed in centrifugation.Draw supernatant liquid, add the polyacrylamide of 0.42 gram, stirred 2 minutes, add 5.4 ml deionized water, solid is removed in centrifugation, obtains biofuel.
Embodiment 4:
Under agitation, 0.05 gram hexadecyl trimethyl ammonium bromide is dissolved in 200 milliliters of propyl carbinols of 100 ℃, slowly drips 100 milliliters of the aqueous solution of 0.05 gram polyvinyl alcohol 800, continue to stir 4 hours.The 600 ml water solution that will contain 5.7 gram nitrate of baryta and 4.3 gram Magnesium dichloride hexahydrates slowly are added drop-wise in the above-mentioned system, stir 2 hours.160 ℃ of dryings 24 hours are warming up to 900 ℃ with the speed of 1 ℃/min from 30 ℃ then, and at 900 ℃ of calcinings 4 hours, multi-hole type solid alkali DK2.
3.2 gram methyl alcohol, 0.72 gram ethanol and 8.5 gram leprosy fruit oil are joined in 500 milliliters the round-bottomed flask putting 0.51 gram DK2 in advance well, install prolong and drying tube, be warming up to 40 ℃ of reactions 0.8 hour, stopped reaction under stirring.When maintaining the temperature at 40 ℃, under slowly stirring, methyl alcohol and ethanol are reclaimed in underpressure distillation under the vacuum tightness of-0.08MPa, till vacuum tightness no longer includes variation.Solid particulate is removed in centrifugation.Liquid in the centrifuge tube is divided into two-layer, and the upper strata is a coarse biodiesel, and lower floor is a glycerine.With the supernatant liquid sucking-off, place 250 ml beakers, add 0.017 gram citric acid, to stir 10 minutes, precipitation is removed in centrifugation.Draw supernatant liquid, add 1.7 milligrams the methylcellulose gum that contracts, stirred 2 minutes, add 5.4 ml deionized water, solid is removed in centrifugation, obtains biofuel.
Embodiment 5:
Under agitation, with 3.3 gram magnesium chlorides, 2.1 nitrocalcite and 0.5 strontium nitrate are distributed in 120 milliliters of dimethyl formamides, stir to stop after two hours stirring, and 117 milliliters MCM-41 molecular sieve is joined in the above-mentioned system.After 30 minutes, drain solvent under 60 ℃, product obtains porous ABO/ carrier composite material FH1 600 ℃ of calcinings 2 hours
3.6 gram ethanol and 8.5 gram leprosy fruit oil are joined in 500 milliliters the round-bottomed flask putting 0.77 gram FH1 in advance well, install prolong and drying tube, be warming up to 60 ℃ of reactions 9 hours, stopped reaction under stirring.When treating that temperature is reduced to 35 ℃, under slowly stirring, ethanol is reclaimed in underpressure distillation under the vacuum tightness of-0.09MPa, till vacuum tightness no longer includes variation.Stop heating, static 24 hours, solid particulate was deposited on the bottom of flask; Liquid is divided into two-layer, and the upper strata is a coarse biodiesel, and lower floor is a glycerine.With the supernatant liquid sucking-off, place 250 ml beakers, add 0.03 gram citric acid, to stir 10 minutes, precipitation is removed in centrifugation.Draw supernatant liquid, add the polyacrylic acid of 0.084 gram, stirred 2 minutes, add 3 ml deionized water, solid is removed in centrifugation, obtains biofuel.
Embodiment 6:
5 gram calcium nitrate tetrahydrates and 4.3 gram Magnesium dichloride hexahydrates are joined in 400 milliliters of ethanol ultra-sonic dispersion 30 minutes.Under the vigorous stirring, in above-mentioned solution, slowly drip 20 milliliter of 1,6 hexanediamine, continue to stir 5 minutes, stop to stir, then 85 milliliters ceramic honey comb is joined in the said mixture.Slowly stir 20 minutes after-filtration separate solid products with glass stick,, obtain porous ABO/ carrier composite material FH2 through 800 ℃ of calcinings 3 hours.
