CN101474571A - Solid base catalyst for preparing biodiesel - Google Patents

Solid base catalyst for preparing biodiesel Download PDF

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Publication number
CN101474571A
CN101474571A CNA2009100088172A CN200910008817A CN101474571A CN 101474571 A CN101474571 A CN 101474571A CN A2009100088172 A CNA2009100088172 A CN A2009100088172A CN 200910008817 A CN200910008817 A CN 200910008817A CN 101474571 A CN101474571 A CN 101474571A
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solid base
base catalyst
catalyst
biodiesel
metal ion
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矫庆泽
何杨
陈魁
刘小可
孙冲波
曾超群
赵芸
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Beijing Institute of Technology BIT
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Beijing Institute of Technology BIT
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Abstract

The invention discloses a solid base catalyst for preparing bio-diesel oil. The solid base catalyst is an anionic layered compound--hydrotalcite-like compound with controllable components. The solid base catalyst of the invention has simple preparation technology, high catalytic activity during the ester exchange reaction between the grease and the short-chain alcohol to synthesize the bio-diesel oil and high yield of the bio-diesel oil and can reuse the catalyst. The solid base catalyst solves the problems such as complexity of the catalyst preparation technology in the prior art and energy consumption, etc.

Description

A kind of solid base catalyst that is used to prepare biodiesel
Technical field
The present invention relates to a kind of solid base catalyst, particularly a kind of solid base catalyst that is used to prepare biodiesel belongs to catalyst field.
Background technology
Along with the development of World Economics, existing crude resources can not satisfy growing demand.Being the biodiesel that raw material is produced with the natural oil, is the oil-fired substitute of high-quality, have renewable, easily biological-degradable, nontoxic, sulfur content is low and waste gas in advantages such as the discharge of poisonous waste amount is little, belong to environmentally friendly fuel.Be subjected at present the common concern of countries in the world.
With vegetable oil, animal oil, waste edible oil etc. is that raw material carries out ester exchange reaction with alcohol (short chain alcohol such as methyl alcohol, ethanol), and product is biodiesel (fatty acid ester), and byproduct is a glycerine.Existing industrial process mostly adopts the acid (sulfuric acid, hydrochloric acid etc.) of homogeneous phase, alkali (NaOH, potassium hydroxide etc.) to be the catalyst ester exchange reaction, cause the ester interchanged prod separation difficulty, and product need neutralize washing and bring a large amount of industrial wastewaters, cause environmental pollution, the post processing complexity.Adopting solid acid or solid base catalyst to substitute homogeneous catalyst, is the best approach of avoiding environmental pollution, because catalyst separates easily with product, product quality is improved.Wherein the solid base catalyst cost is low, and it is simple to be used for the ester exchange reaction production technology, the product convenient post-treatment, and no waste water produces.
The solid base catalyst of having reported comprises that it is the composite oxide catalysts that presoma is made that CaO system, MgO reach with the hydrotalcite.
CN1962824 discloses a kind of preparation method who is used for the supported solid catalyst of production biodiesel, is KF, the CaF of 3-20% with hydrotalcite or houghite dip loading concentration 2, ZnF 2, NaF or K 2CO 3At least a, 400～800 ℃ of calcinings 2-10 hour, pulverize then.This catalyst is to be to pass through high-temperature roasting again, complicated process of preparation and power consumption behind the carrier loaded fluoride with hydrotalcite.
CN101314131 provides the preparation method of the modified hydrotalcite solid base catalyst of preparation biodiesel, is in 400-800 ℃ of calcining 3-5 hour down, then with itself and KF, CaF with hydrotalcite or houghite 2, ZnF 2, at least a in the NaF crystal, by the 5%-100% quality than mixed grinding to there not being granular sensation, and then oven dry is ground into the solid base catalyst powder.Again the solid base catalyst powder is added bonding agent, moulding, bonding agent is removed in calcining then, forms the moulding solid base catalyst.Place steam to restore 10 minutes-10 hours the formation solid base catalyst, make because of calcining the hydrotalcite layered structure that destroys once more and recovered, the porous support type that finally obtains moulding is the solid base catalyst of carrier with the hydrotalcite.This invent at first synthetic hydrotalcite then after high-temperature calcination as carrier loaded fluoride, with steam hydrotalcite layered structure is restored again, be to be the catalyst of carrier with the hydrotalcite equally, catalyst preparation process is more complicated, power consumption is bigger.
