CN102965203B - Method for preparing biodiesel through catalysis of natural biomass solid acid catalyst - Google Patents
Method for preparing biodiesel through catalysis of natural biomass solid acid catalyst Download PDFInfo
- Publication number
- CN102965203B CN102965203B CN201210427077.8A CN201210427077A CN102965203B CN 102965203 B CN102965203 B CN 102965203B CN 201210427077 A CN201210427077 A CN 201210427077A CN 102965203 B CN102965203 B CN 102965203B
- Authority
- CN
- China
- Prior art keywords
- solid acid
- acid catalyst
- biomass
- biodiesel
- biomass solid
- 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.)
- Expired - Fee Related
Links
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
Landscapes
- Liquid Carbonaceous Fuels (AREA)
- Fats And Perfumes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing biodiesel through catalysis of a natural biomass solid acid catalyst. The method comprises the following steps: 1, washing, drying and crushing the natural biomass, weighing and impregnating the crushed biomass, and taking out and drying the biomass; 2, impregnating acidified biomass in a metal salt solution, taking out and drying; 3, placing the biomass loaded with metal salt in a muffle furnace for roasting to obtain a natural biomass solid acid catalyst; and 4, adding the prepared biomass solid acid catalyst, short chain alcohol and oil into a batch reactor for esterification and an ester exchange reaction; after the reaction, conducting reduced pressure distillation to remove excessive short chain alcohol; and standing to delaminate glycerol and biodiesel produced in the reaction, wherein the biodiesel product is on an upper layer. According to the invention, natural renewable biomass is used as a raw material for direct acidification, without carbonization, so as to realize low cost and high biological diesel oil yield; besides, the prepared catalyst has advantages of good mechanical strength, particle size conducive to recovery, and no secondary pollution.
Description
Technical field
The present invention relates to biodiesel, be specifically related to a kind of method of the solid acid catalyst catalysis for preparing biodiesel oil take natural biomass as raw material.
Background technology
Biodiesel is reclaimed oil.In recent years, along with the day by day exhaustion of petroleum resources and the progressively deterioration of environment, this renewable resource of biodiesel comes into one's own day by day.Now be widely accepted gradually the substitute of the petrifaction diesel that becomes high-quality, low-sulfur, low toxicity.At present in the process of production biodiesel, originally catalyst used be acid solution catalysis, and as the concentrated sulfuric acid, but its product separates with catalyst difficulty, and to the seriously corroded of consersion unit, side reaction is many, and environmental pollution is large.Afterwards, introduce solid acid alkali catalytic agent, solved the problem that catalyst is difficult to separate with product, but also had problems simultaneously.The patent CN of Dalian University of Technology 200810012062.9 has proposed a kind of method of preparing carbon-based solid acid and biodiesel with natural biomass such as wood chips through carbonization, sulfonation.The patent CN102247888A of Beijing University of Chemical Technology, the patent CN102125874A of South China Science & Engineering University, the patent CN101396668A of Fujian Normal University and the patent CN102218342A of East China University of Science etc. also proposed to use different living beings, with the first carbonization of diverse ways, then the method for carbon-based solid acid is prepared in sulfonation.But above-mentioned preparation method has slatterned the major part organic matter in natural biomass, charcoal base material after carbonization not only volume, weight all significantly reduces, and the relative natural biomass of its mechanical strength also has reduction significantly, after using, catalyst forms extremely small carbon powder, industrial being difficult to reclaims, and very easily causes secondary pollution.
Summary of the invention
The problem that object of the present invention exists for above-mentioned prior art, provides a kind of method of natural biomass solid acid catalyst catalysis for preparing biodiesel oil, and it,, take the living beings of natural reproducible as the direct acidifying of raw material, does not carry out carbonization treatment.Reach cost low, biodiesel yield is high, and the catalyst mechanical strength of preparation is good, and granular size is beneficial to recovery, does not cause the object of secondary pollution.
