CN103623863A - Preparation for solid acid catalyst with glycerin as raw material and research on catalytic esterification reaction thereof - Google Patents
Preparation for solid acid catalyst with glycerin as raw material and research on catalytic esterification reaction thereof Download PDFInfo
- Publication number
- CN103623863A CN103623863A CN201210312374.8A CN201210312374A CN103623863A CN 103623863 A CN103623863 A CN 103623863A CN 201210312374 A CN201210312374 A CN 201210312374A CN 103623863 A CN103623863 A CN 103623863A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- glycerin
- acid
- glycerine
- esterification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
Abstract
The invention relates to a catalyst which can efficiently catalyze esterification reactions of oleic acid and ethanol (or methanol), and glycerin and acetic acid for preparation of biodiesel and diesel oil additives and an application method thereof. The catalyst is a carbonized sulfonated product of glycerin and sulfuric acid with glycerin as a carrier and the active component is sulfonic acid group -SO3H. The preparation method for the catalyst is as follows: glycerin and sulfuric acid with certain weight mass ratios are mixed uniformly on an electric hot plate and heated slowly to a certain temperature; glycerin is carbonized and sulfonated continuously; then the carbonized sulfonated product is cooled to room temperature, washed with water and dried. The application method of the catalyst is as follows: a three-necked flask connection device is placed on a constant-temperature magnetic stirring device for experiments; the catalyst has high catalytic activity under optimal reaction conditions which are studied in a laboratory; when the catalyst is used for esterification reactions of oleic acid and ethanol (or methanol), and glycerin and acetic acid, the experiment esterification rate can reach 92.5% and 100% respectively, and the catalyst still has good activity after circulation usage for five times.
Description
Technical field
The invention belongs to the technical field of catalyst preparation technology research and development, be specifically related to the preparation of the carbon-based solid acids catalyst of synchronous carbonization sulfonation glycerine, and by this catalyst for the production of diesel oil and diesel fuel additives laboratory preparation in carry out catalytic reaction research.
Background technology
Global energy demand growth drives the problems such as price of oil going up sky-high, energy resource supply safety, climate change to make countries in the world all find the new energy.Biodiesel, as a kind of regenerative resource, has feature biodegradable, non-toxic, low pollution emission, is a kind of alternative green energy resource of exhausted fossil energy day by day.For domestic product diesel oil industry development present situation, the waste grease of take is prepared biodiesel as raw material and is applicable to China's national situation and has economically feasibility, yet because the high acid value feature of this feedstock oil has restricted the application of a lot of catalyst, although liquid acid catalyst catalytic efficiency is high, there is the problem of contaminated environment, according to the carried heteropoly acid catalyst that research is reported recently, although the catalyst environmental protection such as carbon-based solid acid catalyst, yet preparation method's more complicated, therefore find a kind of more effective, more environmental protection and preparation method are simple, the new catalyst can be recycled becomes the key point of Biodieselization development.
At present, the solid acid catalyst that utilizes chemical method to prepare biodiesel mainly comprises solid super-strong acid, load-type solid acid, metal oxide, molecular sieve, storng-acid cation exchange resin and carbon-based solid acids catalyst.Wherein carbon-based solid acids catalyst, is showing good catalytic activity as a kind of green catalyst aspect esterification, and the raw material of Kaolinite Preparation of Catalyst has wide material sources, characteristic renewable, with low cost, has good development prospect.The people such as Zong (Zong M H, Duan Z Q, Lou W Y.Preparation of a Sugar Catalyst and its Use for Highly Efficient Production of Biodiesel[J] .Green Chemistry, 2007,9 (5): 434-437.) use for the first time this carbon-supported catalysts catalysis waste edible oil to prepare biodiesel, free fatty acid content is that 27.8% waste oil 5g reacts with 5.54g methyl alcohol, catalyst amount 0.5g, under 80 ℃ of conditions, react 15h, methyl esters productive rate can reach 90%.The people such as Lou (Lou W Y, Zong M H, Duan Z Q.Ef
cient Production of Biodiesel from High Free Fatty Acid-Containing Waste Oils Using Various Carbohydrate-Derived Solid Acid Catalysts[J] .Bioresource Technology.2008, 99 (18): 8752-8758.) use glucose, sucrose, starch, lignin is made carbon-supported catalysts, and its catalytic activity has been carried out to detailed comparison, the catalyst activity that discovery is made by starch is the highest, esterification conversion ratio for oleic acid can reach 95%, particularly catalyst is after reusing 50 times, catalytic activity still can keep original 93%.Large quantity research is found, carbon-supported catalysts generally by sulfonation natural materials after first carbonization as acquisitions such as glucose, its carbonization sulfonated bodies has very high activity, it is a kind of green catalyst, but its preparation process is numerous and diverse, conventionally need to pass through 15h, the incomplete carbonization of 400 ℃, and 15h, 150 ℃ of incomplete carbide of sulfonation are to introduce sulfonic group-SO3H.For this reason, the synchronous carbonization sulfonation of the people's research and utilization sulfuric acid glycerine preparations such as Prabhavathi Devi have the sulfonic solid acid catalyst of high density, its manufacturing process is simple, preparation temperature is low, catalyst esterification efficiency is high, and stable in properties, and can solve the problem of outlet of biological diesel oil byproduct glycerin, for improving the economic worth of biodiesel, provide a practical way.
