CN105080606A - Polyoxometallate catalyst for preparing biodiesel - Google Patents

Polyoxometallate catalyst for preparing biodiesel Download PDF

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CN105080606A
CN105080606A CN201410188733.2A CN201410188733A CN105080606A CN 105080606 A CN105080606 A CN 105080606A CN 201410188733 A CN201410188733 A CN 201410188733A CN 105080606 A CN105080606 A CN 105080606A
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catalyst
oil
biodiesel
polyoxometallate
methyl alcohol
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王晓红
张丹
乔红阳
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Northeast Normal University
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Northeast Normal University
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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

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Abstract

The invention relates to a polyoxometallate catalyst for preparing biodiesel. The catalyst is a polyoxometallate compound which has a Keggin structure or a Dawson structure. Biodiesel is catalytically prepared by the catalyst. The catalyst has high catalytic activity and repeatability and wide raw material applicability. The whole preparation process is free of waste water, so that the catalyst is green and environmental-friendly.

Description

A kind of polyoxometallate catalyst preparing biodiesel
Technical field
The present invention relates to a kind of polyoxometallate catalyst preparing biodiesel.
Technical background
Fossil fuel oil plays a part very important in the development of national economy, but it is non-renewable and the pollution of environment is also govern simultaneously to the sustainable development of Chinese national economy.Energy shortage and environment worsen the key subjects becoming countries in the world institute facing.For meeting the demand of social development to the energy, realizing the continuous utilization of resource, maintaining and promoting resource, environment, socioeconomic coordinated development, various countries drop into a large amount of manpower and materials and remove the reproducible new forms of energy of research and development safety.Utilizing inexhaustible, nexhaustible biomass resource to produce fuel and petrochemicals, is the important directions of Green Chemistry.Biodiesel is a kind of recyclable fuel resource coming from animal or plant, has excellent biodegradability, be called as the renewable resource that 21 century has development potentiality most together with solar energy, wind energy, tide energy.The upsurge developing biodiesel resource is just being started at present in countries in the world.Various countries are one after another according to national conditions, select suitable vegetable oil to carry out development and production biodiesel energetically, as the U.S. select that soya-bean oil, Germany and some European countries select rape oil, Malaysia utilizes abundant palm oil successfully preparing biological diesel oil start sizable application.China starts late to biodiesel R and D, within 2000, just starts the research formally paying attention to biodiesel, now the actual annual production in the whole nation
Be also only about ten thousand tons, the production of biodiesel technology of China is only in the junior stage.
At present, the production method of biodiesel mainly contains: chemical method production biodiesel, under acid or base catalyst and high temperature (230-250 DEG C), carry out transesterification by the waste oil of animal and plant grease or catering trade and the low-carbon alcohols such as methyl alcohol or ethanol, generate corresponding fatty acid methyl ester or ethyl ester, then be drying to obtain biodiesel through washing.Methyl alcohol or ethanol can be recycled in process of production, and production equipment is identical with general liquefaction equipment, can produce the byproduct glycerine of about 10% in production process.Production cost is about equivalent to 3 times of petroleum based diesel.Catalyst mainly liquid acid as H 2sO 4, liquid alkali catalyst is as NaOH, KOH.Bibliography MeherL.C., VidyaSagarD., andNaikS.N., RenewableandSustainableEnergyReviews, 2006,10,248)
There is certain problem in chemical catalysis ester-interchange method:
1, reaction speed is slow, and need excessive methanol, alcohol oil rate is high, and subsequent processes is more loaded down with trivial details.
2, transesterification reaction temperature is high, and make the unrighted acid in feedstock oil at high temperature perishable, biodiesel color and luster is dark.
3, biodiesel yield and quality are subject to free aliphatic acid in glyceride stock oil and water mitigation, and feedstock oil is needed to dehydration, reduces free fatty acid content.The existence of free fatty makes reaction rate reduce, and base catalyst generation saponification, and glycerine in product cannot be separated with fatty acid methyl ester generation emulsification.When there being water to exist in reaction system, grease hydrolysis can being made and give birth to soap with alkali.Therefore for base catalyst, require the acid value <1 of feedstock oil, moisture content is lower than 0.06%.For liquid acid catalyst as H 2sO 4, <0.5% is required to feedstock oil moisture content, if hypervolia, acid reduction, catalysqt deactivation.