The technical solution adopted in the present invention is: a kind of method of natural biomass solid acid catalyst catalysis for preparing biodiesel oil, comprises the following steps:
1. natural biomass is washed, is dried, is pulverized, taking living beings after pulverizing, to be immersed in mass fraction be 1.5 ~ 5h in 15% ~ 75% acid solution, takes out at latter 80 ℃ ~ 100 ℃ and dry;
2. the living beings after acidifying are immersed in to 1 ~ 5h in metal salt solution, after taking out, at 80 ~ 100 ℃, dry;
3. the living beings of loading metal-salt are placed in to roasting 2h at 100 ~ 270 ℃ of Muffle furnaces, naturally cool to room temperature, obtain natural biomass solid acid catalyst;
4. prepared biomass solid acid catalyst, short chain alcohol and grease are dropped in batch reactor, heating at 60 ~ 120 ℃, stirring, carry out esterification and ester exchange reaction, reaction time is 2 ~ 10h, reaction finishes the unnecessary short chain alcohol of rear pressure reducing and steaming, leave standstill glycerine and delamination of biodiesel that reaction is produced, upper strata is biodiesel product; The consumption of described biomass solid acid catalyst accounts for 3 ~ 7% of grease gross weight, and described short chain alcohol and the mol ratio of grease are 3 ~ 12:1.
Step of the present invention batch reactor 4. also can be fixed bed reactors, now continuous the mixed liquor of short chain alcohol and grease flowing through is filled with to the fixed bed of biomass solid acid catalyst, at 60 ℃ ~ 120 ℃, carry out esterification and ester exchange reaction 4 ~ 6h, the reactant liquor flowing out is carried out to decompression distillation, remove short chain alcohol and water, leave standstill or centrifugation glycerine after, obtain biodiesel.Described short chain alcohol and the mol ratio of grease are 3 ~ 12:1, and the consumption of described biomass solid acid catalyst accounts for 10% ~ 15% of fixed bed volume.
Described natural biomass is at least one in wood chip, bamboo bits, cotton and cotton products, lignin, cellulose, shell, rice husk, crop stem, bagasse.
Step 1. described acid solution comprise the inorganic or organic acid such as sulfuric acid, phosphoric acid, nitric acid, perchloric acid and benzene sulfonic acid any one.
Step 2. described metal salt solution for containing K
+, Na
+, Mg
2+, Cu
2+(or Cu
+), Zn
2+, Ti
2+(or Ti
4+) and Fe
2+(or Fe
3+) in the salting liquid of any one metal ion, concentration is 0.01 ~ 0.1mol/L.
Step 4. described short chain alcohol is the one in methyl alcohol, ethanol, propyl alcohol and isopropyl alcohol.
Step 4. described short chain alcohol and the mol ratio of grease is 3-5:1.
The method of described a kind of natural biomass solid acid catalyst catalysis for preparing biodiesel oil, comprises the following steps:
1. to be immersed in mass fraction be 3h in 45% perchloric acid solution to the crop stem particle 10kg by cleaning, after drying and crushing, takes out at latter 90 ℃ and dry;
2. the crop stem after acidifying is immersed in to 4h in the copper-bath of 0.05mol/L, takes out at latter 70 ℃ and dry;
3. the crop stem of load copper sulphate is placed in to calcination activation 2h at 135 ℃ of Muffle furnaces, naturally cools to room temperature, obtain crop stem solid acid catalyst;
4. drop in batch reactor by prepared crop stem solid acid catalyst 5kg, ethanol 26kg and through the waste oil 100kg of predrainage, removing impurities processing, be heated with stirring to 90 ℃, carry out esterification and ester exchange reaction, reaction time 6h, reaction finishes the unnecessary ethanol of rear pressure reducing and steaming, standing separation is removed crop stem solid acid catalyst and glycerine, and upper strata is biodiesel product.
Grease of the present invention can be crude vegetal, animal fat, waste oil and all kinds of acidification oil, natural animal-plant aliphatic acid.Take waste oil in the time that raw material is prepared biodiesel, to dewater in advance, removing impurities processing.
