CN101024189A - Magnetic solid alkalic catalyst, its preparing method and use - Google Patents

Magnetic solid alkalic catalyst, its preparing method and use Download PDF

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Publication number
CN101024189A
CN101024189A CNA2007100516744A CN200710051674A CN101024189A CN 101024189 A CN101024189 A CN 101024189A CN A2007100516744 A CNA2007100516744 A CN A2007100516744A CN 200710051674 A CN200710051674 A CN 200710051674A CN 101024189 A CN101024189 A CN 101024189A
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magnetic
catalyst
solid base
base catalyst
mixture
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鲁晓勇
鲍德艳
李浔
苏明华
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ZHONGXING ENERGY TECHNOLOGY (WUHAN) Co Ltd
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ZHONGXING ENERGY TECHNOLOGY (WUHAN) Co Ltd
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Priority to CNA2007100516744A priority Critical patent/CN101024189A/en
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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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Abstract

This invention involves magnetic solid base catalyst, its components including magnetic material and metal oxide or magnetic vector with a mixture of metal salt as a catalyst, activity group is alkali metal salts. Their preparation methods: magnetic material and metal oxide or metal salts fully mixed grinding and dispersed evenly to join the binder, and then roasted and insulation, get a magnetic catalyst carrier; put active component into deionized water prepared impregnating solution; Magnetic catalyst carrier parked in the above impregnated solution to response, static aging, drying, calcination and insulation, then get a magnetic solid base catalyst. The invention magnetic solid base catalyst production process is simple, low cost, used for the preparation of the bio-diesel in transesterification reaction, catalytic function is superior, separation and recovery is convenient after transesterification reaction.

Description

A kind of magnetic solid base catalyst and method for making and application
Technical field
The present invention relates to a kind of support type magnetic solid base catalyst and preparation method thereof, and be applied to the biodiesel ester exchange reaction.
Background technology
Biodiesel is referred to as " regeneration fuel oil ", is to be raw material with vegetable oil and animal fat, and through catalyst action, fatty acid methyl ester that cracking processes or fatty-acid ethyl ester class mixture are a kind of fine-quality diesel oil substitutes.Oil crops such as soybean, peanut, rapeseed, wild oil fruit such as oil palm and Chinese pistache, oil plant water plants such as little algae, animal fat, even the discarded wet goods after hotel's cooking can be used for refining biodiesel.Biodiesel molecular weight and diesel oil are close, to mineral diesel similar burning and dynamic characteristics are arranged, and have the unexistent environmental friendliness characteristic of mineral diesel.
At present, biodiesel mostly adopts the preparation of homogeneous phase ester exchange reaction, though its catalytic efficiency is higher, reaction finishes rear catalyst and product separation difficulty, and has a large amount of spent acid alkali lye to discharge and contaminated environment.Adopt the catalyzed by solid base ester exchange reaction to prepare biodiesel and have the reactivity height, the reaction condition gentleness, selectivity is good, and product is easy to separate, can be recycled, consersion unit is corroded advantages such as little, but the specific area of solid base is less, if make nano particle, though increased its specific area, improved catalytic activity, but particle diameter just difficult more separation and recovery of small catalyst more reclaimed application for its industry and brought difficulty.In the existing document, Tian Danbi. carrier nanometer catalyst KF/Al 2O 3Preparation and application study thereof. Nanjing University of Technology's doctorate paper, 2004, it uses the Al of nanoscale 2O 3As preparing carriers nanocatalyst KF/Al 2O 3Though catalytic activity significantly improves, increased separating difficulty.Existing patent CN1470323A, adopt liquid-liquid reactions to prepare the magnetic Nano solid base catalyst, comprise the preparation of nano-magnetic nuclear powder, magnetic precursor preparation, three step of magnetic catalyst preparation preparation process, wherein the preparation of nano-magnetic nuclear powder and magnetic precursor is finished in be all-trans mixed liquid film reactor and crystallizing kettle, must strictly control the sample pH value value, reaction condition requires high, and manufacturing cycle is long, is unfavorable for industrialization.
Summary of the invention
The present invention is directed to the problems referred to above a kind of magnetic solid base catalyst and preparation method thereof and application are provided, the magnetic solid base catalyst production technology is simple, and is with low cost, is used for the ester exchange reaction of biodiesel manufacture, catalytic performance is superior, and ester exchange reaction finishes the back and separates recovery conveniently.