4, liquid acid, the liquid alkali as a catalyst of homogeneous phase, although the conversion ratio of oil is high, but catalyst can not with product separation, product has to pass through neutralization &washing, produce a large amount of acid (alkali) property sewage, cause secondary pollution to environment, homogeneous phase acidand basecatalysts flows out with product simultaneously, can not reuse, improve the cost of biodiesel.
5, liquid acidand basecatalysts has corrosion to equipment.The solid catalyst of efficient, the low alcohol oil rate of development of new, remains a urgency problem leaved for development.As Japanese Yonemoto seminar (bibliography YonenotoT., ChemicalEngineering, 2005,12,7) develop a kind of alternative catalysts of biodiesel, utilize cationic ion-exchange resin and the double-fluidized-bed reactor of anion exchange resin, realize the conversion of biodiesel.But anion and cation exchange resin is used for ester exchange reaction, easy in inactivation (bibliography SmithK., El-HitiG.A., JayneA.J., ButtersM., Org.Biomol.Chem., 2003,1,1560) Amberlyst catalyst inactivation after 2 hours, Nafion4.5 hour inactivation, is not suitable for the production of serialization.Industrialized project is only utilize cationic ion-exchange resin in the esterification preprocessing process of free acid.
Polyoxometallate is the metal oxygen cluster inorganic compound that a class formation is determined.General structure can be expressed as structure with Keggin Y nh m-n[XM 12o 40] xH 2(X is P, Si, Ge, B to O; M is W, Mo) and Dawson structure Y nh m-n[X 2m 18o 62] xH 2(X is P to O; M is Mo, W), wherein atom centered by X, M is for joining atom, Y and H is gegenion, and H2O is the crystallization water.In the structure of polyoxometallate, XM 12o 40or X 2m 18o 62for the anion frame structure of polyoxometallate, also referred to as primary structure; XM 12o 40or X 2m 18o 62adding gegenion, is secondary structure; XM 12o 40or X 2m 18o 62with gegenion, crystallization water composition tertiary structure.The primary structure of polyoxometallate and the total mol ratio of gegenion are 1:3-6, and gegenion can be hydrogen ion and metal ion simultaneously, and when the gegenion of hydrogen ion as a part, the mol ratio of metal ion and polyoxometallate is 1:1.5-6.
Polyoxometallate is in homogeneous phase and heterogeneous system, show the soda acid of excellent performance, redox catalysis is active, particularly the acid strength of polyoxometallate depends on the quantity of component, counter ion counterionsl gegenions type and content, the crystallization water, can by changing component, regulating gegenion and the crystallization water to control acid amount, to adapt to the requirement of different catalytic reaction.
Utilize polyoxometallate can solve an a lot of technical difficult problem as catalyst in preparation of biodiesel:
1, polyoxometallate is the catalyst that glyceride ester exchange generates fatty acid methyl ester on the one hand; On the other hand,
Catalysis free fatty acid methyl estersization can generate fatty acid methyl ester,
Esterification, ester exchange reaction complete simultaneously.Solve free acid to the impact of catalyst activity, make product be easy to be separated.
2, polyoxometallate is solid acid catalyst.
Polyoxometallate as out-phase catalysts, is easy to be separated from reaction system, does not produce a large amount of pollution sewage in vegetable oil reaction system, and reusable, reduces catalyst use cost.
3, polyoxometallate solid catalyst reaction in " false liquid-phase system ".
Utilize polyoxometallate can form the feature of false liquid-phase system by organic solvent, methyl alcohol and organic solvent is used in the ester exchange reaction of vegetable oil, first solid polyoxometallate forms false liquid phase, forms rich oil single_phase system with vegetable oil again with mixed solvent, so greatly shorten vegetable oil reaction time of esterification, reduce alcohol oil rate and esterification reaction temperature, reaction cost is reduced.
4, vegetable oils does not need pretreatment of dewatering.
5, the adjustability of polyoxometallate catalysis of solid catalyst activity.
By the polyoxometallate catalyst of the different composition of design and synthesis, different-shape, different crystal water content, different acid strength, the vegetable oils of different vegetable oil esterification reaction needed, particularly high acid value can be met, practical.