Biomass solid acid catalyst of the present invention is take the living beings of natural reproducible as raw material, and environmental protection is cheap.The preparation of catalyst is directly carried out acidifying to raw material, does not carry out carbonization treatment, and the catalyst mechanical strength making is high, and granular size is suitable, is beneficial to recovery, can not cause secondary pollution; Repeatedly dipping, to reach good load capacity.
The living beings of the present invention after to acidifying are carried out again the dip loading of slaine, have further improved the catalytic activity of catalyst.Reacted solid acid catalyst is convenient to separate with product.
The method of biomass solid acid catalyst catalysis for preparing biodiesel oil of the present invention, is applicable to grease take various acid numbers as the qualified biodiesel of the raw material quality of production.The biodiesel product of producing meets the quality standard of national 0# diesel oil completely.
The specific embodiment
The method of a kind of natural biomass solid acid catalyst catalysis for preparing biodiesel oil of the present invention, comprises the following steps:
1. natural biomass is washed, is dried, is pulverized, taking living beings after pulverizing, to be immersed in mass fraction be 1.5 ~ 5h in 15% ~ 75% acid solution, take out at latter 80 ℃ ~ 100 ℃ and dry,
2. the living beings after acidifying are immersed in to 1 ~ 5h in metal salt solution, after taking out, at 80 ~ 100 ℃, dry,
3. the living beings of loading metal-salt are placed in to roasting 2h at 100 ~ 270 ℃ of Muffle furnaces, naturally cool to room temperature, obtain natural biomass solid acid catalyst,
4. prepared biomass solid acid catalyst, short chain alcohol and grease are dropped in batch reactor, heating at 60 ~ 120 ℃, stirring, carry out esterification and ester exchange reaction, reaction time is 2 ~ 10h, reaction finishes the unnecessary short chain alcohol of rear pressure reducing and steaming, leaves standstill glycerine and delamination of biodiesel that reaction is produced, and upper strata is biodiesel product, the consumption of described biomass solid acid catalyst accounts for 3 ~ 7% of grease gross weight, and described short chain alcohol and the mol ratio of grease are 3 ~ 12:1.
Step of the present invention batch reactor 4. also can be fixed bed reactors, now continuous the mixed liquor of short chain alcohol and grease flowing through is filled with to the fixed bed of biomass solid acid catalyst, at 60 ℃ ~ 120 ℃, carry out esterification and ester exchange reaction 4 ~ 6h, the reactant liquor flowing out is carried out to decompression distillation, remove short chain alcohol and water, leave standstill or centrifugation glycerine after, obtain biodiesel.Described short chain alcohol and the mol ratio of grease are 3 ~ 12:1, and the amount of described biomass solid acid catalyst accounts for 10% ~ 15% of fixed bed volume.
Described natural biomass is at least one in wood chip, bamboo bits, cotton and cotton products, lignin, cellulose, shell, rice husk, crop stem, bagasse.
Step 1. described acid solution comprise the inorganic or organic acid such as sulfuric acid, phosphoric acid, nitric acid, perchloric acid and benzene sulfonic acid any one, mass fraction is 15 ~ 75%.
Step 2. described metal salt solution for containing K
+, Na
+, Mg
2+, Cu
2+(or Cu
+), Zn
2+, Ti
2+(or Ti
4+) and Fe
2+(or Fe
3+) in the salting liquid of any one metal ion, concentration is 0.01 ~ 0.1mol/L.
Step 4. described short chain alcohol is the one in methyl alcohol, ethanol, propyl alcohol and isopropyl alcohol.
Preferred steps 4. described short chain alcohol is that 3-5:1 is the best with the mol ratio of grease.
Grease of the present invention can be crude vegetal, animal fat, waste oil and all kinds of acidification oil, natural animal-plant aliphatic acid.Take waste oil in the time that raw material is prepared biodiesel, to dewater in advance, removing impurities processing.