Magnetic solid base catalyst of the present invention, its composition comprise the magnetic carrier of the mixture of magnetisable material and metal oxide or slaine as catalyst, and active component is an alkali metal salt.Its mass percent is respectively:
Carrier: magnetisable material 20-40%
Metal oxide or slaine 30-60%
Active component: alkali metal salt 10-50%
Described magnetisable material is Fe 3O 4, Fe 2O 3, NiO, CoO, Mn 2O 3, at least a in the iron-nickel alloy, ferroaluminium; Described special metal oxide or slaine are CaO, Ca (Ac) 2, CaCO 3, Al 2O 3In at least a; Described alkali metal salt is KF, K 2CO 3, KNO 3In at least a.
The preparation method of magnetic solid base catalyst of the present invention is as follows:
Method one: magnetisable material and metal oxide or the abundant mixed grinding of slaine are got mixture by described catalyst proportion, and the binding agent (is the polyvinyl alcohol water solution of 5wt%-10wt% as concentration) that adds 1wt%-10wt% is uniformly dispersed it in said mixture, cross the 80-120 mesh sieve, then in 400-600 ℃ of roasting and be incubated 2-4h, obtain magnetic catalyst carrier, check its magnetic with magnet; Take by weighing active component by described catalyst proportion, add deionized water, be mixed with the dipping solution that concentration is 10wt%-40wt%; Magnetic catalyst carrier is placed above-mentioned dipping solution, be warming up to 50 ± 10 ℃ and make its dipping reaction 1-6h, still aging 10-16h is then in 80-120 ℃ of dry 12-24h; In 500-700 ℃ of calcining and insulation 2-6h, promptly get magnetic solid base catalyst then.
Method two: with metal oxide or slaine in Muffle furnace in 400-600 ℃ of roasting and be incubated 2-4h, product of roasting and magnetisable material get mixture by the abundant mixed grinding of described proportioning, and the binding agent (is the polyvinyl alcohol water solution of 5wt%-10wt% as concentration) that adds 1wt%-10wt% is uniformly dispersed it in said mixture, crosses the 80-120 mesh sieve; In 400-600 ℃ of roasting and be incubated 2-4h, obtain magnetic catalyst carrier then, check its magnetic with magnet; Take by weighing the active component in the described proportioning, add deionized water, be mixed with the dipping solution that concentration is 10wt%-40wt%; Magnetic catalyst carrier is placed above-mentioned dipping solution, be warming up to 50 ± 10 ℃ and make its dipping reaction 1-6h, still aging 10-16h is then in 80-120 ℃ of dry 12-24h; In 500-700 ℃ of calcining and insulation 2-6h, promptly get magnetic solid base catalyst then.
Above-mentioned dipping is reflected under supersonic oscillations dipping or the magnetic stirrer and carries out.
The technical scheme that magnetic solid base catalyst of the present invention is applied to biodiesel manufacture is as follows:
In the there-necked flask that thermometer, condenser pipe, electric mixer are housed, with soybean oil, rapeseed oil or palm wet goods is raw material, magnetic solid base is a catalyst, molar ratio of methanol to oil 6-12 during reaction: 1, catalyst amount is 65 ± 5 ℃, reaction time 2-6h for the heavy 1-4% of oil, cosolvent oxolane (THF) for heavy 0-15%, the reaction temperature of oil.After reaction finishes solid base catalyst is separated recovery, again liquid reaction mixture is carried out centrifugation or standing separation, promptly get biodiesel and byproduct glycerine.
The reaction of the present invention rear catalyst that finishes can realize that by the control to externally-applied magnetic field the technical scheme of catalyst recovery is as follows according to requirement of experiment:
After ester exchange reaction finishes, through magnetic separator, utilize this solid base catalyst itself to have magnetic products therefrom, the magnetic field intensity of regulating magnetic separator reclaims its magnetic separation.
Magnetic solid base catalyst production technology of the present invention is simple, with low cost, is used for the ester exchange reaction of biodiesel manufacture, and catalytic performance is superior, and ester exchange reaction finishes the back and separates recovery conveniently.
