CN1891787A - Production technology for preparing biodiesel by solid magnetic catalyst - Google Patents

Production technology for preparing biodiesel by solid magnetic catalyst Download PDF

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CN1891787A
CN1891787A CNA2005100829222A CN200510082922A CN1891787A CN 1891787 A CN1891787 A CN 1891787A CN A2005100829222 A CNA2005100829222 A CN A2005100829222A CN 200510082922 A CN200510082922 A CN 200510082922A CN 1891787 A CN1891787 A CN 1891787A
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oil
solid magnetic
magnetic catalyst
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kilograms
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CN1891787B (en
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阮榕生
高荫榆
林向阳
陈文伟
刘玉环
白松
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Nanchang University
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Nanchang University
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock

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Abstract

The invention relates to the production technology used solid magnetism catalysis to make biological diesel oil. It mixes low carbon alcohol with animal and vegetable oils to do ester interchange reaction by catalyst at certain temperature. After it has finished, the upper layer is the coarse biological diesel oil; and the under is the mixture of glycerol and low carbon alcohol. The upper layer coarse product is purified at the following conditions: the mol ratio of the carbon alcohol and the animal and vegetable oils is 3-40:1; the catalyst is the solid magnetism; the ester interchange is at 40-100 centigrade degree for 1-5 hours; and the weight of the added catalyst are 1%-10% of the animal and vegetable oils. The solid magnetism catalysis contains Ni2O3, Co2O3, and Fe2O3. Thus, it can separate from the liquid state biological diesel oil well and reduce the pollution. And it can be used circularly and has no corrode for conversion unit.

Description

The production technology of preparing biodiesel by solid magnetic catalyst
Technical field
The present invention relates to a kind of production technology of the production technology for preparing biofuel, especially preparing biodiesel by solid magnetic catalyst.The present invention is raw material with the vegetables oil.
Background technology
Development along with modern high technology and industry and commerce, people are also gone up to the use amount of oil thereupon, and the fossil energies such as the coal that develops of containing on the earth and oil will be respectively 200 years and 30 to 40 years with interior exhaustion, natural gas also can only be with 60 years by reserve-production ratio.Therefore, the energy shortage problem will perplex the development of human society for a long time, and the environmental pollution that the waste gas of discharging causes after the simultaneously oil product burning also is big a problem, particularly CO of facing mankind 2Always showing property increase of content.Therefore, reproducible, the environmental protection of exploitation, substituting green fuel have become one of human most important problem of 21 century.
Biofuel (Biodiesel), claim that again fatty acid monoester (Fatty Acid Ester) is to make raw material with Vegetable oil lipoprotein or animal tallow oil, the edible wet goods of depleted, obtains through lactide reaction (Transesterification reaction) with alcohols (methyl alcohol, ethanol).Fuel value and petrifaction diesel are approaching, and cetane value is higher than petrifaction diesel, be a kind of can clean-burning capable of regeneration green fuel oil, can be used as the substitute of petrifaction diesel.Or mix use with petrifaction diesel.
The biofuel sulphur content is extremely low, and aromatic hydrocarbon content is few, the oxygen level height, and the cetane value height, the flash-point height, waste gas is overflowed few; In the waste gas of overflowing in the burning back, micropartical (PM), total hydrocarbons (HC) and carbon monoxide content are few; In addition, it still is a kind of avirulent material.This is the advantage of biofuel, has environmental friendliness and health effect.Compare with other alternative fuel such as compressed natural gas, liquid natural gas, liquefied petroleum gas (LPG), methyl alcohol, ethanol etc., use biofuel system less investment, original engine, bunkering facilities, storage facilities, maintain equipment etc. need not be changed substantially; It both can be used as fuel and had used, and also can be used as additive and mixed with arbitrary proportion with ordinary diesel oil.
Not only can reduce environmental pollution with preparing biological diesel oil by animal plant lipid, and, strengthen problem of Chinese energy safety, and promote the comprehensive development and utilization of agricultural byproducts that great profound significance is arranged for alleviating China's energy dilemma.
The catalyst of ester exchange process mostly is homogeneous catalyst in the biodiesel preparation process at present, generally all adopts NaOH, KOH, metal sodium alkoxide and dense H 2SO 4NaOH, KOH, metal sodium alkoxide and dense H 2SO 4Deng mainly being cheap being easy to get as catalyzer, but there is important disadvantages in it, corrosive equipment, and the aftertreatment complexity can cause the three wastes, contaminate environment.
NaOH, KOH, metal sodium alkoxide and dense H 2SO 4Must separate fully with final biofuel Deng material, otherwise can influence the quality and the performance of biofuel.Aftertreatment need consume a large amount of water could be with NaOH, KOH, metal sodium alkoxide and dense H 2SO 4Deng the material washes clean, this has just brought a large amount of three wastes, contaminate environment.And the residual water in the biofuel can not surpass certain limit, otherwise also can influence the quality and the performance of biofuel.For water and biofuel effectively being separated needs expensive separating device investment and complicated separating technology.
And solid magnetic catalyst separates with reaction system in chemical reaction easily; Mean that isolating cost and facility investment are low, be more suitable for industrialization.Post catalyst reaction is regenerated easily, can save spending, and NaOH, KOH, metal sodium alkoxide and dense H 2SO 4Cannot regenerate; Solid magnetic catalyst is to not corrosion of conversion unit.Therefore, the solid magnetic catalyst of development of new replaces existing homogeneous catalyst, and significance is arranged in catalyzed reaction.