Summary of the invention
The object of this invention is to provide a kind of polyoxometallate catalyst preparing biodiesel.It is as catalyst, and the waste oil of catalysis vegetable and animals oils, catering trade prepares biodiesel.
A kind of polyoxometallate catalyst for the preparation of biodiesel provided by the invention, it is the polyoxometallate chemical combination with structure with Keggin or Dawson structure; The described general formula with the polyoxometalates of structure with Keggin is:
Y nH m-n[XM 12O 40]·xH 2O，
In formula, X is P, Si, Ge or B; M is W or Mo; Y is Cs +, Zn 2+, Zr 4+, NH 4 +or Ce 4+; M=3 or 4; When Y is Cs +or NH 4 +, n=1.5 or 2.5; When Y is Zn 2+, n=0.75 or 1.25; When Y is Zr 4+or Ce 4+, n=0.375 or 0.625; X=1-2.
The described general formula with the polyoxometalates of Dawson structure is:
Y nH m-n[X 2M 18O 62]·xH 2O，
In formula, X is P, M be Mo or W, Y is Cs +, Zn 2+, Zr 4+, NH 4 +or Ce 4+; M=6, when Y is Cs +or NH 4 +, n=1.5 or 2.5, when Y is Zn 2+, n=0.75 or 1.25, when Y is Zr 4+or Ce 4+, n=0.375 or 0.625; X=1-2.
Described polyoxometalates is preferably:
(1), Cs nh 4-n[SiW 12o 40] (n=1.5 or 2.5),
(2), Cs nh 4-n[GeW 12o 40] (n=1.5 or 2.5),
(3), Cs nh 4-n[BW 12o 40] (n=1.5 or 2.5),
(4), Zn nh 3-2n[PW 12o 40] (n=0.75 or 1.25),
(5)、Zn nH 4-2n[SiW 12O 40](n＝0.75,1.25)，
(6), Zn nh 4-2n[GeW 12o 40] (n=0.75 or 1.25),
(7), Zn nh 4-2n[BW 12o 40] (n=0.75 or 1.25),
(8), Zr nh 4-4n[SiW 12o 40] (n=0.375 or 0.625),
(9), Zr nh 4-4n[GeW 12o 40] (n=0.375 or 0.625),
(10), Zr nh 4-4n[BW 12o 40] (n=0.375 or 0.625),
(11), Ce nh 4- 4n[GeW 12o 40] (n=0.375 or 0.625),
(12), Ce nh 4-4n[BW 12o 40] (n=0.375 or 0.625),
(13), (NH 4) nh 3- n[PW 12o 40] (n=1.5 or 2.5),
(14), (NH 4) nh 4-n[SiW 12o 40] (n=1.5 or 2.5),
(15), (NH 4) nh 4- n[GeW 12o 40] (n=1.5 or 2.5),
(16), (NH 4) nh 4-n[BW 12o 40] (n=1.5 or 2.5),
(17), Cs nh 6-n[P 2w 18o 62] (n=1.5 or 2.5),
(18), (NH 4) nh 6-n[P 2w 18o 62] (n=1.5 or 2.5),
(19), Zr nh 6-4n[P 2w 18o 62] (n=0.375 or 0.625),
(20), Ce nh 6-4n[P 2w 18o 62] (n=0.375 or 0.625),
(21), Cs nh 6-n[P 2mo 18o 62] (n=1.5 or 2.5),
(22), (NH 4) nh 6-n[P 2mo 18o 62] (n=1.5 or 2.5),
(23), Zr nh 6-4n[P 2mo 18o 62] (n=0.375 or 0.625) or
(24), Ce nh 6-4n[P 2mo 18o 62] (n=0.375 or 0.625).
The invention provides a kind of prepare the preparation method of the polyoxometallate catalyst of biodiesel step and condition as follows:
1:1.5-6 weighs polyoxometalates H respectively in molar ratio 4[SiW 12o 40] 23H 2o and precipitating reagent, described precipitating reagent is CsCl, Zr (NO 3) 4, Ce (NO 3) 3, Zn (AC) 2or NH 4cl); Polyoxometalates 4 [SiW 12o 40] 23H 2o pours in reactor, and adding mass ratio is 1:5-10 distilled water doubly, is heated to 50-60 DEG C, stirring and dissolving; Add precipitating reagent wherein again, reactant liquor ageing 5-10 hour, separate out solids, filter, precipitate 2-3 time with distilled water flushing, until the pH value of eluate reaches 5-8, be precipitated thing; This sediment is placed in horse still stove, in 150-300 DEG C of sintering 2-6 hour, namely obtains a kind of polyoxometallate catalyst preparing biodiesel.Its productive rate is 84%.