The specific embodiment
Embodiment 1
Take by weighing 4.15g Fe 3O 4, 6.80g Ca (Ac) 2H 2The abundant mixed grinding of O gets mixture, and the concentration that adds mixture quality 1% is that the polyvinyl alcohol water solution of 10wt% is uniformly dispersed it in said mixture, crosses 80 mesh sieves; In Muffle furnace in 400 ℃ of roastings and be incubated 4h, as the carrier of catalyst; Take by weighing 14.15g KF2H 2O adds 70ml deionized water wiring solution-forming as maceration extract; Powder after the roasting is placed above-mentioned dipping solution, utilize magnetic stirring apparatus to be warming up to 50 ℃ and stirring, make it fully flood reaction 4h, still aging 16h is placed on dry 12h in 100 ℃ of drying boxes; Dried sample is placed Muffle furnace,, promptly get KF/CaO/Fe at 500 ℃ of calcinings and insulation 5h 3O 4Magnetic solid base catalyst.
With the soybean oil is raw material, KF/CaO/Fe 3O 4Be catalyst, molar ratio of methanol to oil 9: 1, catalyst amount experimentize for heavy 4wt%, reaction time 3h, the reaction temperature of oil is 65 ℃.Reaction finishes to see the obvious layering of product, and oil reservoir is slightly light yellow than clarification, and solid catalyst falls to drag.It is isolated solid base catalyst through magnetic separator, then liquefied mixture is placed the pear shape separatory funnel standing separation, upper solution is light yellow, clear after a period of time, is biodiesel, and lower floor is a byproduct glycerine.Record the glycerine percentage composition by titration, converting and obtaining ester conversion rate is 88.23%.
Embodiment 2
Take by weighing 3.04g Fe 3O 4, the abundant mixed grinding of 4.52g CaO gets mixture, and the concentration that adds mixture quality 2% is that the polyvinyl alcohol water solution of 8wt% is uniformly dispersed it in said mixture, crosses 80 mesh sieves; In Muffle furnace in 500 ℃ of roastings and be incubated 4h, as the carrier of catalyst; Take by weighing 12.15g KF2H 2O adds 20ml deionized water wiring solution-forming as maceration extract; Powder after the roasting is placed above-mentioned dipping solution, utilize magnetic stirring apparatus to be warming up to 50 ℃ and stirring, make it fully flood reaction 4h, still aging 10h is placed on dry 12h in 100 ℃ of drying boxes; Dried sample is placed Muffle furnace,, promptly get KF/CaO/Fe at 600 ℃ of calcinings and insulation 6h 3O 4Magnetic solid base catalyst.
With the rapeseed oil is raw material, KF/CaO/Fe 3O 4Be catalyst, molar ratio of methanol to oil 12: 1, catalyst amount experimentize for heavy 1wt%, reaction time 5h, the reaction temperature of oil is 60 ℃.Reaction finishes to see the obvious layering of product, and oil reservoir is slightly light yellow than clarification, and solid catalyst falls to drag.It is isolated solid base catalyst through magnetic separator, then liquefied mixture is placed the pear shape separatory funnel standing separation, upper solution is light yellow, clear after a period of time, is biodiesel, and lower floor is a byproduct glycerine.Record the glycerine percentage composition by titration, converting and obtaining ester conversion rate is 78.93%.
Embodiment 3
Take by weighing 18.68g Fe 3O 4, 23.36g CaCO 3Fully mixed grinding gets mixture, and the concentration that adds mixture quality 10% is that the polyvinyl alcohol water solution of 5wt% is uniformly dispersed it in said mixture, crosses 120 mesh sieves; In Muffle furnace in 400 ℃ of roastings and be incubated 2h, as the carrier of catalyst; Take by weighing 7.56gKF2H 2O adds 40ml deionized water wiring solution-forming as maceration extract; Powder after the roasting is placed above-mentioned dipping solution, utilize ultrasonic cleaner to be warming up to 60 ℃ of vibrations, make it fully flood reaction 3h, still aging 16h is placed on dry 24h in 100 ℃ of drying boxes; Dried sample is placed Muffle furnace,, promptly get KF/CaO/Fe at 600 ℃ of calcinings and insulation 5h 3O 4Magnetic solid base catalyst.