3.2 gram methyl alcohol, 0.72 gram ethanol and 8.5 gram soybean oil are joined in 500 milliliters the round-bottomed flask putting 0.17 gram FH2 in advance well, install prolong and drying tube, be warming up to 60 ℃ of reactions 9 hours, stopped reaction under stirring.When treating that temperature is reduced to 35 ℃, under slowly stirring, methyl alcohol and ethanol are reclaimed in underpressure distillation under the vacuum tightness of-0.09MPa, till vacuum tightness no longer includes variation.Solid particulate is removed in centrifugation.Liquid in the centrifuge tube is divided into two-layer, and the upper strata is a coarse biodiesel, and lower floor is a glycerine.With the supernatant liquid sucking-off, place 250 ml beakers, add 0.034 gram volatile salt, to stir 10 minutes, precipitation is removed in centrifugation.Draw supernatant liquid, add 1.7 milligrams polyacrylic acid, stirred 2 minutes, add 5.4 ml deionized water, solid is removed in centrifugation, obtains biofuel.
Embodiment 7:
3.2 gram methyl alcohol, 0.72 gram ethanol and 8.5 gram soybean oil are joined in 500 milliliters the round-bottomed flask putting 0.77 gram FH2 in advance well, install prolong and drying tube, be warming up to 60 ℃ of reactions 9 hours, stopped reaction under stirring.When treating that temperature is reduced to 35 ℃, under slowly stirring, methyl alcohol and ethanol are reclaimed in underpressure distillation under the vacuum tightness of-0.09MPa, till vacuum tightness no longer includes variation.Stop heating, static 36 hours, solid particulate was deposited on the bottom of flask; Liquid is divided into two-layer, and the upper strata is a biofuel, and lower floor is a glycerine.The careful supernatant liquid of drawing obtains biofuel.
Embodiment 8:
3.6 gram ethanol and 8.5 gram Oleum Gossypii semens are joined in 500 milliliters the round-bottomed flask putting 0.34 gram FH2 in advance well, install prolong and drying tube, be warming up to 60 ℃ of reactions 9 hours, stopped reaction under stirring.When treating that temperature is reduced to 35 ℃, under slowly stirring, ethanol is reclaimed in underpressure distillation under the vacuum tightness of-0.09MPa, till vacuum tightness no longer includes variation.Stop heating, to be cooled after room temperature, use supercentrifuge, descended centrifugal 2 hours at 5000 rev/mins.System is divided into three layers, and solid particulate is deposited on the bottom of centrifuge tube; Liquid is divided into two-layer, and the upper strata is a coarse biodiesel, and lower floor is a glycerine.With the supernatant liquid sucking-off, obtain biofuel.
Embodiment 9:
19.2 gram methyl alcohol and 85 gram coptis wood oils are joined in 500 milliliters the round-bottomed flask putting 1.7 gram SX1 in advance well, install prolong and drying tube, be warming up to 90 ℃ of reactions 2.5 hours, stopped reaction under stirring.When treating that temperature is reduced to 60 ℃, under slowly stirring, methyl alcohol is reclaimed in underpressure distillation under the vacuum tightness of-0.1MPa, till vacuum tightness no longer includes variation.Solid particulate is removed in centrifugation.Liquid in the centrifuge tube is divided into two-layer, and the upper strata is a coarse biodiesel, and lower floor is a glycerine.With the supernatant liquid sucking-off, place 500 ml beakers, add 2.55 gram citric acids, to stir 10 minutes, precipitation is removed in centrifugation.Draw supernatant liquid, add the polyvinyl alcohol of 0.017 gram, stirred 2 minutes, add 1.8 ml deionized water, stirred 10 minutes, solid is removed in centrifugation, obtains biofuel.