Summary of the invention
In order to overcome numerous and diverse this deficiency of carbon back class catalyst preparation process, the invention provides a kind of catalyst, this catalyst not only has the catalytic activity higher than other carbon-supported catalysts, and this catalyst is applied to take after synchronous carbonization sulfonation in biodiesel preparation process that high acid value oil is raw material, it has shown higher catalytic activity.Meanwhile, the price of catalyst, far below other carbon-supported catalysts, significantly reduces the preparation cost of catalyst.
The technical scheme that the technical problem that the present invention solves adopts is: a certain proportion of glycerine is mixed in beaker with sulfuric acid, be placed in after being heated to uniform temperature on electric hot plate and continue to keep this temperature certain hour, obtain carbonization sulfonated bodies, after subsequent treatment, obtain carbon-based solid catalyst.
A solid acid catalyst of preparing biodiesel and diesel fuel additives, this catalyst is the carbonization sulfonated bodies of glycerine and sulfuric acid.Its preparation method is characterised in that: get the glycerine of certain mass in beaker, add a certain amount of sulfuric acid (as the sulfuric acid of 4 times of qualities of glycerin), mix.Then beaker is put in to slowly heating on electric hot plate, is heated to the rear heating 20min-40mim that continues of uniform temperature (being as the criterion with edible oil temperature in beaker on electric hot plate), make glycerine continue carbonization sulfonation.Heat completely, by carbonization sulfonated bodies cool to room temperature, then under the condition stirring, by the deionized water of uniform temperature, repeatedly rinse, until washing lotion is neutrality.Finally, be placed in baking oven and dry.
This catalyst, its efficient catalytic oleic acid is in there-necked flask, to react under the condition of temperature constant magnetic stirring with the method characteristic of the esterification of ethanol.
The invention is characterized in, by the synchronous carbonization sulfonation of sulfuric acid glycerine, on discovery catalyst-and SO3H number is a lot, and the catalyst of preparation has very high sour density, is the principal element that affects catalyst activity.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further described.
Fig. 1 is that glycerin catalytic agent oleic acid in there-necked flask at differential responses temperature of embodiment 1 and reference examples 1 preparation is tested situation with the esterification of ethanol.
Fig. 2 is that embodiment 2 prepares glycerin catalytic agent and in different glycerine and sulfuric acid quality, carries out in there-necked flask the esterification experiment situation of oleic acid and ethanol under than condition.
Fig. 3 is that the esterification yield of testing catalysis oleic acid and methyl alcohol for 5 times that circulates in there-necked flask of the catalyst under the optimal conditions of embodiment 1 and embodiment 2 preparations contrasts.
Fig. 4 is that the esterification yield of testing catalyzing glycerol and acetic acid for 5 times that circulates in there-necked flask of the catalyst under the optimal conditions of embodiment 1 and embodiment 2 preparations contrasts.
The specific embodiment
By specific embodiment, introduce realization of the present invention and beneficial effect below, but should to the practical range of this case, not form any restriction accordingly.
The activity rating method of catalyst:
Use hot ethanol titration.