With the palm oil is raw material, KF/CaO/Fe 3O 4Be catalyst, molar ratio of methanol to oil 12: 1, catalyst amount experimentize for heavy 2wt%, reaction time 5h, the reaction temperature of oil is 65 ℃.Reaction finishes to see the obvious layering of product, and oil reservoir is slightly light yellow than clarification, and solid catalyst falls to drag.It is isolated solid base catalyst through magnetic separator, then liquefied mixture is placed the pear shape separatory funnel standing separation, upper solution is light yellow, clear after a period of time, is biodiesel, and lower floor is a byproduct glycerine.Record the glycerine percentage composition by titration, converting and obtaining ester conversion rate is 90.44%.
Embodiment 4
Take by weighing 4.00g Fe 3O 4, 6.56gCa (Ac) 2H 2The abundant mixed grinding of O gets mixture, and the concentration that adds mixture quality 3% is that the polyvinyl alcohol water solution of 7wt% is uniformly dispersed it in said mixture, crosses 80 mesh sieves; In Muffle furnace in 400 ℃ of roastings and be incubated 2h, as the carrier of catalyst; Take by weighing 15.15gKF2H 2O adds 70ml deionized water wiring solution-forming as maceration extract; Powder after the roasting is placed above-mentioned dipping solution, utilize ultrasonic cleaner to be warming up to 60 ℃ of vibrations, make it fully flood reaction 3h, still aging 16h is placed on dry 24h in 100 ℃ of drying boxes; Dried sample is placed Muffle furnace,, promptly get KF/CaO/Fe at 600 ℃ of calcinings and insulation 5h 3O 4Magnetic solid base catalyst.
With the soybean oil is raw material, KF/CaO/Fe 3O 4Be catalyst, molar ratio of methanol to oil 12: 1, catalyst amount experimentize for heavy 4wt%, reaction time 5h, the reaction temperature of oil is 65 ℃.Reaction finishes to see the obvious layering of product, and oil reservoir is slightly light yellow than clarification, and solid catalyst falls to drag.It is isolated solid base catalyst through magnetic separator, then liquefied mixture is placed the pear shape separatory funnel standing separation, upper solution is light yellow, clear after a period of time, is biodiesel, and lower floor is a byproduct glycerine.Record the glycerine percentage composition by titration, converting and obtaining ester conversion rate is 94.74%.
Embodiment 5
Take by weighing 11.00gAl 2O 3Place Muffle furnace in 500 ℃ of calcination activations; Take by weighing 9.00g Fe 2O 3With the Al after the roasting 2O 3Fully mixed grinding gets mixture, and the concentration that adds mixture quality 1% is that the polyvinyl alcohol water solution of 9wt% is uniformly dispersed it in said mixture, crosses 80 mesh sieves; 500 ℃ of roastings and be incubated 4h in Muffle furnace are as the carrier of catalyst; Take by weighing 28.30gKF2H 2O adds 120ml deionized water wiring solution-forming as maceration extract; Powder after the roasting is placed above-mentioned dipping solution, utilize magnetic stirring apparatus to be warming up to 50 ℃ and stirring, make it fully flood reaction 2h, still aging 16h is placed on dry 12h in 100 ℃ of drying boxes; Dried sample is placed Muffle furnace,, promptly get KF/Al at 600 ℃ of calcinings and insulation 3h 2O 3/ Fe 2O 3Magnetic solid base catalyst.
With the soybean oil is raw material, KF/Al 2O 3/ Fe 2O 3Be catalyst, molar ratio of methanol to oil 9: 1, catalyst amount experimentize for heavy 4wt%, reaction time 3h, the reaction temperature of oil is 65 ℃.Reaction finishes to see the obvious layering of product, and oil reservoir clarifies slightly maroon, and solid catalyst falls to drag.It is isolated solid base catalyst through magnetic separator, then liquefied mixture is placed the pear shape separatory funnel standing separation, upper solution is light yellow, clear after a period of time, is biodiesel, and lower floor is a byproduct glycerine.Record the glycerine percentage composition by titration, converting and obtaining ester conversion rate is 90.74%.