Embodiment 10:
19.2 gram methyl alcohol and 85 gram shinyleaf yellowhorn oils are joined in 500 milliliters the round-bottomed flask putting 1.7 gram SX1 in advance well, install prolong and drying tube, be warming up to 90 ℃ of reactions 2.5 hours, stopped reaction under stirring.When treating that temperature is reduced to 60 ℃, under slowly stirring, methyl alcohol is reclaimed in underpressure distillation under the vacuum tightness of-0.1MPa, till vacuum tightness no longer includes variation.Solid particulate is removed in centrifugation.Liquid in the centrifuge tube is divided into two-layer, and the upper strata is a coarse biodiesel, and lower floor is a glycerine.With the supernatant liquid sucking-off, place 500 ml beakers, add 2.55 gram citric acids, to stir 10 minutes, precipitation is removed in centrifugation.Draw supernatant liquid, add the polyvinyl alcohol of 0.017 gram, stirred 2 minutes, add 1.8 ml deionized water, stirred 10 minutes, solid is removed in centrifugation, obtains biofuel.
Embodiment 11:
19.2 gram methyl alcohol and the grey daughter nucleus oil of 85 Keshans oil are joined in 500 milliliters the round-bottomed flask putting 1.7 gram SX1 in advance well, install prolong and drying tube, be warming up to 90 ℃ of reactions 2.5 hours, stopped reaction under stirring.When treating that temperature is reduced to 60 ℃, under slowly stirring, methyl alcohol is reclaimed in underpressure distillation under the vacuum tightness of-0.1MPa, till vacuum tightness no longer includes variation.Solid particulate is removed in centrifugation.Liquid in the centrifuge tube is divided into two-layer, and the upper strata is a coarse biodiesel, and lower floor is a glycerine.With the supernatant liquid sucking-off, place 500 ml beakers, add 2.55 gram citric acids, to stir 10 minutes, precipitation is removed in centrifugation.Draw supernatant liquid, add the polyvinyl alcohol of 0.017 gram, stirred 2 minutes, add 1.8 ml deionized water, stirred 10 minutes, solid is removed in centrifugation, obtains biofuel.
Embodiment 12:
3.6 gram ethanol and 8.5 gram sunflower seed oils are joined in 500 milliliters the round-bottomed flask putting 0.34 gram FH2 in advance well, install prolong and drying tube, be warming up to 60 ℃ of reactions 9 hours, stopped reaction under stirring.When treating that temperature is reduced to 35 ℃, under slowly stirring, ethanol is reclaimed in underpressure distillation under the vacuum tightness of-0.09MPa, till vacuum tightness no longer includes variation.Stop heating, to be cooled after room temperature, use supercentrifuge, descended centrifugal 2 hours at 5000 rev/mins.System is divided into three layers, and solid particulate is deposited on the bottom of centrifuge tube; Liquid is divided into two-layer, and the upper strata is a coarse biodiesel, and lower floor is a glycerine.With the supernatant liquid sucking-off, obtain biofuel.
Embodiment 13:
3.2 gram methyl alcohol, 0.72 gram ethanol and 8.5 gram genetically engineered soybean oil are joined in 500 milliliters the round-bottomed flask putting 0.77 gram FH2 in advance well, install prolong and drying tube, be warming up to 60 ℃ of reactions 9 hours, stopped reaction under stirring.When treating that temperature is reduced to 35 ℃, under slowly stirring, methyl alcohol and ethanol are reclaimed in underpressure distillation under the vacuum tightness of-0.09MPa, till vacuum tightness no longer includes variation.Stop heating, static 36 hours, solid particulate was deposited on the bottom of flask; Liquid is divided into two-layer, and the upper strata is a biofuel, and lower floor is a glycerine.The careful supernatant liquid of drawing obtains biofuel.
Embodiment 14:
3.2 gram methyl alcohol, 0.72 gram ethanol and 8.5 gram palm fibres are put oil join in 500 milliliters the round-bottomed flask putting 0.77 gram FH2 in advance well, install prolong and drying tube, be warming up to 60 ℃ of reactions 9 hours, stopped reaction under stirring.When treating that temperature is reduced to 35 ℃, under slowly stirring, methyl alcohol and ethanol are reclaimed in underpressure distillation under the vacuum tightness of-0.09MPa, till vacuum tightness no longer includes variation.Stop heating, static 36 hours, solid particulate was deposited on the bottom of flask; Liquid is divided into two-layer, and the upper strata is a biofuel, and lower floor is a glycerine.The careful supernatant liquid of drawing obtains biofuel.