Concrete operation method: accurately weigh 40g oleic acid, reaction temperature is lower than the boiling point of ethanol, vigorous stirring, condensing reflux, the consumption of catalyst is the 6%-12% of oleic acid quality, investigates oleic acid conversion ratio temporal evolution situation.
Evaluation method: the catalytic capability of catalyst adopts the differential responses condition of oleic acid esterification: mole recently evaluation of reaction time, reaction temperature, catalyst amount and oleic acid and ethanol.Under differential responses condition, the esterification yield computational methods of esterification are: oleic acid and ethanol synthesis generate ethyl oleate, and because oily acid number is determined by oleic acid, the variation of the acid number of oil can reflect have how much oleic acid to be converted into biodiesel by the conversion ratio of oleic acid; The titration method of acid number is according to the acid number of the hot ethanol titration measuring grease in GB/T5530-2005/ISO 660:1996 < < animal and plant fat acid number and acidity assaying > >.Its conventional method is for getting certain volume ethanol in flask, and add phenolphthalein indicator, be heated to boiling, then with a certain amount of NaOH, be titrated to redness, then be poured in the flask that known oil quality is housed, be heated to boiling, be again titrated to redness, 20s does not move back, and can calculate the acid number of grease according to the amount of NaOH used.
Change the heating-up temperature of glycerine and sulfuric acid, adjust the speed of sulfuric acid carbonization sulfonation glycerine.Glycerine and the sulfuric acid of getting certain mass ratio mix, be placed in respectively on the electric hot plate of 100 ℃, 150 ℃, 200 ℃ and 250 ℃ after slowly heating, maintaining this temperature certain hour continues after carbonization sulfonation glycerine, be cooled to room temperature, washed with de-ionized water by uniform temperature, until washing lotion is neutrality, the catalyst after drying is used for to catalyst activity evaluation experimental.
Reference examples 1
Method for preparing catalyst with embodiment 1; glycerine and the sulfuric acid getting mass ratio and be 1: 4 mix; having under the condition of nitrogen protection; be placed in respectively on the electric hot plate of 100 ℃, 150 ℃, 200 ℃ and 250 ℃ after slowly heating; maintain this temperature certain hour and make glycerine continue, after carbonization sulfonation, to be cooled to room temperature, by the washed with de-ionized water of uniform temperature; until washing lotion is neutrality, the catalyst after drying is used for to catalyst activity evaluation experimental.
Reference examples 2
Preparation is with the glycerin catalytic agent of embodiment 1, with SBA-15 load glycerine: add 0.2ml glycerine and a certain proportion of sulfuric acid in 4.7ml deionized water, mix.Then solution is poured in the SBA-15 of certain mass, after 1 hour, put it into baking oven, programming rate with 1 ℃/min is heated to 100 ℃ by room temperature, at 100 ℃, keep 6h, then temperature is elevated to 160 ℃, and keeps 6h, in order to make glycerine carbonization sulfonation in SBA-15 hole, the mixture of 0.05ml glycerine and certain volume sulfuric acid, deionized water is joined in carbonized product, it is heated to 1h in 100 ℃ of baking ovens.Then by mixture under the condition of nitrogen protection, by room temperature, be heated to 600 ℃ (programming rate is 1 ℃/min) and keep 5h with carbonized polymers; Sulfonation is about to carbonized product and is positioned in autoclave, and every 1g carbonized product mixes with the 10ml concentrated sulfuric acid, at 160 ℃ of heating 15h.Mixture rinses repeatedly by deionized water, until there is no SO42-in washing lotion, then uses finite concentration hydrofluoric acid dissolution SBA-15, and stirring overnight, finally uses hot deionized water rinsing catalyst, dries.Catalyst after drying is used for to catalyst activity evaluation experimental
Method for preparing catalyst with embodiment 1, glycerine and the sulfuric acid of getting respectively mass ratio and be 1: 3,1: 4,1: 5 and 1: 6 mix, be placed on the electric hot plate of 100 ℃ after slowly heating, maintaining this temperature certain hour continues after carbonization sulfonation glycerine, be cooled to room temperature, by the washed with de-ionized water of uniform temperature, until washing lotion is neutrality, the catalyst after drying is used for to catalyst activity evaluation experimental.