Summary of the invention
The object of the present invention is to provide a kind of technology of solid magnetic catalyst catalysis for preparing biodiesel oil, solid magnetic catalyst is recyclable, and has solved the problems such as contaminate environment that adopt traditional catalyzer to bring.
Technical scheme of the present invention:
The production technology of preparing biodiesel by solid magnetic catalyst, under catalyst action and under the certain temperature, low-carbon alcohol is mixed with animal-plant oil and stir and carry out transesterification reaction, after reaction finishes, the upper strata is the thick product of biofuel, lower floor is the mixture of glycerine and low-carbon alcohol, biofuel thick purifying products in upper strata is got biofuel, wherein: the mol ratio of low-carbon alcohol and animal-plant oil is 3-40: 1, catalyzer adopts solid magnetic catalyst, transesterify is carried out under 40-100 ℃, and the reaction times is 1-5 hour, and the catalyzer of adding is the 1%-10% of animal-plant oil weight.
Solid magnetic catalyst of the present invention contains Ni 2O 3, Co 2O 3, Fe 2O 3Etc. the magnetic material, so sintering solid magnetic catalyst together can under the effect in magnetic field, better separate with the biodiesel of liquid condition.Thereby can reduce a large amount of washing water.Reduce sewage pollution.
The thick purifying products technology of biofuel is a prior art, the thick purifying products technology of biofuel that a lot of bibliographical informations arranged.
The production technology of preparing biodiesel by solid magnetic catalyst, wherein: transesterify is carried out under 40-60 ℃.
The production technology of preparing biodiesel by solid magnetic catalyst, wherein: the raw glycerine that lower floor is distilled out after the low-carbon alcohol obtains byproduct glycerine behind resin purification, the low-carbon alcohol that distills out recycles.
The production technology of preparing biodiesel by solid magnetic catalyst, wherein: solid magnetic catalyst comprises the Ni that calculates with oxide 2O 3Or Co 2O 3, ZrO 2, Fe 2O 3, its element mol ratio that forms by Ni or Co, Zr, Fe is 1-3: 2-6: 5-15; Solid magnetic catalyst obtains by following method: 4 moles FeSO 47H 2O, 2 moles Fe 2(SO 4) 3The distilled water that adds 10 moles, the control temperature is 50 ℃, slowly adds uniformly 0.8 mole ammoniacal liquor in 2 hours, stirs, and drips off rear ageing 1 hour, obtains the precipitation of glossy black look, the supernatant that inclines adds then the distilled water cyclic washing and is precipitated to neutrality, and do not have SO 4 2-, it is for subsequent use to get intermediate A; Add in molar ratio the Ni after pulverizing in the intermediate A 2O 3Or Co 2O 3, ZrO 2, stir into pasty state, add again 15 moles distilled water, in 3 hours, slowly add uniformly 2 moles ammoniacal liquor, stir, be warming up to 60 ℃ after dripping off and continue to stir ageing 6 hours, be precipitated, the supernatant that inclines adds then the distilled water cyclic washing and is precipitated to neutrality, and it is for subsequent use to get intermediate B; With intermediate B in 80 ℃ of vacuum drying 12 hours; Again 500 ℃ of calcination 10 hours in muffle furnace are transformed into composite oxides, and these composite oxides are solid magnetic catalyst.
The production technology of preparing biodiesel by solid magnetic catalyst, wherein: solid magnetic catalyst comprises MgO or CaO, the Al that calculates with oxide 2O 3, Fe 2O 3, its element mol ratio that forms by Mg or Ca, Al, Fe is 6-18: 2-6: 3-9; Solid magnetic catalyst obtains by following method: 4 moles FeSO 47H 2O, 2 moles Fe 2(SO 4) 3The distilled water that adds 10 moles, the control temperature is 50 ℃, slowly adds uniformly 0.8 mole ammoniacal liquor in 2 hours, stirs, and drips off rear ageing 1 hour, obtains the precipitation of glossy black look, the supernatant that inclines adds then the distilled water cyclic washing and is precipitated to neutrality, and do not have SO 4 2-, it is for subsequent use to get intermediate A; Add in molar ratio MgO or CaO, Al after pulverizing in the intermediate A 2O 3, stir into pasty state, add again 15 moles distilled water, in 3 hours, slowly add uniformly 2 moles ammoniacal liquor, stir, be warming up to 60 ℃ after dripping off and continue to stir ageing 6 hours, be precipitated, the supernatant that inclines adds then the distilled water cyclic washing and is precipitated to neutrality, and it is for subsequent use to get intermediate B; With intermediate B in 80 ℃ of vacuum drying 12 hours; Again 500 ℃ of calcination 10 hours in muffle furnace are transformed into composite oxides, and these composite oxides are solid magnetic catalyst.
The production technology of preparing biodiesel by solid magnetic catalyst, wherein: the mixture of glycerine and low-carbon alcohol is reclaimed respectively.
The production technology of preparing biodiesel by solid magnetic catalyst, wherein: described animal-plant oil is any one or a few the mixture in soybean oil, genetically engineered soybean oil, rapeseed oil, transgenosis rapeseed oil, Oleum Gossypii semen, Chinese vegetable tallow, Viscotrol C, plam oil, peanut oil, sesame oil, Semen Maydis oil, sunflower seed oil, sweet oil, safflower oil, pine nut oil, walnut oil, Prunus amygdalus oil, raisin seed oil, wheatgerm oil, rice germ oil, Rice pollard oil, tea-seed oil, fruit of cubeb litsea tree oil, lard, butter, sheep oil, fish oil, the discarded edible oil.