Embodiment 15:
3.2 gram methyl alcohol, 0.72 gram ethanol and 8.5 gram transgenosis rapeseed oils are joined in 500 milliliters the round-bottomed flask putting 0.77 gram FH2 in advance well, install prolong and drying tube, be warming up to 60 ℃ of reactions 9 hours, stopped reaction under stirring.When treating that temperature is reduced to 35 ℃, under slowly stirring, methyl alcohol and ethanol are reclaimed in underpressure distillation under the vacuum tightness of-0.09MPa, till vacuum tightness no longer includes variation.Stop heating, static 36 hours, solid particulate was deposited on the bottom of flask; Liquid is divided into two-layer, and the upper strata is a biofuel, and lower floor is a glycerine.The careful supernatant liquid of drawing obtains biofuel.
The detection index of subordinate list 1 biofuel
| Project name | Data unit | The sample of preparation | |
| Measured value | Method standard | ||
| Density, 20 ℃ | g/cm 3 | 0.8784 | SH/T 0604 |
| Kinematic viscosity, 20 ℃ | mm 2/s | 7.320 | GB/T 265 |
| Calorific value (height) | Cal/g | 9489(35MJ/L) | GB/T 384 |
| Flash-point (remaining silent) | ℃ | ＞170 | GB/T 261 |
| Condensation point | ℃ | +1 | GB/T 3535 |
| Trace carbon residue | ％ | ＜0.05 | GB/T 17144 |
| Sulphated ash | ％ | ＜0.005 | GB/T 2433 |
| S content | mg/L | 32(0.0036％) | SH/T 253-92 |
| Cetane value | 56.1 | Actual measurement | |
Annotate: be the data after converting in the bracket.
Claims (6)
1. one kind prepares method of bio-diesel oil, it is characterized in that this method carries out as follows:
1) 0.4～9% the solid base catalyst that takes by weighing the vegetables oil weight that intend to drop into is packed in the reaction vessel; This solid base catalyst is made up of alkaline-earth metal and alkali-metal oxide compound, described alkaline-earth metal is one or more among Mg, Ca, Sr and the Ba, described basic metal is one or more among Li, Na, K and the Rb, and wherein the mol ratio of basic metal and alkaline-earth metal is not more than 2/3; Described solid base catalyst is full particle or porous grain type, and wherein porous grain type comprises particle itself that have the porous pattern and with the porous complex body of solid base catalyst attached to the surperficial gained of porous material; This solid base catalyst is a raw material with one or more of alkaline-earth metal and alkali-metal oxyhydroxide, oxide compound, oxysalt and non-oxysalt, by the precipitator method, sol-gel method, support method or the auxiliary synthesis method preparation of template;
2) take by weighing the pure and mild vegetables oil of short-chain fat, join in the reaction vessel, wherein the mol ratio of the pure and mild vegetables oil of short-chain fat is 3.5～12: 1;
3) under whipped state, be heated to 40～90 ℃, after reaction in 0.8～20 hour, stopped reaction;
When 4) treating that temperature is reduced to 30～60 ℃, stir and vacuum state under underpressure distillation recovery short chain fatty alcohol, till vacuum tightness no longer included variation, described vacuum tightness was-0.08～-0.1MPa;
5) product obtains coarse biodiesel and glycerine after solid particulate is removed in centrifugation;
6) impurity in the resulting coarse biodiesel of removing makes biofuel.
2. preparation method of bio-diesel oil according to claim 1 is characterized in that: described short chain fatty alcohol is methyl alcohol, ethanol or their mixture.
3. preparation method of bio-diesel oil according to claim 1 is characterized in that: the solid particulate that product is removed through centrifugation in the step 5) uses as catalyst recirculation.