The esterification that the catalyst of four kinds of catalyst of embodiment 1 preparation and reference examples 1, reference examples 2 preparations is carried out to oleic acid and ethanol in there-necked flask under same experimental conditions is investigated respectively the activity of catalyst.The ability of the glycerin catalytic agent catalyzed oil acid esterification that draws the glycerin catalytic agent of nitrogen-less protection and prepare under nitrogen protection condition is basic identical.The catalytic esterification rate of the catalyst of preparing when lower 100 ℃, 150 ℃, 200 ℃ of nitrogen-less protections and 250 ℃ is respectively 47.6%, 30.2%, 31.5%, 32.6%.In the time of 100 ℃, catalyst activity is better than other catalyst.Reaction temperature on the impact of catalyst esterification yield as Fig. 1.
The different glycerine of embodiment 2 preparations and the catalyst of sulfuric acid mass ratio are investigated to its activity respectively at the esterification of carrying out oleic acid and ethanol in there-necked flask under same experimental conditions.Show that glycerine and sulfuric acid mass ratio are that the conversion ratio of the glycerin catalytic agent catalytic esterification prepared under the condition of 1: 3,1: 4,1: 5 and 1: 6 is respectively 34.8%, 47.6%, 43.7%, 40.5%.Under 1: 4 reaction condition, catalyst activity is better than other catalyst.The impact of reactant quality comparison catalyst esterification yield is as Fig. 2.
Catalyst under the optimal conditions of embodiment 1 and embodiment 2 preparations is carried out in there-necked flask to the esterification of oleic acid and ethanol and prepare biodiesel.Differential responses temperature, reaction time, oleic acid and the impact of ethanol mol ratio on catalyst esterification efficiency are investigated respectively in experiment.By reaction condition optimization, the optimal conditions that obtains glycerin catalytic agent catalyzed oil acid esterification is that the mol ratio of oleic acid and ethanol is 1: 6-1: 12, and catalyst amount is the 6%-10% of oleic acid quality, reaction temperature is 63-73 ℃.For ethanol, the reaction time can arrive 8h by proper extension to 6, and uses methyl alcohol, and reaction 4h reaches balance substantially, improves stirring intensity and can promote reaction to carry out sooner.
Catalyst under the optimal conditions of embodiment 1 and embodiment 2 preparations is carried out in there-necked flask to the esterification of glycerine and acetic acid and prepare diesel fuel additives glyceryl triacetate.Differential responses temperature, reaction time, glycerine and acetic acid mol ratio, the impact with the additional proportion of aqua consumption and acetic anhydride and acetic acid on catalyst esterification efficiency are investigated respectively in experiment.Pass through reaction condition optimization, the optimal conditions that obtains glycerine and acetic acidreaction is: the reaction mol ratio of glycerine and acetic acid is 1: 3-1: 6, catalyst amount is the 6%-10% of qualities of glycerin, reaction temperature is 100 ℃---120, reaction is carried out after certain hour, cooling 0.5h adds the acetic anhydride times over glycerine mole in reaction system, promotes further carrying out of reaction.In the situation that reduce the use amount of acetic anhydride, can in reaction system, add band aqua, under the effect of the two, also can obtain higher glyceryl triacetate productive rate.
Embodiment 7
Catalyst under the optimal conditions of embodiment 1 and embodiment 2 preparations 5 oleic acid that circulate in there-necked flask are tested with the esterification of methyl alcohol, investigate the stability in use of catalyst, reaction condition is oleic acid 40g, catalyst amount 2-5g, oleic acid methyl alcohol mol ratio is 1: 6-1: 10, and reaction temperature is 63 ℃-73 ℃, the reaction time is 2h-6h, vigorous stirring, condensing reflux.After every secondary response finishes, use centrifuge separating catalyst, then with ethanol cleaning catalyst repeatedly, clean catalyst is put into the oven for drying of 100 ℃ and is spent the night.Experiment is found, directly heats first three esterification efficiency of glycerin catalytic agent and keeps stable, slightly reduces after the 4th time, after the 5th time, be reduced to and only have 79.2%, illustrate that glycerin catalytic agent is more stable generally, but along with the increase of access times, the activity of catalyst is suppressed.Glycerin catalytic agent recycles the catalysis oleic acid of 5 times and Fig. 3 is shown in the esterification yield contrast of methyl alcohol.