Embodiment 6
Take by weighing 12.00gAl 2O 3Place Muffle furnace in 600 ℃ of calcination activations; Take by weighing the Al after 8.00g ferroaluminium and the roasting 2O 3Fully mixed grinding gets mixture, and the concentration that adds mixture quality 2% is that the polyvinyl alcohol water solution of 6wt% is uniformly dispersed it in said mixture, crosses 80 mesh sieves; 500 ℃ of roastings and be incubated 4h in Muffle furnace are as the carrier of catalyst; Take by weighing 18.25gK 2CO 3, add 70ml deionized water wiring solution-forming as maceration extract; Powder after the roasting is placed above-mentioned dipping solution, utilize magnetic stirring apparatus to be warming up to 60 ℃ and stirring, make it fully flood reaction 4h, still aging 10h is placed on dry 12h in 100 ℃ of drying boxes; Dried sample is placed Muffle furnace,, promptly get K at 700 ℃ of calcinings and insulation 2h 2CO 3/ Al 2O 3/ ferroaluminium magnetic solid base catalyst.
With the rapeseed oil is raw material, K 2CO 3/ Al 2O 3/ ferroaluminium is a catalyst, and molar ratio of methanol to oil 6: 1, catalyst amount experimentize for heavy 4wt%, reaction time 3h, the reaction temperature of oil is 65 ℃.Reaction finishes to see the obvious layering of product, and oil reservoir clarifies slightly maroon, and solid catalyst falls to drag.It is isolated solid base catalyst through magnetic separator, then liquefied mixture is placed the pear shape separatory funnel standing separation, upper solution is light yellow, clear after a period of time, is biodiesel, and lower floor is a byproduct glycerine.Record the glycerine percentage composition by titration, converting and obtaining ester conversion rate is 80.85%.
Embodiment 7
Take by weighing 10.00gAl 2O 3Place Muffle furnace in 600 ℃ of calcination activations; Take by weighing 10.00gFe 3O 4With the Al after the roasting 2O 3Fully mixed grinding gets mixture, and the concentration that adds mixture quality 4% is that the polyvinyl alcohol water solution of 6wt% is uniformly dispersed it in said mixture, crosses 80 mesh sieves; 400 ℃ of roastings and be incubated 4h in Muffle furnace are as the carrier of catalyst; Take by weighing 10.00gKNO 3, add 25ml deionized water wiring solution-forming as maceration extract; Powder after the roasting is placed above-mentioned dipping solution, utilize magnetic stirring apparatus to be warming up to 60 ℃ and stirring, make it fully flood reaction 3h, still aging 16h is placed on dry 12h in 100 ℃ of drying boxes; Dried sample is placed Muffle furnace,, promptly get KNO3/Al at 500 ℃ of calcinings and insulation 3h 2O 3/ Fe 3O 4Magnetic solid base catalyst.
With the soybean oil is raw material, KNO 3/ Al 2O 3/ Fe 3O 4Be catalyst, molar ratio of methanol to oil 9: 1, catalyst amount experimentize for oil heavy 2wt%, cosolvent THF are that heavy 15wt%, reaction time 3h, the reaction temperature of oil is 70 ℃.Reaction finishes to see the obvious layering of product, and oil reservoir clarifies slightly maroon, and solid catalyst falls to drag.It is isolated solid base catalyst through magnetic separator, then liquefied mixture is placed the pear shape separatory funnel standing separation, upper solution is light yellow, clear after a period of time, is biodiesel, and lower floor is a byproduct glycerine.Record the glycerine percentage composition by titration, converting and obtaining ester conversion rate is 82.54%.
Embodiment 8
Take by weighing 12.00gAl 2O 3Place Muffle furnace in 550 ℃ of calcination activations; Take by weighing the Al after 8.00gNiO and the roasting 2O 3Fully mixed grinding gets mixture, and the concentration that adds mixture quality 1% is that the polyvinyl alcohol water solution of 7wt% is uniformly dispersed it in said mixture, crosses 100 mesh sieves; 400 ℃ of roastings and be incubated 4h in Muffle furnace are as the carrier of catalyst; Take by weighing 21.57gKF2H 2O adds 75ml deionized water wiring solution-forming as maceration extract; Powder after the roasting is placed above-mentioned dipping solution, utilize magnetic stirring apparatus to be warming up to 70 ℃ and stirring, make it fully flood reaction 2h, still aging 14h is placed on dry 18h in 100 ℃ of drying boxes; Dried sample is placed Muffle furnace,, promptly get KF/Al at 700 ℃ of calcinings and insulation 5h 2O 3/ NiO magnetic solid base catalyst.