With a kind of polyoxometallate catalyst preparing biodiesel provided by the invention, the method that the waste oil of catalysis vegetable and animals oils, catering trade prepares biodiesel is as follows:
In the reactor, add feedstock oil and methyl alcohol compounded organic solvent that volume ratio is 1:4-72, described methyl alcohol compounded organic solvent is methyl alcohol and oxolane mixed solvent, the volume ratio 1-5:1 of methyl alcohol and oxolane, abundant stirring, and be heated to 45-65 DEG C, add provided by the invention a kind of polyoxometallate catalyst preparing biodiesel of feedstock oil weight 1%, reaction 45min-10h, product is left standstill 2-8 hour, catalyst sedimentation is in reactor bottom, filter out catalyst, recyclablely to recycle, product mixtures is divided into two layers, upper strata is crude fatty acid methyl ester and biodiesel crude product, activated carbon decolorizing process obtains biodiesel.Its productive rate 94%; Lower floor is the mixed layer of glycerine and methyl alcohol compounded organic solvent, and 40 DEG C of decompression distillation steam excessive methanol compounded organic solvent, recycles, obtains refined glycerine.
Described feedstock oil comprises herbaceous plant oil, xylophyta oil or waste oil from restaurant;
Described herbaceous plant oil is soybean oil, rapeseed oil, the mustard oil that rues, siritch, Hippophae Rhamnoides L. Seed, Caragana Microphylla Seed oil, windproof seed oil; Xylophyta oil is shiny-leaved yellowhorn seed oil, jatropha curcas seed oil, tung oil tree seeds of trees oil, wilson dogwood seeds of trees oil, Chinese pistache seeds of trees oil.
A kind of polyoxometallate catalyst preparing biodiesel provided by the invention, there is adaptability to raw materials, high catalytic activity widely, ensure that esterification is carried out under low alcohol oil rate, lower temperature, fatty acid methyl ester conversion rate is high, obtains the product of the standard meeting present stage international bio diesel oil.Solid acid catalysts easily reclaims simultaneously, reusable, overcomes traditional biological diesel fuel synthesis process flow process complicated, and " three wastes " discharge capacity is large, the defect of contaminated environment.Byproduct glycerine is easy to reclaim, refine or deep processing and utilization simultaneously.The strong adaptability of raw material, can comprise herbaceous plant oil, xylophyta oil or waste oil from restaurant with described feedstock oil.Described herbaceous plant oil is soybean oil, rapeseed oil, the mustard oil that rues, siritch, Hippophae Rhamnoides L. Seed, Caragana Microphylla Seed oil, windproof seed oil; Xylophyta oil is shiny-leaved yellowhorn seed oil, jatropha curcas seed oil, tung oil tree seeds of trees oil, wilson dogwood seeds of trees oil, Chinese pistache seeds of trees oil.
Detailed description of the invention
Embodiment 1
Weigh the polyoxometalates H4 [SiW of mol ratio 1:1.5 respectively 12o 40] 23H 2o and precipitating reagent CsCl.Polyoxometalates is poured in reactor, and adding mass ratio is 1:5 distilled water doubly, is heated to 50 DEG C, stirring and dissolving.Add precipitating reagent solid wherein, reactant liquor ageing 10 hours, separate out solid, filter, precipitate 3 times with distilled water flushing, until the pH value of eluate reaches 5.Be deposited in horse still stove, sinter 2 hours in 150 DEG C, namely obtain the solid catalyst of polyoxometalates.Its productive rate is 84%.
The structure infrared spectrum of solid catalyst, ultraviolet spectra are determined.
Embodiment 2
Weigh the polyoxometalates H of mol ratio 1:6 respectively 6[P 2w 18o 62] 23H 2o and precipitating reagent CsCl.Polyoxometalates is poured in reactor, and adding mass ratio is 1:10 distilled water doubly, is heated to 60 DEG C, stirring and dissolving.Add precipitating reagent solid wherein, reactant liquor ageing 2 hours, separate out solid, filter, precipitate 3 times with distilled water flushing, until the pH value of eluate reaches 8.Be deposited in horse still stove, sinter 6 hours in 300 DEG C, namely obtain the solid catalyst of polyoxometalates.Its productive rate is 84%.