Embodiment 8
Catalyst under the optimal conditions of embodiment 1 and embodiment 2 preparations 5 glycerine that circulate in there-necked flask are tested with the esterification of acetic acid, investigate the stability in use of catalyst, reaction condition is: glycerine 15g, catalyst 1-2g, glycerine and acetic acid mol ratio are 1: 3-1: 6, cooling 0.5h after reaction certain hour adds the acid anhydrides that is equivalent to several times of glycerine moles in reaction system.After the cooling end of reaction, start 25min, 1h, the 2h sampling of heating respectively, detect the content of glyceryl triacetate.After reaction finishes, use centrifuge separating catalyst, then use ethanol cyclic washing, finally dry.Experiment is found, in continuous first twice of using of catalyst, it is stable that catalyst efficiency keeps, from for the third time, along with the increase of catalyst access times, the activity decreased of catalyst, wherein 25min sample point is obvious especially, but can, by extending the reaction time, improve the productive rate (2h sampled point) of glyceryl triacetate.Because can mixing, glyceryl triacetate and diacetine add in diesel oil, as procetane.Therefore actual catalyst access times can also increase, as long as acetin is all converted into diacetine and glyceryl triacetate.Glycerin catalytic agent recycles the catalyzing glycerol of 5 times and Fig. 4 is shown in the esterification yield contrast of acetic acid.
Claims (7)
1. a solid acid catalyst of preparing biodiesel and diesel fuel additives, this catalyst is the carbonization sulfonated bodies of glycerine and sulfuric acid.
2. catalyst according to claim 1, its carrier is glycerine, active component is sulfonic acid group-SO
3h.
3. catalyst according to claim 2, its preparation method is characterised in that:
Get the glycerine of certain mass in beaker, add a certain amount of sulfuric acid (as the sulfuric acid of 4 times of qualities of glycerin), mix.Then beaker is put in to slowly heating on electric hot plate, is heated to the rear heating 20min-40mim that continues of uniform temperature (being as the criterion with edible oil temperature in beaker on electric hot plate), make glycerine continue carbonization sulfonation.Heat completely, by carbonization sulfonated bodies cool to room temperature, then under the condition stirring, by the deionized water of uniform temperature, repeatedly rinse, until washing lotion is neutrality.Finally, be placed in baking oven and dry.
4. catalyst according to claim 3, this catalyst, its efficient catalytic oleic acid is in there-necked flask, to react under the condition of temperature constant magnetic stirring with the method characteristic of the esterification of ethanol.
5. the using method of catalyst according to claim 4, there-necked flask is to be connected by spherical reflux condensing tube, thermometer, frosted mouth bottle stopper.In experiment, the there-necked flask device connecting is placed in constant temperature blender with magnetic force, adopts constant temperature to test.
6. according to claim 5, under the method catalyst for the esterification of efficient catalytic oleic acid and methyl alcohol, glycerine and acetic acid recycle 1-5 time after still keep good stability.