Embodiment: a kind of method of natural biomass solid acid catalyst catalysis for preparing biodiesel oil can have following multiple embodiment:
1, concrete steps are:
1. to be immersed in mass fraction be 1.5h in 15% sulfuric acid solution to the wood pellet 10kg by cleaning, after drying and crushing, takes out at latter 80 ℃ and dry;
2. the wood chip after acidifying is immersed in to 1h in the Klorvess Liquid of 0.01mol/L, takes out at latter 80 ℃ and dry;
3. the wood chip of load potassium chloride is placed in to calcination activation 2h at 100 ℃ of Muffle furnaces, naturally cools to room temperature, obtain natural wood chip solid acid catalyst;
4. drop in batch reactor by prepared solid acid catalyst 3kg, methyl alcohol 11kg and through the waste oil 100kg of predrainage, removing impurities processing, be heated with stirring to 60 ℃, carry out esterification and ester exchange reaction, reaction time 2h, reaction finishes the unnecessary methyl alcohol of rear pressure reducing and steaming, standing separation is removed catalyst and glycerine, and upper strata is biodiesel product.Product yield 71%.
2, concrete steps are:
1. to be jointly immersed in mass fraction be 5h in 75% phosphoric acid solution to lignin particle 6kg, the cellulose grain 4kg by cleaning, after drying and crushing, takes out at latter 100 ℃ and dry;
2. the 5h in the metabisulfite solution of 0.1mol/L by the lignin after acidifying and cellulosic impregnation mixture, takes out at latter 80 ℃ and dries;
3. the lignin of load sodium sulphate and cellulosic mixture are placed in to calcination activation 2h at 270 ℃ of Muffle furnaces, naturally cool to room temperature, obtain biomass solid acid catalyst;
4. prepared solid acid catalyst 3kg, ethanol 62kg and crude vegetal 100kg are dropped in batch reactor, be heated with stirring to 120 ℃, carry out esterification and ester exchange reaction, reaction time 10h, reaction finishes the unnecessary ethanol of rear pressure reducing and steaming, standing separation is removed catalyst and glycerine, and upper strata is biodiesel product.Product yield 73%.
3, concrete steps are:
1. to be immersed in mass fraction be 1.5h in 15% benzene sulfonic acid solution to the shell particle 10kg by cleaning, after drying and crushing, takes out at latter 80 ℃ and dry;
2. the shell after acidifying is immersed in to 1h in the solution of ferrous chloride of 0.01mol/L, takes out at latter 80 ℃ and dry;
3. the shell of load frerrous chloride is placed in to calcination activation 2h at 100 ℃ of Muffle furnaces, naturally cools to room temperature, obtain natural shell solid acid catalyst;
4. continuous the flowing through of mixed liquor of propyl alcohol 20kg and animal fat 100kg is filled with to the fixed bed of biomass solid acid catalyst, the consumption of solid acid catalyst accounts for 10% of fixed bed volume, at 60 ℃, carry out esterification and ester exchange reaction 4h, reaction finishes rear to the unnecessary propyl alcohol of reactant liquor pressure reducing and steaming flowing out, standing separation is removed catalyst and glycerine, and upper strata is biodiesel product.Product yield 75%.
4, concrete steps are:
1. to be immersed in mass fraction be 5h in 75% salpeter solution to the bagasse particle 10kg by cleaning, after drying and crushing, takes out at latter 100 ℃ and dry;
2. the bagasse after acidifying is immersed in to 5h in the solution of zinc sulfate of 0.1mol/L, takes out at latter 80 ℃ and dry;
3. the bagasse of load zinc sulfate is placed in to calcination activation 2h at 270 ℃ of Muffle furnaces, naturally cools to room temperature, obtain natural bagasse solid acid catalyst;
4. by isopropyl alcohol 81kg be filled with the fixed bed of biomass solid acid catalyst through continuous the flowing through of mixed liquor of the waste oil 100kg of predrainage, removing impurities processing, the consumption of biomass solid acid catalyst accounts for 15% of fixed bed volume, at 120 ℃, carry out esterification and ester exchange reaction 6h, reaction finishes rear to the unnecessary isopropyl alcohol of reactant liquor pressure reducing and steaming flowing out, standing separation is removed catalyst and glycerine, and upper strata is biodiesel product.Product yield 72%.
