CN105642266B - Composite solid base catalyst for preparing biodiesel by glycerol-free method and preparation method thereof - Google Patents
Composite solid base catalyst for preparing biodiesel by glycerol-free method and preparation method thereof Download PDFInfo
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- CN105642266B CN105642266B CN201410640235.7A CN201410640235A CN105642266B CN 105642266 B CN105642266 B CN 105642266B CN 201410640235 A CN201410640235 A CN 201410640235A CN 105642266 B CN105642266 B CN 105642266B
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- carbonate
- biodiesel
- glycerol
- base catalyst
- composite solid
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- 239000003225 biodiesel Substances 0.000 title claims abstract description 61
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 239000007787 solid Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 38
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 238000001704 evaporation Methods 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 230000008020 evaporation Effects 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000004519 grease Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical group [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 claims description 7
- 229940044172 calcium formate Drugs 0.000 claims description 7
- 235000019255 calcium formate Nutrition 0.000 claims description 7
- 239000004281 calcium formate Substances 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000001639 calcium acetate Substances 0.000 claims description 4
- 229960005147 calcium acetate Drugs 0.000 claims description 4
- 235000011092 calcium acetate Nutrition 0.000 claims description 4
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000292 calcium oxide Substances 0.000 abstract description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 55
- 238000003756 stirring Methods 0.000 description 12
- JFMGYULNQJPJCY-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxolan-2-one Chemical compound OCC1COC(=O)O1 JFMGYULNQJPJCY-UHFFFAOYSA-N 0.000 description 9
- 238000000926 separation method Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- -1 so that on one hand Substances 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
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
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- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a composite solid base catalyst for preparing biodiesel by a glycerol-free method and a preparation method thereof. The preparation method comprises the following steps: 1) dissolving calcium salt in a solvent, wherein the mass of the solvent is 5-20 times of that of the calcium salt; 2) adding carbonate into the solution to obtain a mixture, wherein the mass of the carbonate is 5-20 times that of the calcium salt; 3) evaporating the solvent in the mixture to dryness; 4) heating the mixture after evaporation to dryness at 800-1000 ℃ for 4-10 hours, and cooling to room temperature to obtain the composite solid base catalyst for preparing the biodiesel by the glycerol-free method. The invention loads calcium oxide on carbonate in an indirect manner to prepare the composite solid base catalyst of super-strong base and weak base, and the composite solid base catalyst is applied to the field of biodiesel preparation, thereby being beneficial to upgrading the biodiesel preparation process and improving the economic benefit of the biodiesel industry.
Description
Technical Field
The invention relates to a composite solid base catalyst for preparing biodiesel by a glycerol-free method, and a preparation method and application thereof, belonging to the technical field of biodiesel preparation.
Background
In recent years, the problem of energy shortage is severe, the international oil price is rising all the way, the world countries are promoted to actively research and develop renewable alternative energy, the biodiesel is taken as a biological energy with great development prospect, and the large-scale production of the biodiesel is concerned by the academic world and the industrial world.
However, 1 ton of crude glycerol is produced per 9 tons of biodiesel, and the yield of the traditional glycerol (natural glycerol, fermented glycerol and synthetic glycerol) is relatively large, so that the market reservation of the glycerol is far greater than the demand. It is estimated that the glycerol market reserves exceed 1.2 million tons in 2010, so that how to effectively and comprehensively utilize low-price crude glycerol generated in the biodiesel production process becomes a serious and critical problem for the biodiesel industry.
Biodiesel as a blending stock must meet the requirements of relevant standards before being marketed, wherein ASTM D6751 and European Commission Standard EN 14214 make corresponding regulations on the specifications of biodiesel, limiting the amount of free glycerol and the amount of glycerides in the biodiesel. Free glycerol is a by-product in biodiesel production, mono-, di-, and tri-glycerides are contaminants in biodiesel, and high levels of free glycerol and glycerides can lead to increased engine deposits.