7. according to claim 6, under the method, catalyst efficient catalytic esterification is prepared biodiesel and diesel fuel additives has better activity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210312374.8A CN103623863A (en) | 2012-08-29 | 2012-08-29 | Preparation for solid acid catalyst with glycerin as raw material and research on catalytic esterification reaction thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210312374.8A CN103623863A (en) | 2012-08-29 | 2012-08-29 | Preparation for solid acid catalyst with glycerin as raw material and research on catalytic esterification reaction thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103623863A true CN103623863A (en) | 2014-03-12 |
Family
ID=50205526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210312374.8A Pending CN103623863A (en) | 2012-08-29 | 2012-08-29 | Preparation for solid acid catalyst with glycerin as raw material and research on catalytic esterification reaction thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103623863A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941680A (en) * | 2014-03-31 | 2015-09-30 | 中国科学院大连化学物理研究所 | Glyceryl solid acid catalyst and application thereof |
| CN105419885A (en) * | 2015-11-24 | 2016-03-23 | 华东理工大学 | Synthesis method for preparing carboxylic ester with low content of residual acids under catalysis of solid super acid |
| CN111420685A (en) * | 2019-01-10 | 2020-07-17 | 欧阳峰 | FSBi-doped TiO for efficiently degrading acrylonitrile wastewater by sunlight catalysis2/SiO2Preparation and use of the catalyst |
-
2012
- 2012-08-29 CN CN201210312374.8A patent/CN103623863A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| BETHALA L. A. PRABHAVATHI DEVI ET AL.: "A Glycerol-based Carbon Catalyst for the Preparation of Biodiesel", 《CHEMSUSCHEM》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941680A (en) * | 2014-03-31 | 2015-09-30 | 中国科学院大连化学物理研究所 | Glyceryl solid acid catalyst and application thereof |
| CN104941680B (en) * | 2014-03-31 | 2017-10-20 | 中国科学院大连化学物理研究所 | Glycerine based solid acid catalyst and its application |
| CN105419885A (en) * | 2015-11-24 | 2016-03-23 | 华东理工大学 | Synthesis method for preparing carboxylic ester with low content of residual acids under catalysis of solid super acid |
| CN105419885B (en) * | 2015-11-24 | 2017-05-10 | 华东理工大学 | Synthesis method for preparing carboxylic ester with low content of residual acids under catalysis of solid super acid |
| CN111420685A (en) * | 2019-01-10 | 2020-07-17 | 欧阳峰 | FSBi-doped TiO for efficiently degrading acrylonitrile wastewater by sunlight catalysis2/SiO2Preparation and use of the catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104475074B (en) | The preparation of boron doping hollow carbon balls and the application in cathode in direct methanol fuel cells | |
| CN101670299A (en) | Preparation method of nanometer carbon-based solid acid | |
| CN101327437B (en) | Microwave-absorption type solid acid catalyst and use thereof in preparing biodiesel | |
| CN101597508A (en) | A kind of method of preparing alkane by high fatty acid ester | |
| CN103638973A (en) | Preparation method of sulfoacid-type cation exchange resin catalyst | |
| CN103801282B (en) | A kind of solid base catalyst and Synthesis and applications thereof | |
| CN1935946A (en) | Method for preparing biodiesel by microwave assisted lewis base catalysis | |
| CN101020864A (en) | Stepped high valent acid vegetable oil catalyzing process for preparing fatty acid methyl ester | |
| CN103623863A (en) | Preparation for solid acid catalyst with glycerin as raw material and research on catalytic esterification reaction thereof | |
| CN109776460A (en) | A method of Furfural Production from Xylose is catalyzed using solid acid catalyst | |
| CN103611539B (en) | A kind of magnetic calcium based solid alkali method for preparing catalyst of biodiesel synthesis | |
| Kushwaha et al. | Esterification of oleic acid to biodiesel using biowaste‐based solid acid catalyst under microwave irradiation | |
| CN101884931A (en) | Method for preparing solid super acidic catalyst and application | |
| CN102513132B (en) | Dedicated DYD catalyst for one-step bio-diesel production and production method thereof | |
| CN106423214A (en) | Method for preparing carbon-based solid acid with high specific surface area and high acid content from corncob hydrolysis residues | |
| CN101293209B (en) | Nano-solid heteropoly acid, heteropolybase catalyst suitable for producing biological diesel oil and application thereof | |
| CN101126029B (en) | Technique for preparing biological diesel oil by microwave catalyzing and film separating method | |
| CN100375780C (en) | Production of biological diesel oil with solid alkali | |
| CN101406842B (en) | Al-pillared paligorskite modified solid acid catalyst and preparation and application thereof | |
| CN101148599B (en) | Method for preparing biological diesel oil from waste animals and plants grease with high acid value | |
| CN101402059B (en) | Process for producing shell powder supported solid acid biodiesel catalyst | |
| CN103418365A (en) | Graphene based solid base catalyst preparation and application thereof in biodiesel production | |
| CN102698800B (en) | Resin catalyst for producing fatty acid methyl ester from high-acid-value oil | |
| CN114602512A (en) | Preparation method of esterification reaction catalyst | |
| CN100348314C (en) | Synthesis reaction catalyst for loading type alkali metal biodiesel oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140312 |