With the rapeseed oil is raw material, KF/Al 2O 3/ NiO is a catalyst, and alcohol oil rate 10: 1, catalyst amount experimentize for oil heavy 3wt%, cosolvent THF are that heavy 15wt%, reaction time 3h, the reaction temperature of oil is 65 ℃.Reaction finishes to see the obvious layering of product, and oil reservoir clarifies slightly maroon, and solid catalyst falls to drag.It is isolated solid base catalyst through magnetic separator, then liquefied mixture is placed the pear shape separatory funnel standing separation, upper solution is light yellow, clear after a period of time, is biodiesel, and lower floor is a byproduct glycerine.Record the glycerine percentage composition by titration, converting and obtaining ester conversion rate is 86.06%.
Embodiment 9
Solid catalyst after the embodiment 4 reaction end is recycled.When reaction finishes the gained mixture is isolated solid base catalyst through magnetic separator, with its recycling, the rate of recovery reaches 97.52%.
With the soybean oil is raw material, the KF/CaO/Fe of recovery 3O 4Be catalyst, molar ratio of methanol to oil 12: 1, catalyst amount experimentize for heavy 2wt%, reaction time 3h, the reaction temperature of oil is 65 ℃.Reaction finishes to see the obvious layering of product, and oil reservoir clarifies slightly maroon, and solid catalyst falls to drag.It is isolated solid base catalyst through magnetic separator, then liquefied mixture is placed the pear shape separatory funnel standing separation, upper solution is light yellow, clear after a period of time, is biodiesel, and lower floor is a byproduct glycerine.Record the glycerine percentage composition by titration, converting and obtaining ester conversion rate is 91.22%.After repeating to recycle 4-6 time, record ester exchange rate and still reach 85.56%.

Claims (7)

1. a magnetic solid base catalyst is characterized in that comprising magnetic carrier and active component, and magnetic carrier is the mixture of magnetisable material and metal oxide or slaine, and active component is an alkali metal salt; Wherein:
Carrier: magnetisable material 20-40wt%
Metal oxide or slaine 30-60wt%
Active component: alkali metal salt 10-50wt%
Described magnetisable material is Fe 3O 4, Fe 2O 3, NiO, CoO, Mn 2O 3, at least a in the iron-nickel alloy, ferroaluminium; Described metal oxide or slaine are CaO, Ca (Ac) 2, CaCO 3, Al 2O 3In at least a; Described alkali metal salt is KF, K 2CO 3, KNO 3In at least a.
2. the preparation method of the described magnetic solid base catalyst of claim 1, step is as follows:
(1) preparation of magnetic carrier
By described catalyst proportion magnetisable material and metal oxide or the abundant mixed grinding of slaine are got mixture, and the binding agent that adds the 1wt%-10wt% of mixture quality is uniformly dispersed it in said mixture, cross the 80-120 mesh sieve, in 400-600 ℃ of roasting and be incubated 2-4h, promptly get magnetic catalyst carrier then; Perhaps with metal oxide or slaine in 400-600 ℃ of roasting and be incubated 2-4h, product of roasting and magnetisable material get mixture by the abundant mixed grinding of described catalyst proportion, and the binding agent that adds 1wt%-10wt% is uniformly dispersed it in said mixture, cross the 80-120 mesh sieve, in 400-600 ℃ of roasting and be incubated 2-4h, promptly get magnetic catalyst carrier then;
(2) preparation of support type magnetic solid base catalyst
Take by weighing active component by described catalyst proportion, add deionized water, be mixed with the dipping solution that concentration is 10wt%-40wt%; The magnetic catalyst carrier that obtains in the step (1) is placed above-mentioned dipping solution, be warming up to 50 ± 10 ℃ and make its dipping reaction 1-6h, still aging 10-16h is then in 80-120 ℃ of dry 12-24h; In 500-700 ℃ of calcining and insulation 2-6h, promptly get magnetic solid base catalyst then.
3. preparation method as claimed in claim 2 is characterized in that: binding agent is the polyvinyl alcohol water solution of 5wt%-10wt%.
4. as claim 2 or 3 described preparation methods, it is characterized in that: described dipping is reflected under supersonic oscillations dipping or the magnetic stirrer and carries out.
5. the described magnetic solid base catalyst of claim 1 prepares application in the biodiesel in the homogeneous phase ester exchange reaction.