The double ester exchange method is a new biodiesel preparation method in recent years, and the method adopts the reaction of natural oil and methyl esterification reagent (such as dimethyl carbonate) to convert glycerol into carbonate while preparing biodiesel, thereby not only solving the problem of glycerol residue in the traditional biodiesel production, but also obtaining high-added-value glycerol carbonate, highly integrating multiple steps of biodiesel preparation, byproduct separation and the like, being beneficial to the upgrading of the biodiesel preparation process, and improving the economic benefit of the biodiesel industry.
Although the prior report of synchronously preparing the biodiesel and the glycerol carbonate by adopting the reaction of the natural oil and the dimethyl carbonate exists, the method has the defects of long reaction time, extremely easy saponification of raw materials and products, low final yield, difficult separation of saponified substances and the like.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a composite solid base catalyst for preparing biodiesel by a glycerol-free method, which has high activity in a reaction for preparing biodiesel by a glycerol-free method, and can reduce saponification problems and simplify a separation process.
The invention also aims to provide a preparation method and application of the composite solid base catalyst for preparing the biodiesel by the glycerol-free method.
In order to achieve the aim, the invention provides a preparation method of a composite solid base catalyst for preparing biodiesel by a glycerol-free method, which comprises the following steps:
firstly, dissolving calcium salt in a solvent, wherein the mass of the solvent is 5-20 times of that of the calcium salt;
secondly, adding carbonate into the solution to obtain a mixture, wherein the mass of the carbonate is 5-20 times that of the calcium salt;
thirdly, evaporating the solvent in the mixture to dryness;
fourthly, heating the mixture after evaporation to dryness at the temperature of 800-1000 ℃ for 4-10 hours, and cooling to room temperature to obtain the composite solid base catalyst for preparing the biodiesel by the glycerol-free method.
In the above preparation method, preferably, the calcium salt is calcium formate, calcium acetate or calcium nitrate, and the purity thereof is preferably at least chemical purity.
In the above preparation method, preferably, the solvent is methanol or ethanol, and the purity thereof is preferably at least chemical purity.
In the above preparation method, preferably, the carbonate is sodium carbonate, potassium carbonate or cesium carbonate, and the purity thereof is preferably at least chemical purity.
The invention also provides a composite solid base catalyst for preparing biodiesel by a glycerol-free method, and the catalyst is prepared by the preparation method.
The invention also provides the application of the composite solid base catalyst for preparing the biodiesel by the glycerol-free method in the preparation of the biodiesel.
In the above application, it preferably comprises the steps of:
mixing oil, methanol and dimethyl carbonate, and adding the composite solid base catalyst for preparing the biodiesel by the glycerol-free method for reaction, wherein: the mass ratio of the grease, the methanol and the dimethyl carbonate is 1:5-10: 1-3.
In the above application, preferably, the amount of the composite solid base catalyst is 1 to 15% of the amount of the fatty substance.
In the above application, the grease, methanol, dimethyl carbonate and the composite solid base catalyst are preferably reacted under reflux conditions for 1 to 6 hours, more preferably 2 to 6 hours.
The invention prepares the composite solid base catalyst of super-strong base and weak base by loading calcium oxide on carbonate in an indirect way; the catalyst is applied to a grease-methanol-dimethyl carbonate reaction system for preparing biodiesel, so that on one hand, grease, methanol and dimethyl carbonate can be simultaneously activated, the reaction speed is accelerated, and the reaction yield is improved; on the other hand, the calcium oxide is loaded on the surface of potassium carbonate/sodium carbonate, so that the dispersibility is good, the utilization rate is high, and the stability of the calcium oxide is enhanced. The catalyst catalyzes the reaction of grease-methanol-dimethyl carbonate to synchronously prepare biodiesel and glycerol carbonate, and the conversion rate of the grease can reach more than 95 percent.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a preparation method of a composite solid base catalyst for preparing biodiesel by a glycerol-free method, which comprises the following steps:
dissolving calcium salt in a solvent with the mass 5 times that of the calcium salt, stirring the solution to dissolve the calcium salt, wherein the calcium salt is chemically pure calcium formate, and the solvent is chemically pure methanol;
secondly, adding carbonate into the solution while stirring to obtain a mixture, wherein the mass of the carbonate is 5 times that of the calcium salt, and the carbonate is chemically pure potassium carbonate;
thirdly, evaporating the solvent in the mixture to dryness;
and fourthly, placing the mixture after evaporation to dryness in a muffle furnace, heating for 10 hours at 800 ℃, and cooling to room temperature to obtain the composite solid base catalyst for preparing the biodiesel by the glycerol-free method.
