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 PDFInfo
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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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- biodiesel
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000011973 solid acid Substances 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 239000003513 alkali Substances 0.000 title claims abstract description 18
- 239000002283 diesel fuel Substances 0.000 title description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 69
- 235000011187 glycerol Nutrition 0.000 claims abstract description 31
- 239000003225 biodiesel Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 150000004702 methyl esters Chemical class 0.000 claims abstract description 11
- 241001465754 Metazoa Species 0.000 claims abstract description 10
- 239000010775 animal oil Substances 0.000 claims abstract description 9
- 238000005119 centrifugation Methods 0.000 claims abstract description 7
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 5
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract 7
- 239000008158 vegetable oil Substances 0.000 claims abstract 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 238000005815 base catalysis Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 6
- 229960001545 hydrotalcite Drugs 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 229910020068 MgAl Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910003321 CoFe Inorganic materials 0.000 claims description 2
- 229910003023 Mg-Al Inorganic materials 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 238000009388 chemical precipitation Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- 238000002207 thermal evaporation Methods 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 3
- 239000003930 superacid Substances 0.000 claims 2
- -1 Carbon alcohols Chemical class 0.000 claims 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 16
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract 2
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 239000002551 biofuel Substances 0.000 description 25
- 239000003921 oil Substances 0.000 description 16
- 235000019198 oils Nutrition 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 230000009466 transformation Effects 0.000 description 14
- 235000013311 vegetables Nutrition 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000008157 edible vegetable oil Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 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
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
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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
本发明涉及一种用纳米级固体酸或碱催化制备脂肪酸低碳烷基酯——生物柴油的方法，它采用纳米固体酸或碱催化剂，催化剂加入量为动植物油重量的1～20％，低碳醇与动植物油摩尔比为3.5～40∶1，加热搅拌反应，反应罐的压力：常压～25Mp，温度：40－100℃，反应后离心分离出粗甲酯和甘油相，将粗甲酯和甘油相分别蒸馏出低碳醇，即得到中性的生物柴油和甘油。本发明采用纳米固体酸或碱催化剂催化动植物油脂酯交换反应，生物柴油转化率达到96％以上，得率99％以上，产品技术指标符合ASTM D 6751－02标准。采用纳米固体酸或碱催化剂可反复使用3～100次后生物柴油转化率仍在96％左右。得到的产品不需要中和洗涤等后处理，无污水排放。解决了传统液相酸或液相碱催化剂制备生物柴油中，存在的诸多问题。
The invention relates to a method for preparing low-carbon alkyl esters of fatty acids—biodiesel catalyzed by nano-scale solid acid or alkali. It adopts nano-scale solid acid or alkali catalyst, and the amount of catalyst added is 1-20% of the weight of animal and vegetable oil, which is low. The molar ratio of carbon alcohol to animal and vegetable oil is 3.5-40:1, heated and stirred to react, the pressure of the reaction tank: normal pressure to 25Mp, the temperature: 40-100°C, after the reaction, the crude methyl ester and glycerin phase are separated by centrifugation, and the crude methyl The lower alcohols are distilled from the ester and glycerin phases to obtain neutral biodiesel and glycerin. The invention adopts nanometer solid acid or alkali catalyst to catalyze the transesterification reaction of animal and vegetable oils, the biodiesel conversion rate reaches over 96%, the yield rate exceeds 99%, and the technical index of the product conforms to the ASTM D 6751-02 standard. The biodiesel conversion rate is still about 96% after the nanometer solid acid or alkali catalyst can be used repeatedly for 3 to 100 times. The obtained product does not require post-treatment such as neutralization and washing, and has no sewage discharge. The method solves many problems existing in the preparation of biodiesel with traditional liquid-phase acid or liquid-phase alkali catalysts.
Description
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)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100192454A CN100503786C (en) | 2006-06-02 | 2006-06-02 | Method for preparing biodiesel with nanometer solid acid or base catalysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100192454A CN100503786C (en) | 2006-06-02 | 2006-06-02 | Method for preparing biodiesel with nanometer solid acid or base catalysis |
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