The production technology of preparing biodiesel by solid magnetic catalyst, wherein: described low-carbon alcohol is methyl alcohol, ethanol or the mixture of the two.
Advantage of the present invention is: adopt solid magnetic catalyst can avoid adopting homogeneous catalyst such as sodium hydroxide, potassium hydroxide, sodium methylate or dense H 2SO 4Required washing and the neutralization procedure of technology, do not produce waste streams.Solid magnetic catalyst reclaims easily and can reuse under the effect in magnetic field, and does not cause the corrosion to consersion unit.Standing demix after the reaction, the upper strata is the thick product of biodiesel, lower floor is the mixture of glycerine and methyl alcohol (ethanol).Byproduct reclaims convenient.Compare and adopt alkaline catalysts, acid catalyst, enzyme catalyst, solid magnetic catalyst is renewable, and is promptly reusable after 2 hours 50 ℃ of calcination; Save cost.
Embodiment
Embodiment one: raw material: plam oil, solid magnetic catalyst, methyl alcohol.
Solid magnetic catalyst comprises MgO, the Al that calculates with oxide 2O 3, Fe 2O 3, its element mol ratio that forms by Mg, Al, Fe is 5: 1: 4.
Solid magnetic catalyst obtains by following method: 4 moles FeSO 47H 2O, 2 moles Fe 2(SO 4) 3The distilled water that adds 10 moles, controlled temperature is 50 ℃, slowly adds 0.8 mole ammoniacal liquor in 2 hours uniformly, stirs, and drips off back ageing 1 hour, obtains the precipitation of glossy black look, the supernatant liquor that inclines adds the distilled water repetitive scrubbing then and is precipitated to neutrality, and do not have SO 4 2-, it is standby to get intermediate A; The element mol ratio of pressing Mg, Al, Fe adds MgO, the Al after pulverizing in intermediate A 2O 3, stir into pasty state, add 15 moles distilled water again, in 4 hours, slowly add 4 moles ammoniacal liquor uniformly, stir, be warming up to 60 ℃ after dripping off and continue to stir ageing 6 hours, obtain precipitation, the supernatant liquor that inclines adds the distilled water repetitive scrubbing then and is precipitated to neutrality, intermediate B is standby; With intermediate B in 80 ℃ of vacuum-dryings 12 hours; 500 ℃ of calcination 10 hours in muffle furnace again are transformed into composite oxides, and these composite oxides are solid magnetic catalyst.
50.0 kilograms palm oils and 12.0 kilograms of methyl alcohol are added in the reactor, stir, add 1.5 kilograms of solid magnetic catalysts, under 40 ℃, carry out ester exchange reaction, reacted 2.0 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 42.1 kilograms of biodiesel behind the purifying of upper strata.
Embodiment two: raw material: soybean oil, solid magnetic catalyst, methyl alcohol.
Solid magnetic catalyst comprises MgO, the Al that calculates with oxide 2O 3, Fe 2O 3, its element mol ratio that forms by Mg, Al, Fe is 8: 5: 3; All the other are with embodiment one.
50.0 kilograms soybean oils and 8.0 kilograms of methyl alcohol are added in the reactor, stir, add 2.0 kilograms of solid magnetic catalysts, under 70 ℃, carry out ester exchange reaction, reacted 4.0 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 48.2 kilograms of biodiesel behind the purifying of upper strata.
It is promptly reusable after 2 hours 50 ℃ of calcination to reclaim solid magnetic catalyst.Other gets 50.0 kilograms soybean oil and 8.0 kilograms of methyl alcohol and adds in the reactor, stirs, and adds the solid magnetic catalysts of 2.0 kilograms of recovery calcination, carries out ester exchange reaction under 70 ℃, reacts 4.0 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 46.9 kilograms of biodiesel behind the purifying of upper strata.
The solid magnetic catalyst calcination that proof reclaims is renewable after 2 hours.And very little to the oil productivity impact.
Embodiment three: raw material: Oleum Gossypii semen, solid magnetic catalyst, ethanol.
Solid magnetic catalyst comprises MgO, the Al that calculates with oxide 2O 3, Fe 2O 3, its element mol ratio that forms by Mg, Al, Fe is 12: 3: 5; All the other are with embodiment one.
50.0 kilograms cottonseed oils and 20.0 kilograms of ethanol are added in the reactor, stir, add 4.0 kilograms of solid magnetic catalysts, under 50.0 ℃, carry out ester exchange reaction, reacted 3.0 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and ethanol, gets 48.5 kilograms of biodiesel behind the purifying of upper strata.
Embodiment four: raw material: catering trade waste oil, solid magnetic catalyst, ethanol.
Solid magnetic catalyst comprises MgO, the Al that calculates with oxide 2O 3, Fe 2O 3, its element mol ratio that forms by Mg, Al, Fe is 11: 2: 4; All the other are with embodiment one.
50.0 kilograms waste oil from restaurants and 18.0 kilograms of ethanol are added in the reactor, stir, add 1.5 kilograms of solid magnetic catalysts, under 90 ℃, carry out ester exchange reaction, reacted 2.0 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and ethanol, gets 46.2 kilograms of biodiesel behind the purifying of upper strata.
Embodiment five: raw material: rapeseed oil, solid magnetic catalyst, methyl alcohol.