5, concrete steps are:
1. to be immersed in mass fraction be 3h in 45% perchloric acid solution to the crop stem particle 10kg by cleaning, after drying and crushing, takes out at latter 90 ℃ and dry;
2. the crop stem after acidifying is immersed in to 4h in the copper-bath of 0.05mol/L, takes out at latter 70 ℃ and dry; 3. the crop stem of load copper sulphate is placed in to calcination activation 2h at 135 ℃ of Muffle furnaces, naturally cools to room temperature, obtain crop stem solid acid catalyst;
4. drop in batch reactor by prepared solid acid catalyst 5kg, ethanol 26kg and through the waste oil 100kg of predrainage, removing impurities processing, be heated with stirring to 90 ℃, carry out esterification and ester exchange reaction, reaction time 6h, reaction finishes the unnecessary ethanol of rear pressure reducing and steaming, standing separation is removed catalyst and glycerine, and upper strata is biodiesel product.Product yield 83%.
6, concrete steps are:
1. to be immersed in mass fraction be 3h in 30% salpeter solution for the rice husk particle 2kg by cleaning, after drying and crushing and bamboo bits particle 8kg, takes out at latter 100 ℃ and dry;
2. the 5h in the liquor zinci chloridi of 0.06mol/L by the rice husk after acidifying and bamboo bits impregnation mixture, takes out at latter 80 ℃ and dries;
3. the rice husk of load zinc chloride and bamboo bits mixture is placed in to calcination activation 2h at 200 ℃ of Muffle furnaces, naturally cools to room temperature, obtain natural biomass solid acid catalyst;
4. continuous the flowing through of mixed liquor of propyl alcohol 54kg and tallow fatty acid 100kg is filled with to the fixed bed of biomass solid acid catalyst, the consumption of biomass solid acid catalyst accounts for 12% of fixed bed volume, at 80 ℃, carry out esterification and ester exchange reaction 5h, reaction finishes rear to the unnecessary propyl alcohol of reactant liquor pressure reducing and steaming flowing out, catalyst and glycerine are removed in centrifugation, and upper strata is biodiesel product.Product yield 78%.
7, concrete steps are:
1. to be immersed in mass fraction be 3h in 45% perchloric acid solution to the crop stem particle 10kg by cleaning, after drying and crushing, takes out at latter 90 ℃ and dry;
2. the crop stem after acidifying is immersed in to 4h in the copper-bath of 0.05mol/L, takes out at latter 70 ℃ and dry;
3. the crop stem of load copper sulphate is placed in to calcination activation 2h at 135 ℃ of Muffle furnaces, naturally cools to room temperature, obtain crop stem solid acid catalyst;
4. prepared biomass solid acid catalyst 5kg, methyl alcohol 14kg and acidification oil 100kg are dropped in batch reactor, be heated with stirring to 90 ℃, carry out esterification and ester exchange reaction, reaction time 6h, reaction finishes the unnecessary methyl alcohol of rear pressure reducing and steaming, standing separation is removed catalyst and glycerine, and upper strata is biodiesel product.Product yield 79%.
Acidization of the present invention also can be carried out the suitable thermal agitation that adds, and its temperature control, at 30 ~ 150 ℃, is conducive to the load of catalyst activity component.
Claims (2)
1. a method for natural biomass solid acid catalyst catalysis for preparing biodiesel oil, is characterized in that: comprise the following steps:
1. to be immersed in mass fraction be 3h in 45% perchloric acid solution to the crop stem particle 10kg by cleaning, after drying and crushing, takes out at latter 90 ℃ and dry;
2. the crop stem after acidifying is immersed in to 4h in the copper-bath of 0.05mol/L, takes out at latter 70 ℃ and dry;
3. the crop stem of load copper sulphate is placed in to calcination activation 2h at 135 ℃ of Muffle furnaces, naturally cools to room temperature, obtain crop stem solid acid catalyst;
4. drop in batch reactor by prepared crop stem solid acid catalyst 5kg, ethanol 26kg and through the waste oil 100kg of predrainage, removing impurities processing, be heated with stirring to 90 ℃, carry out esterification and ester exchange reaction, reaction time 6h, reaction finishes the unnecessary ethanol of rear pressure reducing and steaming, standing separation is removed crop stem solid acid catalyst and glycerine, and upper strata is biodiesel product.