Embodiment 3
Weigh the polyoxometalates H of mol ratio 1:2.5 respectively 4[SiW 12o 40] 23H 2o and precipitating reagent NH 4cl.Polyoxometalates is poured in reactor, and adding mass ratio is 1:8 distilled water doubly, is heated to 55 DEG C, stirring and dissolving.Add precipitating reagent solid wherein, reactant liquor ageing 6 hours, separate out solid, filter, precipitate 3 times with distilled water flushing, until the pH value of eluate reaches 7.Be deposited in horse still stove, sinter 4 hours in 150 DEG C, namely obtain the solid catalyst of polyoxometalates.Its productive rate is 84%.
Embodiment 4
In the reactor of 1L, add rue mustard oil and methyl alcohol compounded organic solvent that volume ratio is 1:4, (methyl alcohol compounded organic solvent is methyl alcohol and oxolane mixed solvent to methyl alcohol compounded organic solvent, volume ratio 5:1) mixing, abundant stirring, and be heated to 45 DEG C, add provided by the invention a kind of polyoxometallate catalyst (NH preparing biodiesel of feedstock oil weight 1% 4) 1.5h 1.5[PW 12o 40], reaction 45min, product is left standstill 8 hours, and catalyst sedimentation is in reactor bottom, filter out catalyst, recyclablely to recycle, product mixtures is divided into two layers, upper strata is crude fatty acid methyl ester and biodiesel, and activated carbon decolorizing simple process obtains biodiesel, its productive rate 94%; Lower floor is the mixed layer of glycerine and methyl alcohol compounded organic solvent, and 40 DEG C of decompression distillation steam excessive methanol compounded organic solvent, recycles, obtains refined glycerine.
The conversion ratio of the biodiesel that the method obtains is determined by hydrogen nuclear magnetic spectrogram.Its productive rate 94%.
Embodiment 5
In the reactor of 1L, add soybean oil and methyl alcohol compounded organic solvent that volume ratio is 1:18, (methyl alcohol compounded organic solvent is methyl alcohol and oxolane mixed solvent to methyl alcohol compounded organic solvent, volume ratio 1:1) mixing, abundant stirring, and be heated to 65 DEG C, add provided by the invention a kind of polyoxometallate catalyst Cs preparing biodiesel of feedstock oil weight 1% 2.5h 1.5[BW 12o 40], reaction 2h, product is left standstill 6 hours, and catalyst sedimentation is in reactor bottom, filter out catalyst, recyclablely to recycle, product mixtures is divided into two layers, upper strata is crude fatty acid methyl ester and biodiesel, and activated carbon decolorizing simple process obtains biodiesel, its productive rate 94%; Lower floor is the mixed layer of glycerine and methyl alcohol compounded organic solvent, and 40 DEG C of decompression distillation steam excessive methanol compounded organic solvent, recycles, obtains refined glycerine.
Embodiment 6
In the reactor of 1L, add feedstock oil and methyl alcohol compounded organic solvent that volume ratio is 1:72, (methyl alcohol compounded organic solvent is methyl alcohol and oxolane mixed solvent to methyl alcohol compounded organic solvent, volume ratio 3:1) mixing, abundant stirring, and be heated to 65 DEG C, add provided by the invention a kind of polyoxometallate catalyst Ce preparing biodiesel of feedstock oil weight 1% 0.625h 3.5[P 2mo 18o 62], reaction 10h, product is left standstill 6 hours, and catalyst sedimentation is in reactor bottom, filter out catalyst, recyclablely to recycle, product mixtures is divided into two layers, upper strata is crude fatty acid methyl ester and biodiesel, and activated carbon decolorizing simple process obtains biodiesel, its productive rate 84%; Lower floor is the mixed layer of glycerine and methyl alcohol compounded organic solvent, and 40 DEG C of decompression distillation steam excessive methanol compounded organic solvent, recycles, obtains refined glycerine.