Solid magnetic catalyst comprises CaO, the Al that calculates with oxide 2O 3, Fe 2O 3, its element mol ratio that forms by Ca, Al, Fe is 8: 3: 7.
Solid magnetic catalyst obtains by following method: 4 moles FeSO 47H 2O, 2 moles Fe 2(SO 4) 3The distilled water that adds 10 moles, controlled temperature is 50 ℃, slowly adds 0.8 mole ammoniacal liquor in 2 hours uniformly, stirs, and drips off back ageing 1 hour, obtains the precipitation of glossy black look, the supernatant liquor that inclines adds the distilled water repetitive scrubbing then and is precipitated to neutrality, and do not have SO 4 2-, it is standby to get intermediate A; The element mol ratio of pressing Ca, Al, Fe adds CaO, the Al after pulverizing in intermediate A 2O 3, stir into pasty state, add 15 moles distilled water again, in 4 hours, slowly add 4 moles ammoniacal liquor uniformly, stir, be warming up to 60 ℃ after dripping off and continue to stir ageing 6 hours, obtain precipitation, the supernatant liquor that inclines adds the distilled water repetitive scrubbing then and is precipitated to neutrality, intermediate B is standby; With intermediate B in 80 ℃ of vacuum-dryings 12 hours; 500 ℃ of calcination 10 hours in muffle furnace again are transformed into composite oxides, and these composite oxides are solid magnetic catalyst.
50.0 kilograms rapeseed oils and 10.0 kilograms of methyl alcohol are added in the reactor, stir, add 3.0 kilograms of solid magnetic catalysts, under 40 ℃, carry out ester exchange reaction, reacted 2.0 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 42.5 kilograms of biodiesel behind the purifying of upper strata.
It is promptly reusable after 2 hours 50 ℃ of calcination to reclaim solid magnetic catalyst.Other gets 50.0 kilograms rapeseed oil and 10.0 kilograms of methyl alcohol and adds in the reactor, stirs, and adds the solid magnetic catalysts of 3.0 kilograms of recovery calcination, carries out ester exchange reaction under 40 ℃, reacts 2.0 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 41.9 kilograms of biodiesel behind the purifying of upper strata.
The solid magnetic catalyst calcination that proof reclaims is renewable after 2 hours.And very little to the oil productivity impact.
Embodiment six: raw material: Viscotrol C, solid magnetic catalyst, methyl alcohol.
Solid magnetic catalyst comprises CaO, the Al that calculates with oxide 2O 3, Fe 2O 3, its element mol ratio that forms by Ca, Al, Fe is 11: 2: 5; All the other are with embodiment five.
50.0 kilograms castor oil and 16.0 kilograms of methyl alcohol are added in the reactor, stir, add 2.5 solid magnetic catalysts, under 60 ℃, carry out ester exchange reaction, reacted 2.5 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 49.1 kilograms of biodiesel behind the purifying of upper strata.
Embodiment seven: raw material: lard, solid magnetic catalyst, methyl alcohol.
Solid magnetic catalyst comprises CaO, the Al that calculates with oxide 2O 3, Fe 2O 3, its element mol ratio that forms by Ca, Al, Fe is 10: 5: 3; All the other are with embodiment five.
50.0 kilograms lards and 18.0 kilograms of methyl alcohol are added in the reactor, stir, add 2.5 kilograms of solid magnetic catalysts, under 70 ℃, carry out ester exchange reaction, reacted 3.0 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 48.5 kilograms of biodiesel behind the purifying of upper strata.
Embodiment eight: raw material: plam oil, solid magnetic catalyst, methyl alcohol.
Solid magnetic catalyst comprises the Ni that calculates with oxide 2O 3, ZrO 2, Fe 2O 3, its element mol ratio that forms by Ni, Zr, Fe is 1: 3: 12.
Solid magnetic catalyst obtains by following method: 4 moles FeSO 47H 2O, 2 moles Fe 2(SO 4) 3The distilled water that adds 10 moles, controlled temperature is 50 ℃, slowly adds 0.8 mole ammoniacal liquor in 2 hours uniformly, stirs, and drips off back ageing 1 hour, obtains the precipitation of glossy black look, the supernatant liquor that inclines adds the distilled water repetitive scrubbing then and is precipitated to neutrality, and do not have SO 4 2-, it is standby to get intermediate A; The element mol ratio of pressing Ni, Zr, Fe adds the ZrO after pulverizing in intermediate A 2, Ni 2O 3, stir into pasty state, add 15 moles distilled water again, in 3 hours, slowly add 2 moles ammoniacal liquor uniformly, stir, be warming up to 60 ℃ after dripping off and continue to stir ageing 6 hours, obtain precipitation, the supernatant liquor that inclines adds the distilled water repetitive scrubbing then and is precipitated to neutrality, intermediate B is standby; With intermediate B in 80 ℃ of vacuum-dryings 12 hours; 500 ℃ of calcination 10 hours in muffle furnace again are transformed into composite oxides, and these composite oxides are solid magnetic catalyst.
50.0 kilograms palm oils and 24.0 kilograms of methyl alcohol are added in the reactor, stir, add 3.0 kilograms of solid magnetic catalysts, under 80 ℃, carry out ester exchange reaction, reacted 2.0 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 48.2 kilograms of biodiesel behind the purifying of upper strata.
It is promptly reusable after 2 hours 50 ℃ of calcination to reclaim solid magnetic catalyst.Other gets 50.0 kilograms palm oil and 24.0 kilograms of methyl alcohol and adds in the reactor, stirs, and adds 3.0 kilograms of solid magnetic catalysts, carries out ester exchange reaction under 80 ℃, reacts 2.0 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 48.0 kilograms of biodiesel behind the purifying of upper strata.