So, a kind of simple solid base catalyst of preparation technology that is used to prepare biodiesel is now proposed, efficiently solve above problem, do not appear in the newspapers both at home and abroad at present.
Summary of the invention
The purpose of this invention is to provide a kind of simple solid base catalyst of preparation technology that is used to prepare biodiesel, it has reduced the complex process degree, and energy-conservation province consumption has been saved cost greatly.
This catalyst is that a class is formed controlled anion type laminated compound---houghite compound, and its composition general formula is: [M II 1-xM III x(OH) 2] X+(A N-) X/nMH 2O,
M wherein IIAnd M IIICan be divalence and trivalent metal ion, M II-M IIIMetal ion is to also comprising M I-M III(as Li-Al) and M II-M IV(as Co-Tr) is positioned at the octahedral interstices on the main body laminate, and bivalent metal ion has: Mg, Zn, Ni, Mn and Cu etc.; Trivalent metal ion has: Al, Fe and Cr etc., A N-But the anion for stable existence in alkaline solution is positioned at interlayer, comprises inorganic anion such as Cl -, Br -, NO 3 -, OH -, CO 3 2-, SO 4 2-, PO 4 3-With organic anion such as terephthaldehyde's acid group, adipic acid radical ion.The x value is between 0.1～0.5, and promptly the mol ratio of divalence and trivalent metal ion can be from 1.6:1--10:1.M=1-Nx/n, wherein N is the position number that anion occupies, n is anionic electric charge.
The preparation technology of solid base catalyst of the present invention----houghite is as follows: adopt coprecipitation to prepare houghite.Concrete steps are: A. salting liquid preparation: solubility divalent metal salt and trivalent metal salt is soluble in water, be mixed with mixing salt solution, described divalent metal salt and trivalent metal salt be nitrate, sulfate or hydrochloride one of, bivalent metal ion [M wherein 2+] concentration be 0.1-4.0mol/L, trivalent metal ion [M 3+] concentration is 0.05-2.0mol/L, the mol ratio [M of bivalent metal ion and trivalent metal ion 2+]/[M 3+] be 1.6:1--10:1; B. aqueous slkali preparation: with one of NaOH, sodium carbonate, ammoniacal liquor, ammonium carbonate, potassium hydroxide, potash, urea, calcium hydroxide or the water-soluble aqueous slkali that is mixed with of its mixture, if the proportionate relationship during mixture be arbitrary proportion all can, hydroxide ion [OH wherein -] concentration is 0.2-4.0mol/l, carbanion [CO 3 2-] concentration is 0-4.0mol/L, mol ratio [the OH.]/([M of hydroxide ion and divalence and trivalent metal ion mixture 2+]+[M 3+]) be 0.6-3.5.C. coprecipitation reaction: stir down salting liquid and aqueous slkali are mixed, more than 0.5 hour, generate precipitation in crystallization under the temperature more than 40 ℃ then, described speed of agitator is for surpassing 80 commentaries on classics/per minutes; Hybrid mode adds salting liquid in the aqueous slkali or aqueous slkali adds in the salting liquid, in addition, can also drip salting liquid and aqueous slkali simultaneously, makes its mixing, its volume ratio 1:1, and the adding mode is dropping or pours drop rate 5-30 ml/min into; D. separate, washing, drying: will precipitate with centrifugal or suction funnel and separate, be washed with water to neutrality,, promptly get houghite 70-100 ℃ of drying.
It is as follows that solid base catalyst of the present invention prepares the biodiesel process: natural oil and short chain alcohol are added there-necked flask with certain pure oil quality than (3:1-20:1), described grease is the waste edible oil in vegetable fat, animal tallow or the production process, described short chain alcohol is methyl alcohol, ethanol, propyl alcohol or butanols, add the houghite catalyst of oil quality 1%-5%, at stirring reaction under the temperature more than 60 ℃ more than 0.5 hour.Reaction is removed catalyst after finishing, the product standing demix, and the upper strata is a biodiesel, lower floor is a glycerin layer.Product yield adopts look-matter coupling analytical calculation.
Beneficial effect of the present invention is: the preparation technology of solid base catalyst is simple, and it is effective to be used to prepare biodiesel yield height, and catalyst is reusable.
The specific embodiment
The effect of the preparation method of solid base catalyst of the present invention, preparation biodiesel is further specified by the following examples.