2. the method for a kind of natural biomass solid acid catalyst catalysis for preparing biodiesel oil as claimed in claim 1, it is characterized in that: step 4. described batch reactor can be fixed bed reactors, at this moment continuous the mixed liquor of short chain alcohol and grease flowing through is filled with to the fixed bed of biomass solid acid catalyst, at 60 ℃ ~ 120 ℃, carry out esterification and ester exchange reaction 4 ~ 6h, the reactant liquor flowing out is carried out to decompression distillation, remove short chain alcohol and water, leave standstill or centrifugation glycerine after, obtain biodiesel; Described short chain alcohol and the mol ratio of grease are 3 ~ 12:1, and the consumption of described biomass solid acid catalyst accounts for 10% ~ 15% of fixed bed volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210427077.8A CN102965203B (en) | 2012-10-31 | 2012-10-31 | Method for preparing biodiesel through catalysis of natural biomass solid acid catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210427077.8A CN102965203B (en) | 2012-10-31 | 2012-10-31 | Method for preparing biodiesel through catalysis of natural biomass solid acid catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102965203A CN102965203A (en) | 2013-03-13 |
| CN102965203B true CN102965203B (en) | 2014-06-25 |
Family
ID=47795639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210427077.8A Expired - Fee Related CN102965203B (en) | 2012-10-31 | 2012-10-31 | Method for preparing biodiesel through catalysis of natural biomass solid acid catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102965203B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103266017B (en) * | 2013-06-17 | 2014-10-29 | 长沙理工大学 | Method for increasing synthesis reaction efficiency of biodiesel |
| CN103421613A (en) * | 2013-08-23 | 2013-12-04 | 华南理工大学 | Preparation method for environment-friendly hydraulic oil base oil |
| CN103468414A (en) * | 2013-09-29 | 2013-12-25 | 天津理工大学 | Method for preparing biodiesel by using composite solid acid catalyst |
| CN106938196A (en) | 2015-12-10 | 2017-07-11 | 财团法人工业技术研究院 | Solid catalyst and preparation method of saccharide using the same |
| CN105419889B (en) * | 2015-12-25 | 2017-07-28 | 江西西林科股份有限公司 | A kind of preparation method of diesel antiwear additive |
| CN108114746A (en) * | 2016-11-29 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of preparation method and application of lignin-base acidic catalyst |
| CN109692690B (en) * | 2018-12-24 | 2020-08-25 | 华中科技大学 | Catalyst for producing levoglucosenone and preparation method thereof |
| US11414623B2 (en) * | 2019-05-29 | 2022-08-16 | King Fahd University Of Petroleum And Minerals | Efficient biomass carbon-based solid acid esterification catalyst for producing biodiesel |
| CN113019465B (en) * | 2021-03-24 | 2022-05-03 | 湖北碧美新能源科技有限公司 | Solid acid catalyst of biodiesel and method for preparing biodiesel |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594504A (en) * | 2004-07-08 | 2005-03-16 | 武汉化工学院 | Process for supercritical preparation of biologic diesel oil |
| CN1746264A (en) * | 2005-09-28 | 2006-03-15 | 王建业 | Production of diesel oil from trench oil and methyl alcohol |
| CN1821348A (en) * | 2006-03-14 | 2006-08-23 | 杨慈闵 | Method and device for producing biological diesel oil |
| CN101298566A (en) * | 2008-06-27 | 2008-11-05 | 大连理工大学 | Method for preparing biocarbon solid acid catalyst and biodiesel |
| CN101314138A (en) * | 2008-07-07 | 2008-12-03 | 大连理工大学 | Carbonaceous solid acid catalyst prepared by direct sulphonation of biomass |
| CN102247871A (en) * | 2011-05-16 | 2011-11-23 | 中国科学院广州能源研究所 | Preparation method of solid acid catalyst used for biomass hydrolysis |
-
2012
- 2012-10-31 CN CN201210427077.8A patent/CN102965203B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594504A (en) * | 2004-07-08 | 2005-03-16 | 武汉化工学院 | Process for supercritical preparation of biologic diesel oil |