6. application as claimed in claim 5, it is characterized in that: methyl alcohol, the described magnetic solid base catalyst of claim 1 and cosolvent oxolane are mixed with soybean oil, rapeseed oil or palm oil phase, be warming up to 65 ± 5 ℃, react 2-6h under stirring condition, reaction finishes the back centrifugation or standing separation promptly gets biodiesel and byproduct glycerine; Wherein methyl alcohol and soybean oil or rapeseed oil or palmitic mol ratio are 6-12: 1, the described magnetic solid base catalyst of claim 1 is that 1-4%, the cosolvent oxolane of soybean oil or rapeseed oil or palm oil quality are the 0-15% of soybean oil or rapeseed oil or palm oil quality.
7. as claim 5 or 6 described application, it is characterized in that: reaction finishes the back and reclaims magnetic solid base catalyst by externally-applied magnetic field.
CNA2007100516744A 2007-03-15 2007-03-15 Magnetic solid alkalic catalyst, its preparing method and use Pending CN101024189A (en)

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CN101829585A (en) * 2010-04-16 2010-09-15 北京化工大学 Magnetic nano base metal fluoride load type solid base catalyst and preparation method thereof
WO2012111023A1 (en) 2011-02-14 2012-08-23 Council Of Scientific & Industrial Research (An Indian Registered Body Incorporated Under The Registration Of Societies Act (Act Xxxi Of 1860) Improved process for the preparation of fatty acid alkyl esters (biodiesel) from triglyceride oils using eco-friendly solid base catalysts
US9029583B2 (en) 2011-02-14 2015-05-12 Council Of Scientific & Industrial Research Process for the preparation of fatty acid alkyl esters (biodiesel) from triglyceride oils using eco-friendly solid base catalysts
CN102161933A (en) * 2011-03-10 2011-08-24 四川大学 Method for preparing biodiesel by one step based on lepra fruits as raw material
CN102302942A (en) * 2011-07-04 2012-01-04 中国科学院广州能源研究所 Nano-magnetic bifunctional solid alkali catalyst for transesterification reaction and preparation method thereof
CN102335607A (en) * 2011-07-20 2012-02-01 北京工业大学 Preparation method and application of magnetic solid base catalyst for synthesizing biodiesel
CN102321044B (en) * 2011-07-20 2013-08-07 江西华邦药业有限公司 Preparation method of 3-(2-bromo propionyl)-spiro[2H-1,3-benzoxazine-2,1'-cyclohexane]-4(3H)-one
CN102321044A (en) * 2011-07-20 2012-01-18 江西华邦药业有限公司 Preparation method of 3-(2-bromo propionyl)-spiro[2H-1,3-benzoxazine-2,1'-cyclohexane]-4(3H)-one
CN104388195A (en) * 2014-08-08 2015-03-04 内蒙古科技大学 Method for synthesizing fatty acid methyl ester by using magnetic solid base to catalyze in-situ transesterification of navicula sp.
CN104388195B (en) * 2014-08-08 2017-02-01 内蒙古科技大学 Method for synthesizing fatty acid methyl ester by using magnetic solid base to catalyze in-situ transesterification of navicula sp.
CN105032431A (en) * 2014-12-12 2015-11-11 北京恩泽福莱科技有限公司 Magnetic solid alkali catalyst and preparation method thereof
CN106215939A (en) * 2016-06-29 2016-12-14 中国石油天然气股份有限公司 The preparation method of biodiesel solid catalyst
CN106215939B (en) * 2016-06-29 2019-02-15 中国石油天然气股份有限公司 The preparation method of biodiesel solid catalyst
CN107469852A (en) * 2017-08-07 2017-12-15 江南大学 A kind of carbon-based magnetic solid base catalyst of biodiesel synthesis and preparation method thereof
CN109046417A (en) * 2018-08-17 2018-12-21 湘潭大学 A kind of K2CO3The method of/MgLa catalyzed by solid base biodiesel synthesis
CN109576018A (en) * 2018-12-20 2019-04-05 谢家传 A kind of B20 biology blending fuel and preparation method thereof
CN110052293A (en) * 2019-05-24 2019-07-26 山东建筑大学 A kind of biodiesel magnetic solid base catalyst and its preparation method and application
JP2023011537A (en) * 2021-07-12 2023-01-24 華北理工大学 Catalyst and preparation method of bio-diesel using the catalyst

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