The solid magnetic catalyst calcination that proof reclaims is renewable after 2 hours.And very little to the oil productivity impact.
Embodiment nine: raw material: soybean oil, solid magnetic catalyst, methyl alcohol.
Solid magnetic catalyst comprises the Ni that calculates with oxide 2O 3, ZrO 2, Fe 2O 3, its element mol ratio that forms by Ni, Zr, Fe is 2: 5: 7.All the other are with embodiment eight.
50.0 kilograms soybean oils and 20.0 kilograms of methyl alcohol are added in the reactor, stir, add 2.5 kilograms of solid magnetic catalysts, under 70 ℃, carry out ester exchange reaction, reacted 4.0 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 47.7 kilograms of biodiesel behind the purifying of upper strata.
Embodiment ten: raw material: Oleum Gossypii semen, solid magnetic catalyst, methyl alcohol.
Solid magnetic catalyst comprises the Ni that calculates with oxide 2O 3, ZrO 2, Fe 2O 3, its element mol ratio that forms by Ni, Zr, Fe is 3: 2: 10.All the other are with embodiment eight.
50.0 kilograms cottonseed oils and 20.0 kilograms of methyl alcohol are added in the reactor, stir, add 3.0 kilograms of solid magnetic catalyst catalyst, under 90 ℃, carry out ester exchange reaction, reacted 3.0 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 48.9 kilograms of biodiesel behind the purifying of upper strata.
Embodiment 11: raw material: frying oil, solid magnetic catalyst, ethanol.
Solid magnetic catalyst comprises the Ni that calculates with oxide 2O 3, ZrO 2, Fe 2O 3, its element mol ratio that forms by Ni, Zr, Fe is 2: 3: 15.All the other are with embodiment eight.
50.0 kilograms waste oil from restaurants and 18.0 kilograms of ethanol are added in the reactor, stir, add 3.5 kilograms of solid magnetic catalysts, under 90 ℃, carry out ester exchange reaction, reacted 2.0 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and ethanol, gets 48.8 kilograms of biodiesel behind the purifying of upper strata.
Embodiment 12: raw material: rapeseed oil, solid magnetic catalyst, methyl alcohol.
Solid magnetic catalyst comprises the Co that calculates with oxide 2O 3, ZrO 2, Fe 2O 3, its element mol ratio that forms by Co, Zr, Fe is 1: 6: 6.
Solid magnetic catalyst obtains by following method: 4 moles FeSO 47H 2O, 2 moles Fe 2(SO 4) 3The distilled water that adds 10 moles, controlled temperature is 50 ℃, slowly adds 0.8 mole ammoniacal liquor in 2 hours uniformly, stirs, and drips off back ageing 1 hour, obtains the precipitation of glossy black look, the supernatant liquor that inclines adds the distilled water repetitive scrubbing then and is precipitated to neutrality, and do not have SO 4 2-, it is standby to get intermediate A; The element mol ratio of pressing Co, Zr, Fe adds the ZrO after pulverizing in intermediate A 2, Co 2O 3, stir into pasty state, add 15 moles distilled water again, in 2 hours, slowly add 1 mole ammoniacal liquor uniformly, stir, be warming up to 60 ℃ after dripping off and continue to stir ageing 6 hours, obtain precipitation, the supernatant liquor that inclines adds the distilled water repetitive scrubbing then and is precipitated to neutrality, intermediate B is standby; With intermediate B in 80 ℃ of vacuum-dryings 12 hours; 500 ℃ of calcination 10 hours in muffle furnace again are transformed into composite oxides, and these composite oxides are solid magnetic catalyst.
50.0 kilograms rapeseed oils and 28.0 kilograms of methyl alcohol are added in the reactor, stir, add 3.0 kilograms of solid magnetic catalysts, under 90 ℃, carry out ester exchange reaction, reacted 2.0 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 49.6 kilograms of biodiesel behind the purifying of upper strata.
Embodiment 13: raw material: Viscotrol C, solid magnetic catalyst, methyl alcohol.
Solid magnetic catalyst comprises the Co that calculates with oxide 2O 3, ZrO 2, Fe 2O 3, its element mol ratio that forms by Co, Zr, Fe is 3: 2: 11.All the other are with embodiment 12.
50.0 kilograms castor oil and 16.0 kilograms of methyl alcohol are added in the reactor, stir, add 3.5 kilograms of solid magnetic catalysts, under 70 ℃, carry out ester exchange reaction, reacted 2.5 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 46.7 kilograms of biodiesel behind the purifying of upper strata.
Embodiment 14: raw material: peanut oil, solid magnetic catalyst, methyl alcohol.
Solid magnetic catalyst comprises the Co that calculates with oxide 2O 3, ZrO 2, Fe 2O 3, its element mol ratio that forms by Co, Zr, Fe is 1: 3: 8.All the other are with embodiment 12.
50.0 kilograms peanut oil and 18.0 kilograms of methyl alcohol are added in the reactor, stir, add 1.5 kilograms of solid magnetic catalysts, under 70 ℃, carry out ester exchange reaction, reacted 3.0 hours.After reaction finishes, under the effect in magnetic field, reclaim the solid magnets acidic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 46.2 kilograms of biodiesel behind the purifying of upper strata.