When the composite solid base catalyst is applied to a grease-methanol-dimethyl carbonate reaction system, the mass ratio of grease-methanol-dimethyl carbonate substances in the system is 1:5:1, the using amount of the composite solid base catalyst is 5% of the mass of the grease, the reaction system reacts for 5 hours under the reflux condition to obtain the biodiesel, the conversion rate of the grease reaches 96%, and the glycerol is synchronously converted into the glycerol carbonate.
Example 2
The embodiment provides a preparation method of a composite solid base catalyst for preparing biodiesel by a glycerol-free method, which comprises the following steps:
dissolving calcium salt in a solvent with the mass 8 times that of the calcium salt, stirring the solution to dissolve the calcium salt, wherein the calcium salt is chemically pure calcium acetate, and the solvent is chemically pure ethanol;
secondly, adding carbonate into the solution while stirring to obtain a mixture, wherein the mass of the carbonate is 10 times that of the calcium salt, and the carbonate is chemically pure sodium carbonate;
thirdly, evaporating the solvent in the mixture to dryness;
and fourthly, placing the mixture after evaporation to dryness in a muffle furnace, heating for 5 hours at 850 ℃, and cooling to room temperature to obtain the composite solid base catalyst for preparing the biodiesel by the glycerol-free method.
When the composite solid base catalyst is applied to a grease-methanol-dimethyl carbonate reaction system, the mass ratio of grease-methanol-dimethyl carbonate substances in the system is 1:6:1, the using amount of the composite solid base catalyst is 6% of the mass of the grease, the reaction system reacts for 5 hours under the reflux condition to obtain the biodiesel, the conversion rate of the grease reaches 97%, and the glycerol is synchronously converted into the glycerol carbonate.
Example 3
The embodiment provides a preparation method of a composite solid base catalyst for preparing biodiesel by a glycerol-free method, which comprises the following steps:
dissolving calcium salt in a solvent with the mass being 10 times that of the calcium nitrate, stirring the solution to dissolve the calcium salt, wherein the calcium salt is chemically pure calcium nitrate, and the solvent is analytically pure ethanol;
secondly, adding carbonate into the solution while stirring to obtain a mixture, wherein the mass of the carbonate is 10 times that of the calcium salt, and the carbonate is chemically pure cesium carbonate;
thirdly, evaporating the solvent in the mixture to dryness;
and fourthly, placing the mixture after evaporation to dryness in a muffle furnace, heating for 5 hours at 900 ℃, and cooling to room temperature to obtain the composite solid base catalyst for preparing the biodiesel by the glycerol-free method.
When the composite solid base catalyst is applied to a grease-methanol-dimethyl carbonate reaction system, the mass ratio of grease-methanol-dimethyl carbonate substances in the system is 1:8:2, the using amount of the composite solid base catalyst is 5% of the mass of the grease, the reaction system reacts for 3 hours under the reflux condition to obtain the biodiesel, the conversion rate of the grease reaches 96%, and the glycerol is synchronously converted into the glycerol carbonate.
Example 4
The embodiment provides a preparation method of a composite solid base catalyst for preparing biodiesel by a glycerol-free method, which comprises the following steps:
dissolving calcium salt in a solvent with the mass 15 times that of the calcium salt, stirring the solution to dissolve the calcium salt, wherein the calcium salt is analytically pure calcium formate, and the solvent is chemically pure ethanol;
secondly, adding carbonate into the solution while stirring to obtain a mixture, wherein the mass of the carbonate is 20 times that of the calcium salt, and the carbonate is analytically pure cesium carbonate;
thirdly, evaporating the solvent in the mixture to dryness;
and fourthly, placing the mixture after evaporation to dryness in a muffle furnace, heating for 6 hours at 900 ℃, and cooling to room temperature to obtain the composite solid base catalyst for preparing the biodiesel by the glycerol-free method.