4. preparation method of bio-diesel oil according to claim 1, it is characterized in that: described vegetables oil adopts leprosy fruit oil, Oleum Gossypii semen, rapeseed oil, transgenosis rapeseed oil, Viscotrol C, soybean oil, genetically engineered soybean oil, coptis wood oil, shinyleaf yellowhorn oil, Persea cubeba kernel oil, plam oil, sunflower seed oil or peanut oil.
5. according to claim 1,2,3 or 4 described preparation method of bio-diesel oil, it is characterized in that: the impurity of removing in the described step 6) in the coarse biodiesel adopts settling process and centrifugal separation, or elder generation adds the mixture of precipitation agent, flocculation agent or precipitation agent and flocculation agent, the deionized water that adds oil phase volume 2～50% then mixes the back centrifugation and removes impurity; Described precipitation agent adopts ammoniacal liquor, volatile salt, oxalic acid, citric acid or phosphoric acid, the amount of adding be vegetables oil heavy 0.02～5%; Described flocculation agent adopts contract methylcellulose gum, polyvinyl alcohol, polyacrylamide or polyacrylic acid, the amount of adding be vegetables oil heavy 0.02～5%.
6. preparation method of bio-diesel oil according to claim 5, it is characterized in that: in the process of the impurity in removing coarse biodiesel, when adopting the method for the mixture that adds precipitation agent, flocculation agent or precipitation agent and flocculation agent, the water of adding recycles after centrifugation.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009046636A1 (en) * | 2007-09-29 | 2009-04-16 | Huazhong Agricultural University | Method for producing biodiesel using solid acid-base bifunctional catalyst |
| CN101195759B (en) * | 2007-12-19 | 2011-07-20 | 贵州大学 | Technique for producing Chinese tallow tree stillingia oil biological diesel oil with solid base catalyst catalysis |
| CN102146318A (en) * | 2011-02-12 | 2011-08-10 | 青岛福瑞斯生物能源科技开发有限公司 | Method for preparing biodiesel by using palm oil |
| CN102161933A (en) * | 2011-03-10 | 2011-08-24 | 四川大学 | Method for preparing biodiesel by one step based on lepra fruits as raw material |
| CN102942969A (en) * | 2012-11-29 | 2013-02-27 | 青岛福瑞斯生物能源科技开发有限公司 | Method for preparing biodiesel by castor oil |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1580190A (en) * | 2004-05-21 | 2005-02-16 | 北京化工大学 | Method for preparing biodiesel by solid acid-base catalyst |
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2005
- 2005-07-15 CN CNB2005100121948A patent/CN100375780C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009046636A1 (en) * | 2007-09-29 | 2009-04-16 | Huazhong Agricultural University | Method for producing biodiesel using solid acid-base bifunctional catalyst |
| CN101861372B (en) * | 2007-09-29 | 2013-06-19 | 华中农业大学 | Method for producing biodiesel using solid acid-base bifunctional catalyst |
| CN101195759B (en) * | 2007-12-19 | 2011-07-20 | 贵州大学 | Technique for producing Chinese tallow tree stillingia oil biological diesel oil with solid base catalyst catalysis |
| CN102146318A (en) * | 2011-02-12 | 2011-08-10 | 青岛福瑞斯生物能源科技开发有限公司 | Method for preparing biodiesel by using palm oil |
| CN102146318B (en) * | 2011-02-12 | 2013-11-27 | 青岛福瑞斯生物能源科技开发有限公司 | Method for preparing biodiesel by using palm oil |
| CN102161933A (en) * | 2011-03-10 | 2011-08-24 | 四川大学 | Method for preparing biodiesel by one step based on lepra fruits as raw material |
| CN102942969A (en) * | 2012-11-29 | 2013-02-27 | 青岛福瑞斯生物能源科技开发有限公司 | Method for preparing biodiesel by castor oil |
| CN102942969B (en) * | 2012-11-29 | 2015-07-29 | 青岛福瑞斯生物能源科技开发有限公司 | A kind of method of production of biodiesel from castor oil |
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