Embodiment 1
The preparation of solid base catalyst: with 0.36 mole of (88.7 gram) MgSO 47H 2O and 0.1125 mole of (74.9 gram) Al 2(SO 4) 318H 2O is dissolved in 315 ml tap waters and is made into mixing salt solution, with 0.936 mole of (37.4 gram) NaOH and 0.45 mole of (47.7 gram) Na 2CO 3Be dissolved in 315 ml tap waters and be made into mixed ammonium/alkali solutions, under fully stirring, salting liquid and aqueous slkali are added dropwise in 50 ml tap waters simultaneously, and drop rate 15 ml/min dropwise, be warming up to 80 ℃ of crystallization 4 hours, generate white precipitate, use centrifugation, separated products is washed with running water, 90 ℃ of dryings, get magnalium than being the hydrotalcite of 1.6:1: Mg 0.62Al 0.38(OH) 2(CO 3) 0.194H 2O.
Preparation biodiesel: 10g soybean oil and 30g methyl alcohol are added there-necked flask, add the magnalium hydrotalcite catalyst Mg of 0.1g again 0.62Al 0.38(OH) 2(CO 3) 0.194H 2O was 65 ℃ of following stirring reactions 6 hours.Reaction is removed catalyst after finishing, the product standing demix, and the upper strata is a soybean oil methyl esters layer.Product yield is 95%.
Embodiment 2
The preparation of solid base catalyst: with 0.36 mole of (92.3 gram) Mg (NO 3) 26H 2O and 0.12 mole of (45.0 gram) Al (NO 3) 39H 2O is dissolved in 1000 ml tap waters and is made into mixing salt solution, with 0.936 mole of (52.4 gram) KOH and 0.45 mole of (62.1 gram) K 2CO 3Be dissolved in 235 ml tap waters and be made into mixed ammonium/alkali solutions, under fully stirring, aqueous slkali is added dropwise in the salting liquid, and drop rate 30 ml/min dropwise, be warming up to 60 ℃ of crystallization 6 hours, generate white precipitate, use the funnel suction filtration, separated products is washed with running water, 80 ℃ of dryings, get magnalium than being the hydrotalcite of 3:1: Mg 0.75Al 0.25(OH) 2(CO 3) 0.1255H 2O.
Preparation biodiesel: 10g rapeseed oil and 80g ethanol are added there-necked flask, add the magnalium hydrotalcite catalyst Mg of 0.2g again 0.75Al 0.25(OH) 2(CO 3) 0.1255H 2O was 78 ℃ of following stirring reactions 8 hours.Reaction is removed catalyst after finishing, the product standing demix, and the upper strata is the rapeseed oil methacrylate layer.Product yield is 99.5%.
Embodiment 3
The preparation of solid base catalyst: with 0.36 mole of (34.2 gram) MgCl 2With 0.036 mole of (4.8 gram) AlCl 3Be dissolved in 315 ml tap waters and be made into mixing salt solution, with 0.18 mole of (17.3 gram) (NH 4) 2CO 3Be dissolved in the ammoniacal liquor of 100 ml tap waters and 215 milliliter 25% and be made into mixed ammonium/alkali solutions, under fully stirring, salting liquid is poured in the aqueous slkali, heat up then in 40 ℃ of crystallization 10 hours, generate white precipitate, use the funnel suction filtration, separated products is washed with running water, 100 ℃ of dryings, get magnalium than being the hydrotalcite of 10:1:: Mg 0.91Al 0.09(OH) 2(CO 3) 0.0456H 2O.
Preparation biodiesel: 10g rapeseed oil and 150g propyl alcohol are added there-necked flask, add the magnalium hydrotalcite catalyst Mg of 0.4g again 0.91Al 0.09(OH) 2(CO 3) 0.0456H 2O was 97 ℃ of following stirring reactions 2 hours.Reaction is removed catalyst after finishing, the product standing demix, and the upper strata is a rapeseed oil propyl ester layer.Product yield is 96.5%.
Embodiment 4
The preparation of solid base catalyst: with 0.36 mole of (88.7 gram) MgSO 47H 2O and 0.06 mole of (40.0 gram) Al 2(SO 4) 318H 2O is dissolved in 315 ml deionized water and is made into mixing salt solution, 0.952 mole of (38.08 gram) NaOH is dissolved in proportionaling alkali-forming solution in 315 ml deionized water, under fully stirring, aqueous slkali is poured in the salting liquid, heated up then, generate white precipitate in 90 ℃ of crystallization 4 hours, use the funnel suction filtration, separated products is washed with running water, and 90 ℃ of dryings, getting the magnalium ratio is the hydrotalcite of sulfate ion: Mg for 3:1, interlayer ion 0.75Al 0.25(OH) 2(SO 4) 0.1255H 2O.