Embodiment 15: raw material: Semen Maydis oil, solid magnetic catalyst, methyl alcohol.
Solid magnetic catalyst comprises the Co that calculates with oxide 2O 3, ZrO 2, Fe 2O 3, its element mol ratio that forms by Co, Zr, Fe is 2: 5: 9.All the other are with embodiment 12.
50.0 kilograms corn oils and 16.0 kilograms of methyl alcohol are added in the reactor, stir, add 4.0 kilograms of solid magnetic catalysts, under 80 ℃, carry out ester exchange reaction, reacted 2.5 hours.After reacting end, under the effect in magnetic field, reclaim solid magnet acidic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 48.4 kilograms of biodiesel behind the purifying of upper strata.
Embodiment 16: raw material: sunflower seed oil, solid magnetic catalyst, methyl alcohol.All the other are with embodiment 12.
50.0 kilograms sunflower oils and 20.0 kilograms of methyl alcohol are added in the reactor, stir, add 3.0 kilograms of solid magnetic catalysts, under 90 ℃, carry out ester exchange reaction, reacted 2.0 hours.After reacting end, under the effect in magnetic field, reclaim solid magnet acidic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 49.2 jin of biodiesel behind the purifying of upper strata.
Embodiment 17: raw material: sweet oil, solid magnetic catalyst, methyl alcohol.All the other are with embodiment 12.
50.0 kilograms olive oil and 16.0 kilograms of methyl alcohol are added in the reactor, stir, add 2.0 kilograms of solid magnetic catalysts, under 60 ℃, carry out ester exchange reaction, reacted 2.5 hours.After reacting end, under the effect in magnetic field, reclaim solid magnet acidic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 44.3 kilograms of biodiesel behind the purifying of upper strata.
Embodiment 18: raw material: lard, solid magnetic catalyst, methyl alcohol.All the other are with embodiment 12.
50.0 kilograms lards and 18.0 kilograms of methyl alcohol are added in the reactor, stir, add 4.0 kilograms of solid magnetic catalysts, under 60 ℃, carry out ester exchange reaction, reacted 2.5 hours.After reacting end, under the effect in magnetic field, reclaim solid magnet acidic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 45.7 kilograms of biodiesel behind the purifying of upper strata.
Embodiment 19: raw material: wheatgerm oil, solid magnetic catalyst, methyl alcohol.
Solid magnetic catalyst comprises MgO, the Fe that calculates with oxide 2O 3, its element mol ratio that forms by Mg, Fe is 1: 6.All the other are with embodiment one.
50.0 kilograms wheat-germ oils and 12.0 kilograms of methyl alcohol are added in the reactor, stir, add 2.0 kilograms of solid magnetic catalysts, under 50.0 ℃, carry out ester exchange reaction, reacted 1.5 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 47.2 kilograms of biodiesel behind the purifying of upper strata.
Embodiment 20: raw material: Rice pollard oil, solid magnetic catalyst, methyl alcohol.
Solid magnetic catalyst comprises MgO, the Fe that calculates with oxide 2O 3, its element mol ratio that forms by Mg, Fe is 2: 9.All the other are with embodiment one.
50.0 kilograms rice bran oils and 16.0 kilograms of methyl alcohol are added in the reactor, stir, add 2.5 kilograms of solid magnetic catalysts, under 70 ℃, carry out ester exchange reaction, reacted 1.0 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 48.2 kilograms of biodiesel behind the purifying of upper strata.
Embodiment 21: raw material: catering trade waste oil, solid magnetic catalyst, methyl alcohol.
Solid magnetic catalyst comprises MgO, the Fe that calculates with oxide 2O 3, its element mol ratio that forms by Mg, Fe is 2: 7.All the other are with embodiment one.
50.0 kilograms fruit of cubeb litsea tree oil and 28.0 kilograms of methyl alcohol are added in the reactor, stir, add 3.5 kilograms of solid magnetic catalysts, under 70 ℃, carry out ester exchange reaction, reacted 1.0 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 49.5 kilograms of biodiesel behind the purifying of upper strata.
Embodiment 22: raw material: Chinese vegetable tallow, solid magnetic catalyst, methyl alcohol.
Solid magnetic catalyst comprises MgO, the Al that calculates with oxide 2O 3, Fe 2O 3, its element mol ratio that forms by Mg, Al, Fe is 8: 3: 7.All the other are with embodiment one.
50.0 kilograms Chinese tallows and 18.0 kilograms of methyl alcohol are added in the reactor, stir, add 2.0 kilograms of solid magnetic catalysts, under 70 ℃, carry out ester exchange reaction, reacted 2.0 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 49.4 kilograms of biodiesel behind the purifying of upper strata.
Embodiment 23: raw material: Chinese vegetable tallow, solid magnetic catalyst, methyl alcohol.
The element mol ratio of the Co of solid magnetic catalyst, Zr, Fe is 1: 5: 9; All the other are with embodiment 12.
50.0 kilograms Chinese tallows and 20.0 kilograms of methyl alcohol are added in the reactor, stir, add 4.0 kilograms of solid magnetic catalysts, under 80 ℃, carry out ester exchange reaction, reacted 1.5 hours.After reaction finishes, under the effect in magnetic field, reclaim solid magnetic catalyst earlier, then with the reaction mixture sat layering, the upper strata is the thick product of biodiesel, and lower floor is the mixture of glycerine and methyl alcohol, gets 48.3 kilograms of biodiesel behind the purifying of upper strata.