Claims (2)

1. for the preparation of a polyoxometallate catalyst for biodiesel, it is characterized in that, it is the polyoxometalates with structure with Keggin or Dawson structure;
The described general formula with the polyoxometalates of structure with Keggin is:
YnHm-n[XM 12O 40]·xH 2O，
In formula, X is P, Si, Ge or B; M is W or Mo; Y is Cs +, Zn 2+, Zr 4+, NH 4 +or Ce 4+;
M=3 or 4; When Y is Cs +or NH 4 +, n=1.5 or 2.5; When Y is Zn 2+, n=0.75 or 1.25; When Y is Zr 4+or Ce 4+, n=0.375 or 0.625; X=1-2
The described general formula with the polyoxometalates of Dawson structure is:
YnHm-n[X 2M 18O 62]·xH 2O，
In formula, X is P, M be Mo or W, Y is Cs +, Zn 2+, Zr 4+, NH 4 +or Ce 4+;
M=6, when Y is Cs +or NH 4 +, n=1.5 or 2.5, when Y is Zn 2+, n=0.75 or 1.25, when Y is Zr 4+or Ce 4+, n=0.375 or 0.625; X=1-2.
2. a kind of polyoxometallate catalyst for the preparation of biodiesel as claimed in claim 1, is characterized in that, described polyoxometalates is preferably:
(1), CsnH 4-n[SiW 12o 40] (n=1.5 or 2.5),
(2), Cs nh 4-n[GeW 12o 40] (n=1.5 or 2.5),
(3), Cs nh 4-n[BW 12o 40] (n=1.5 or 2.5),
(4), Zn nh 3-2n[PW 12o 40] (n=0.75 or 1.25),
(5)、Zn nH 4-2n[SiW 12O 40](n＝0.75,1.25)，
(6), Zn nh 4-2n[GeW 12o 40] (n=0.75 or 1.25),
(7), Zn nh 4-2n[BW 12o 40] (n=0.75 or 1.25),
(8), Zr nh 4-4n[SiW 12o 40] (n=0.375 or 0.625),
(9), Zr nh 4-4n[GeW 12o 40] (n=0.375 or 0.625),
(10), Zr nh 4-4n[BW 12o 40] (n=0.375 or 0.625),
(11), Ce nh 4-4n[GeW 12o 40] (n=0.375 or 0.625),
(12), Ce nh 4-4n[BW 12o 40] (n=0.375 or 0.625),
(13), (NH4) nh 3-n[PW 12o 40] (n=1.5 or 2.5),
(14), (NH4) nh 4-n[SiW 12o 40] (n=1.5 or 2.5),
(15), (NH4) nh 4-n[GeW 12o 40] (n=1.5 or 2.5),
(16), (NH4) nh 4-n[BW 12o 40] (n=1.5 or 2.5),
(17), Cs nh 6-n[P 2w 18o 62] (n=1.5 or 2.5),
(18), (NH4) nh 6-n[P 2w 18o 62] (n=1.5 or 2.5),
(19), Zr nh 6-4n[P 2w 18o 62] (n=0.375 or 0.625),
(20), Ce nh 6-4n[P 2w 18o 62] (n=0.375 or 0.625),
(21), Cs nh 6-n[P 2mo 18o 62] (n=1.5 or 2.5),
(22), (NH4) nh 6-n[P 2mo 18o 62] (n=1.5 or 2.5),
(23), Zr nh 6-4n[P 2mo 18o 62] (n=0.375 or 0.625) or
(24), Ce nh 6-4n[P 2mo 18o 62] (n=0.375 or 0.625).
CN201410188733.2A 2014-05-06 2014-05-06 Polyoxometallate catalyst for preparing biodiesel Pending CN105080606A (en)

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CN108355700A (en) * 2018-03-02 2018-08-03 河北科技大学 Polyoxometallate and its compound, preparation method and application
CN110055138A (en) * 2019-04-30 2019-07-26 广州市广环环保科技有限公司 A method of utilizing kitchen garbage preparing biological diesel oil and glycerol
CN110055138B (en) * 2019-04-30 2023-02-24 广州市广环环保科技有限公司 Method for preparing biodiesel and glycerol from kitchen waste
CN110201712A (en) * 2019-05-10 2019-09-06 东北师范大学 A kind of ion liquid type polyoxometallate catalyst and its preparation method and application
CN110201712B (en) * 2019-05-10 2021-12-07 东北师范大学 Ionic liquid type polyoxometallate catalyst and preparation method and application thereof

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