Preparation biodiesel: 10g rapeseed oil and 200g butanols are added there-necked flask, add the magnalium hydrotalcite catalyst Mg of 0.5g again 0.75Al 0.25(OH) 2(SO 4) 0.1255H 2O was 118 ℃ of following stirring reactions 0.5 hour.Reaction is removed catalyst after finishing, the product standing demix, and the upper strata is a rapeseed oil butyl ester layer.Product yield is 95%.
Embodiment 5
The preparation of solid base catalyst: with 0.36 mole of (92.3 gram) Mg (NO 3) 26H 2O and 0.12 mole of (45.0 gram) Al (NO 3) 39H 2O is dissolved in 1000 ml tap waters and is made into mixing salt solution, with 0.936 mole of (52.4 gram) KOH and 0.45 mole of (62.1 gram) K 2CO 3Be dissolved in 235 ml tap waters and be made into mixed ammonium/alkali solutions, under fully stirring, aqueous slkali is added dropwise in the salting liquid, drop rate 30 ml/min dropwise, and are warming up to 60 ℃ of crystallization 6 hours, generate white precipitate, use the funnel suction filtration, separated products is washed with running water, and getting the magnalium ratio is the hydrotalcite of carbanion: Mg for 3:1, interlayer ion 0.75Al 0.25(OH) 2(CO 3) 0.1255H 2O.This hydrotalcite and 210g terephthalic acid (TPA) are added in the 100mL ethylene glycol solvent, under 150 ℃, add thermal agitation 1h, filter, and with the distilled water washing, in 70 ℃ of dryings, getting interlayer ion is the magnalium hydrotalcite of terephthaldehyde's acid ion: Mg 0.75Al 0.25(OH) 2[C 6H 4(COO) 2] 0.1255H 2O.
Preparation biodiesel: 10g peanut oil and 80g ethanol are added there-necked flask, add the catalyst Mg of 0.3g again 0.75Al 0.25(OH) 2[C 6H 4(COO) 2] 0.1255H 2O was 78 ℃ of following stirring reactions 8 hours.Reaction is removed catalyst after finishing, the product standing demix, and the upper strata is the peanut oil methacrylate layer.Product yield is 96%.
Embodiment 6
The preparation of solid base catalyst: with 0.36 mole of (94.6 gram) NiSO 46H 2O and 0.06 mole of (40.0 gram) Al 2(SO 4) 318H 2O is dissolved in 315 ml deionized water and is made into mixing salt solution, with 0.936 mole of (37.4 gram) NaOH and 0.45 mole of (47.7 gram) Na 2CO 3Be dissolved in 315 ml tap waters and be made into mixed ammonium/alkali solutions, under fully stirring, aqueous slkali is poured in the salting liquid, heat up then in 90 ℃ of crystallization 4 hours, generate precipitation, use centrifugation, separated products is washed with running water, and 90 ℃ of dryings, getting the nickel aluminum ratio is the hydrotalcite of 3:1: Ni 0.75Al 0.25(OH) 2(CO 3) 0.1255H 2O.
Preparation biodiesel: 10g rapeseed oil and 80g ethanol are added there-necked flask, add the nickel aluminum hydrotalcite catalyst n i of 0.1g again 0.75Al 0.25(OH) 2(CO 3) 0.1255H 2O was 78 ℃ of following stirring and refluxing 8 hours.Reaction is removed catalyst after finishing, the product standing demix, and the upper strata is the rapeseed oil methacrylate layer.Product yield is 99%.
Embodiment 7
The preparation of solid base catalyst: with 0.36 mole of (58.0 gram) ZnSO 4With 0.06 mole of (40.0 gram) Al 2(SO 4) 318H 2O is dissolved in 315 ml deionized water and is made into mixing salt solution, with 0.864 mole of (34.6 gram) NaOH and 0.45 mole of (47.7 gram) Na 2CO 3Be dissolved in 315 ml tap waters and be made into mixed ammonium/alkali solutions, under fully stirring, aqueous slkali is poured in the salting liquid, heat up then in 90 ℃ of crystallization 4 hours, generate white precipitate, use the funnel suction filtration, separated products is washed with running water, and 90 ℃ of dryings, getting the nickel aluminum ratio is the hydrotalcite of 3:1: Zn 0.75Al 0.25(OH) 2(CO 3) 0.1255H 2O.