Embodiment 24: the production technology of preparing biodiesel by solid magnetic catalyst, and wherein: described animal-plant oil is any one or a few the mixture in soybean oil, genetically engineered soybean oil, rapeseed oil, transgenosis rapeseed oil, Oleum Gossypii semen, Chinese vegetable tallow, Viscotrol C, plam oil, peanut oil, sesame oil, Semen Maydis oil, sunflower seed oil, sweet oil, safflower oil, pine nut oil, walnut oil, Prunus amygdalus oil, raisin seed oil, wheatgerm oil, rice germ oil, Rice pollard oil, tea-seed oil, fruit of cubeb litsea tree oil, lard, butter, sheep oil, fish oil, the discarded edible oil; Repeat each example in the above embodiments one to 23 respectively.
Embodiment 25: the production technology of preparing biodiesel by solid magnetic catalyst, wherein: described low-carbon alcohol is a methyl alcohol.Repeat each example in the above embodiments one to 23 respectively.
Embodiment 26: the production technology of preparing biodiesel by solid magnetic catalyst, wherein: described low-carbon alcohol is an ethanol.Repeat each example in the above embodiments one to 23 respectively.
Embodiment 27: the production technology of preparing biodiesel by solid magnetic catalyst, wherein: described low-carbon alcohol is methyl alcohol and alcoholic acid mixture.Repeat each example in the above embodiments one to 23 respectively.
Embodiment 28: the production technology of preparing biodiesel by solid magnetic catalyst, under catalyst action and under the certain temperature, low-carbon alcohol is mixed with animal-plant oil and stir and carry out transesterification reaction, after reaction finishes, the upper strata is the thick product of biofuel, lower floor is the mixture of glycerine and low-carbon alcohol, biofuel thick purifying products in upper strata is got biofuel, wherein: the mol ratio of low-carbon alcohol and animal-plant oil is 3: 1, catalyzer adopts solid magnetic catalyst, transesterify is carried out under 100 ℃, and the reaction times is 1 hour, and the catalyzer of adding is 1% of an animal-plant oil weight.Repeat each example in the above embodiments one to 23 respectively.
Embodiment 29: the production technology of preparing biodiesel by solid magnetic catalyst, under catalyst action and under the certain temperature, low-carbon alcohol is mixed with animal-plant oil and stir and carry out transesterification reaction, after reaction finishes, the upper strata is the thick product of biofuel, lower floor is the mixture of glycerine and low-carbon alcohol, biofuel thick purifying products in upper strata is got biofuel, wherein: the mol ratio of low-carbon alcohol and animal-plant oil is 40: 1, catalyzer adopts solid magnetic catalyst, transesterify is carried out under 40 ℃, and the reaction times is 5 hours, and the catalyzer of adding is 10% of an animal-plant oil weight.Repeat each example in the above embodiments one to 23 respectively.
Embodiment 30: the production technology of preparing biodiesel by solid magnetic catalyst, under catalyst action and under the certain temperature, low-carbon alcohol is mixed with animal-plant oil and stir and carry out transesterification reaction, after reaction finishes, the upper strata is the thick product of biofuel, lower floor is the mixture of glycerine and low-carbon alcohol, biofuel thick purifying products in upper strata is got biofuel, wherein: the mol ratio of low-carbon alcohol and animal-plant oil is 20: 1, catalyzer adopts solid magnetic catalyst, transesterify is carried out under 60 ℃, and the reaction times is 2 hours, and the catalyzer of adding is 3% of an animal-plant oil weight.
Embodiment 31: the production technology of preparing biodiesel by solid magnetic catalyst, wherein: solid magnetic catalyst comprises the Ni that calculates with oxide 2O 3Or Co 2O 3, ZrO 2, Fe 2O 3, its element mol ratio that forms by Ni or Co, Zr, Fe is 1: 6: 5; Solid magnetic catalyst obtains by following method: press embodiment method acquisition from all directions.
Embodiment 32: the production technology of preparing biodiesel by solid magnetic catalyst, wherein: solid magnetic catalyst comprises the Ni that calculates with oxide 2O 3Or Co 2O 3, ZrO 2, Fe 2O 3, its element mol ratio that forms by Ni or Co, Zr, Fe is 3: 2: 15; Solid magnetic catalyst obtains by following method: press embodiment method acquisition from all directions.
Embodiment 33: the production technology of preparing biodiesel by solid magnetic catalyst, wherein: solid magnetic catalyst comprises the Ni that calculates with oxide 2O 3Or Co 2O 3, ZrO 2, Fe 2O 3, its element mol ratio that forms by Ni or Co, Zr, Fe is 2: 4: 10; Solid magnetic catalyst obtains by following method: press embodiment method acquisition from all directions.
Embodiment 34: the production technology of preparing biodiesel by solid magnetic catalyst, wherein: solid magnetic catalyst comprises MgO or CaO, the Al that calculates with oxide 2O 3, Fe 2O 3, its element mol ratio that forms by Mg or Ca, Al, Fe is 6: 2: 3; Solid magnetic catalyst obtains by following method: press embodiment one method and obtain.
Embodiment 35: the production technology of preparing biodiesel by solid magnetic catalyst, wherein: solid magnetic catalyst comprises MgO or CaO, the Al that calculates with oxide 2O 3, Fe 2O 3, its element mol ratio that forms by Mg or Ca, Al, Fe is 18: 6: 9; Solid magnetic catalyst obtains by following method: press embodiment one method and obtain.