| CN1746264A (en) * | 2005-09-28 | 2006-03-15 | 王建业 | Production of diesel oil from trench oil and methyl alcohol |
| CN1821348A (en) * | 2006-03-14 | 2006-08-23 | 杨慈闵 | Method and device for producing biological diesel oil |
| CN101298566A (en) * | 2008-06-27 | 2008-11-05 | 大连理工大学 | Method for preparing biocarbon solid acid catalyst and biodiesel |
| CN101314138A (en) * | 2008-07-07 | 2008-12-03 | 大连理工大学 | Carbonaceous solid acid catalyst prepared by direct sulphonation of biomass |
| CN102247871A (en) * | 2011-05-16 | 2011-11-23 | 中国科学院广州能源研究所 | Preparation method of solid acid catalyst used for biomass hydrolysis |
Non-Patent Citations (1)
| Title |
|---|
| 潘履让.第二节 焙烧过程.《固体催化剂的设计与制备》.南开大学出版社,1993,第290页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102965203A (en) | 2013-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102965203B (en) | Method for preparing biodiesel through catalysis of natural biomass solid acid catalyst | |
| Changmai et al. | Microwave-assisted synthesis of glycerol carbonate by the transesterification of glycerol with dimethyl carbonate using Musa acuminata peel ash catalyst | |
| CN103084187B (en) | Carbon-based solid acid and preparation method thereof | |
| CN102965204B (en) | Method for preparing biodiesel with catalysis of fly ash solid acid catalyst | |
| CN103539119B (en) | Preparation method of activated carbon for electrochemical energy storage device | |
| CN101456555A (en) | Method for preparing high mode number waterglass and active carbon by rice hull ash | |
| CN101314131B (en) | Preparation for modified hydrotalcite solid base catalyst for preparing biological diesel oil | |
| CN101332992A (en) | Method for preparing tung cell-based active carbon by zinc chloride chemical activation method | |
| CN102701220A (en) | Method for preparing white carbon black by oxygen-free high-temperature calcination and thermal activation of coal gangue | |
| CN102502628A (en) | Preparation method of granular activated carbon by chemical activation | |
| CN103539114B (en) | Pretreatment preparation method of active carbon for supercapacitor | |
| CN101130163B (en) | Load type flyash solid base catalyst for producing biological diesel oil and method of producing the same | |
| CN107488519A (en) | A kind of method that acid-base catalysis Bio-Diesel Fuels are loaded using magnetic charcoal | |
| CN102513132B (en) | Dedicated DYD catalyst for one-step bio-diesel production and production method thereof | |
| CN101602511A (en) | A kind of is the method for feedstock production kaliophylite with flyash | |
| CN112844409B (en) | Preparation method and application of biomass straw-based magnetic solid acid catalyst | |
| CN115295319A (en) | Multi-element manganese-iron-carbon-doped composite electrode material based on electrolytic manganese slag and preparation method thereof | |
| CN102319571A (en) | Catalyst for catalyzing hydrocracking of biomass oil and preparation method and application thereof | |
| CN105344344B (en) | Modified eggshell biodiesel catalyst and its preparation method and application | |
| CN115254143A (en) | Preparation method and application of carbon-based solid acid catalyst | |
| CN101418227A (en) | Method for preparing biodiesel by using moleplant seed oil | |
| CN101575530B (en) | Biomass liquefied oil and preparation method thereof | |
| CN103755717A (en) | Method for preparing LAC through catalytic pyrolysis of cellulose/biomass | |
| CN107099380A (en) | A kind of preparation method of biodiesel | |
| CN104893749B (en) | A kind of revolving bed coal catalysis pyrolysis method and system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140625 Termination date: 20151031 |
|
| EXPY | Termination of patent right or utility model |