Preparation biodiesel: 10g rapeseed oil and 80g ethanol are added there-necked flask, add the zinc-aluminium hydrotalcite catalyst Zn of 0.1g again 0.75Al 0.25(OH) 2(CO 3) 0.1255H 2O was 78 ℃ of following stirring and refluxing 8 hours.Reaction is removed catalyst after finishing, the product standing demix, and the upper strata is the rapeseed oil methacrylate layer.Product yield is 95.5%.
Embodiment 8
The preparation of solid base catalyst: with 0.36 mole of (57.6 gram) CuSO 4With 0.06 mole of (40.0 gram) Al 2(SO 4) 318H 2O is dissolved in 315 ml deionized water and is made into mixing salt solution, 0.864 mole of (34.6 gram) NaOH is dissolved in 315 ml tap waters and is made into mixed ammonium/alkali solutions, under fully stirring, aqueous slkali is poured in the salting liquid, heated up then, generate precipitation in 90 ℃ of crystallization 4 hours, use the funnel suction filtration, separated products is washed with running water, and 90 ℃ of dryings, getting the copper aluminum ratio is the hydrotalcite of 3:1: Cu 0.75Al 0.25(OH) 2(CO 3) 0.1255H 2O.
Preparation biodiesel: 10g rapeseed oil and 80g ethanol are added there-necked flask, add the copper aluminum hydrotalcite Catalysts Cu of 0.2g again 0.75Al 0.25(OH) 2(CO 3) 0.1255H 2O was 78 ℃ of following stirring and refluxing 8 hours.Reaction is removed catalyst after finishing, the product standing demix, and the upper strata is the rapeseed oil methacrylate layer.Product yield is 97%.
Embodiment 9
The repeated use of catalyst: the catalyst drying that will be among the embodiment 2 reclaims after the preparation biodiesel, add rapeseed oil again and ethanol reacts, reuse experiment.From table 1 on the service life of catalyst as can be seen, after catalyst used 5 times, the yield of biodiesel still remained on more than 90%, this explanation activity of such catalysts decay of the present invention is slow, has good service life, can be repeatedly used.
Table 1
Figure A200910008817D00111
The above only is preferred embodiment of the present invention, and is in order to restriction the present invention, within the spirit and principles in the present invention not all, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (6)

1. solid base catalyst that is used to prepare biodiesel, it is characterized in that: solid base catalyst is used for the biodiesel manufacture process.
2. solid base catalyst that is used to prepare biodiesel is characterized in that: solid base catalyst is that a class is formed controlled anion type laminated compound---houghite compound, and it is formed general formula and is: [M II 1-xM III x(OH) 2] X+(A N-) X/nMH 2O,
M wherein IIAnd M IIIBe divalence and trivalent metal ion, M II-M IIIMetal ion is to also comprising M I-M IIIAnd M II-M IVA N-Be interlayer anion; The x value is between 0.1～0.5, and promptly the mol ratio of divalence and trivalent metal ion is from 1.6:1--10:1; M=1-Nx/n, wherein N is the position number that anion occupies, n is anionic electric charge.
3. according to the described a kind of solid base catalyst that is used to prepare biodiesel of claim 2, it is characterized in that: A during described catalyst is formed N-Comprise inorganic anion and organic anion.