Embodiment 36: the production technology of preparing biodiesel by solid magnetic catalyst, wherein: solid magnetic catalyst comprises MgO or CaO, the Al that calculates with oxide 2O 3, Fe 2O 3, its element mol ratio that forms by Mg or Ca, Al, Fe is 9: 4: 6; Solid magnetic catalyst obtains by following method: press embodiment one method and obtain.

Claims (7)

1, the production technology of preparing biodiesel by solid magnetic catalyst, under catalyst action and under the certain temperature, low-carbon alcohol is mixed with animal-plant oil and stir and carry out transesterification reaction, after reaction finishes, the upper strata is the thick product of biofuel, lower floor is the mixture of glycerine and low-carbon alcohol, biofuel thick purifying products in upper strata is got biofuel, it is characterized in that: the mol ratio of low-carbon alcohol and animal-plant oil is 3-40: 1, catalyzer adopts solid magnetic catalyst, transesterify is carried out under 40-100 ℃, and the reaction times is 1-5 hour, and the catalyzer of adding is the 1%-10% of animal-plant oil weight.
2, the production technology of preparing biodiesel by solid magnetic catalyst according to claim 2 is characterized in that: transesterify is carried out under 40-60 ℃.
3, the production technology of preparing biodiesel by solid magnetic catalyst according to claim 1 is characterized in that: solid magnetic catalyst comprises the Ni that calculates with oxide 2O 3Or Co 2O 3, ZrO 2, Fe 2O 3, its element mol ratio that forms by Ni or Co, Zr, Fe is 1-3: 2-6: 5-15; Solid magnetic catalyst obtains by following method: 4 moles FeSO 47H 2O, 2 moles Fe 2(SO 4) 3The distilled water that adds 10 moles, the control temperature is 50 ℃, slowly adds uniformly 0.8 mole ammoniacal liquor in 2 hours, stirs, and drips off rear ageing 1 hour, obtains the precipitation of glossy black look, the supernatant that inclines adds then the distilled water cyclic washing and is precipitated to neutrality, and do not have SO 4 2-, it is for subsequent use to get intermediate A; Add in molar ratio the Ni after pulverizing in the intermediate A 2O 3Or Co 2O 3, ZrO 2, stir into pasty state, add again 15 moles distilled water, in 3 hours, slowly add uniformly 2 moles ammoniacal liquor, stir, be warming up to 60 ℃ after dripping off and continue to stir ageing 6 hours, be precipitated, the supernatant that inclines adds then the distilled water cyclic washing and is precipitated to neutrality, and it is for subsequent use to get intermediate B; With intermediate B in 80 ℃ of vacuum drying 12 hours; Again 500 ℃ of calcination 10 hours in muffle furnace are transformed into composite oxides, and these composite oxides are solid magnetic catalyst.
4, the production technology of preparing biodiesel by solid magnetic catalyst according to claim 1 is characterized in that: solid magnetic catalyst comprises MgO or CaO, the Al that calculates with oxide 2O 3, Fe 2O 3, its element mol ratio that forms by Mg or Ca, Al, Fe is 6-18: 2-6: 3-9; Solid magnetic catalyst obtains by following method: 4 moles FeSO 47H 2O, 2 moles Fe 2(SO 4) 3The distilled water that adds 10 moles, the control temperature is 50 ℃, slowly adds uniformly 0.8 mole ammoniacal liquor in 2 hours, stirs, and drips off rear ageing 1 hour, obtains the precipitation of glossy black look, the supernatant that inclines adds then the distilled water cyclic washing and is precipitated to neutrality, and do not have SO 4 2-, it is for subsequent use to get intermediate A; Add in molar ratio MgO or CaO, Al after pulverizing in the intermediate A 2O 3, stir into pasty state, add again 15 moles distilled water, in 3 hours, slowly add uniformly 2 moles ammoniacal liquor, stir, be warming up to 60 ℃ after dripping off and continue to stir ageing 6 hours, be precipitated, the supernatant that inclines adds then the distilled water cyclic washing and is precipitated to neutrality, and it is for subsequent use to get intermediate B; With intermediate B in 80 ℃ of vacuum drying 12 hours; Again 500 ℃ of calcination 10 hours in muffle furnace are transformed into composite oxides, and these composite oxides are solid magnetic catalyst.
5, the production technology of preparing biodiesel by solid magnetic catalyst according to claim 1 is characterized in that: the mixture of glycerine and low-carbon alcohol is reclaimed respectively.
6, the production technology of preparing biodiesel by solid magnetic catalyst according to claim 1 is characterized in that: described animal-plant oil is a soybean oil, genetically engineered soybean oil, rapeseed oil, the transgenosis rapeseed oil, Oleum Gossypii semen, Chinese vegetable tallow, Viscotrol C, plam oil, peanut oil, sesame oil, Semen Maydis oil, sunflower seed oil, sweet oil, safflower oil, pine nut oil, walnut oil, Prunus amygdalus oil, raisin seed oil, wheatgerm oil, rice germ oil, Rice pollard oil, tea-seed oil, fruit of cubeb litsea tree oil, lard, butter, sheep oil, fish oil, the mixture of any one or a few in the discarded edible oil.
7, the production technology of preparing biodiesel by solid magnetic catalyst according to claim 1 is characterized in that: described low-carbon alcohol is methyl alcohol, ethanol or the mixture of the two.
CN2005100829222A 2005-07-07 2005-07-07 Production technology for preparing biodiesel by solid magnetic catalyst Expired - Fee Related CN1891787B (en)

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