4. according to the described a kind of solid base catalyst that is used to prepare biodiesel of claim 2,, it is characterized in that concrete preparation process is:
A. salting liquid preparation; The divalent metal salt and the trivalent metal salt that are used to prepare salting liquid are one of nitrate, sulfate or hydrochloride, wherein bivalent metal ion [M 2+] concentration be 0.1-4.0mol/L, trivalent metal ion [M 3+] concentration is 0.05-2.0mol/L, the mol ratio [M of bivalent metal ion and trivalent metal ion 2+]/[M 3+] be 1.6:1--10:1;
B. aqueous slkali preparation; Be that one of NaOH, sodium carbonate, ammoniacal liquor, ammonium carbonate, potassium hydroxide, potash, urea, calcium hydroxide or its mixture is water-soluble, if during mixture, proportionate relationship is an arbitrary proportion; Hydroxide ion [OH wherein -] concentration be 0.2-4.0mol/l, carbanion [CO 3 2-] concentration be 0.1-4.0mol/L, the mol ratio of hydroxide ion and divalence, trivalent metal ion mixture is 0.6-3.5;
C. coprecipitation reaction; Be under agitation salting liquid and aqueous slkali to be mixed, more than 0.5 hour, generate precipitation in crystallization under the temperature more than 40 ℃ then; The coprecipitation reaction speed of agitator is more than the 80 commentaries on classics/per minutes, the hybrid mode of salting liquid and aqueous slkali is that salting liquid adds in the aqueous slkali, aqueous slkali adds in the salting liquid or drips salting liquid and aqueous slkali simultaneously, make its mixing, its volume ratio is 1:1, the adding mode is dropping or pours drop rate 5-30 ml/min into;
D. separate, washing, drying, houghite.
5. according to the described a kind of preparation method who is used to prepare the solid base catalyst of biodiesel of claim 4, it is characterized in that: described inorganic agent preparation process D--separation, washing, drying; Drying is that precipitation is separated with centrifugal or suction funnel, is washed with water to neutrality, 70-100 ℃ of drying.
6. according to the described a kind of solid base catalyst that is used to prepare biodiesel of claim 1, it is characterized in that concrete purposes is, natural oil and short chain alcohol are added reaction vessel with 3:1-20:1 alcohol oil quality ratio, add the houghite catalyst of oil quality 1%-5%, at stirring reaction under the temperature more than 60 ℃ more than 0.5 hour; Reaction is removed catalyst after finishing, the product standing demix, and the upper strata is a biodiesel, lower floor is a glycerin layer; Product yield adopts look-matter coupling analytical calculation.
CNA2009100088172A 2009-02-06 2009-02-06 Solid base catalyst for preparing biodiesel Pending CN101474571A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102061224A (en) * 2010-10-11 2011-05-18 西安石油大学 Method for preparing biodiesel by catalysis of modified calcium oxide
CN103028403A (en) * 2011-09-30 2013-04-10 北京化工大学 Body type copper-based ester hydrogenation catalyst and preparation method and application thereof
CN103370405A (en) * 2011-02-14 2013-10-23 科学与工业研究委员会 Improved process for the preparation of fatty acid alkyl esters (biodiesel) from triglyceride oils using eco-friendly solid base catalysts
CN103406118A (en) * 2013-08-19 2013-11-27 太原工业学院 Bio-diesel catalyst CaO/M-Al-O and preparation method thereof
CN103447020A (en) * 2013-09-13 2013-12-18 上海大学 Composite metal oxide catalyst for preparing biodiesel
CN105013466A (en) * 2015-07-14 2015-11-04 南京工程学院 Solid catalyst for production of biodiesel and preparation method and application thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102061224A (en) * 2010-10-11 2011-05-18 西安石油大学 Method for preparing biodiesel by catalysis of modified calcium oxide
CN103370405A (en) * 2011-02-14 2013-10-23 科学与工业研究委员会 Improved process for the preparation of fatty acid alkyl esters (biodiesel) from triglyceride oils using eco-friendly solid base catalysts
CN103370405B (en) * 2011-02-14 2016-05-11 科学与工业研究委员会 Use ecological friendly solid base catalyst to prepare improving one's methods of fatty acid alkyl esters (biodiesel) by triglyceride oil
CN103028403A (en) * 2011-09-30 2013-04-10 北京化工大学 Body type copper-based ester hydrogenation catalyst and preparation method and application thereof
CN103406118A (en) * 2013-08-19 2013-11-27 太原工业学院 Bio-diesel catalyst CaO/M-Al-O and preparation method thereof
CN103406118B (en) * 2013-08-19 2015-03-04 太原工业学院 Bio-diesel catalyst CaO/M-Al-O and preparation method thereof
CN103447020A (en) * 2013-09-13 2013-12-18 上海大学 Composite metal oxide catalyst for preparing biodiesel
CN103447020B (en) * 2013-09-13 2016-04-27 上海大学 A kind of O composite metallic oxide catalyst for the preparation of biodiesel
CN105013466A (en) * 2015-07-14 2015-11-04 南京工程学院 Solid catalyst for production of biodiesel and preparation method and application thereof

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