When the composite solid base catalyst is applied to a grease-methanol-dimethyl carbonate reaction system, the mass ratio of grease-methanol-dimethyl carbonate substances in the system is 1:9:3, the using amount of the composite solid base catalyst is 10% of the mass of the grease, the reaction system reacts for 2 hours under the reflux condition to obtain the biodiesel, the conversion rate of the grease reaches 98%, and the glycerol is synchronously converted into the glycerol carbonate.
Example 5
The embodiment provides a preparation method of a composite solid base catalyst for preparing biodiesel by a glycerol-free method, which comprises the following steps:
dissolving calcium salt in a solvent with the mass of 20 times that of the calcium nitrate, stirring to dissolve the calcium salt, wherein the calcium salt is chemically pure calcium nitrate, and the solvent is chemically pure methanol;
secondly, adding carbonate into the solution while stirring to obtain a mixture, wherein the mass of the carbonate is 20 times that of the calcium salt, and the carbonate is chemically pure potassium carbonate;
thirdly, evaporating the solvent in the mixture to dryness;
and fourthly, placing the mixture after evaporation to dryness in a muffle furnace, heating for 6 hours at 850 ℃, and cooling to room temperature to obtain the composite solid base catalyst for preparing the biodiesel by the glycerol-free method.
When the composite solid base catalyst is applied to a grease-methanol-dimethyl carbonate reaction system, the mass ratio of grease-methanol-dimethyl carbonate substances in the system is 1:10:1, the using amount of the composite solid base catalyst is 15% of the mass of the grease, the reaction system reacts for 2 hours under the reflux condition to obtain the biodiesel, the conversion rate of the grease reaches 98%, and the glycerol is synchronously converted into the glycerol carbonate.
Example 6
The embodiment provides a preparation method of a composite solid base catalyst for preparing biodiesel by a glycerol-free method, which comprises the following steps:
dissolving calcium salt in a solvent with the mass being 10 times that of the calcium formate, stirring the solution to dissolve the calcium salt, wherein the calcium salt is analytically pure calcium formate, and the solvent is analytically pure ethanol;
secondly, adding carbonate into the solution while stirring to obtain a mixture, wherein the mass of the carbonate is 15 times that of the calcium salt, and the carbonate is analytically pure potassium carbonate;
thirdly, evaporating the solvent in the mixture to dryness;
and fourthly, placing the mixture after evaporation to dryness in a muffle furnace, heating for 5 hours at 900 ℃, and cooling to room temperature to obtain the composite solid base catalyst for preparing the biodiesel by the glycerol-free method.
When the composite solid base catalyst is applied to a grease-methanol-dimethyl carbonate reaction system, the mass ratio of grease-methanol-dimethyl carbonate substances in the system is 1:8:1.1, the using amount of the composite solid base catalyst is 15% of the mass of the grease, the reaction system reacts for 1 hour under the reflux condition to obtain the biodiesel, the conversion rate of the grease reaches 98%, and the glycerol is synchronously converted into the glycerol carbonate.
Claims (10)
1. A method for preparing a composite solid base catalyst for preparing biodiesel by a glycerol-free method comprises the following steps:
firstly, dissolving calcium salt in a solvent, wherein the mass of the solvent is 5-20 times of that of the calcium salt;
secondly, adding carbonate into the solution to obtain a mixture, wherein the mass of the carbonate is 5-20 times that of the calcium salt;
thirdly, evaporating the solvent in the mixture to dryness;
fourthly, heating the mixture after evaporation to dryness at the temperature of 800-1000 ℃ for 4-10 hours, and cooling to room temperature to obtain the composite solid base catalyst for preparing the biodiesel by the glycerol-free method; wherein,
the calcium salt is calcium formate, calcium acetate or calcium nitrate;
the solvent is methanol or ethanol;
the carbonate is sodium carbonate, potassium carbonate or cesium carbonate.
2. The production method according to claim 1, wherein: the purity of the calcium formate, acetate or nitrate is at least chemical pure.
3. The production method according to claim 1 or 2, wherein: the methanol or ethanol is at least chemically pure.
4. The production method according to claim 1 or 2, wherein: the sodium carbonate, potassium carbonate or cesium carbonate is at least chemically pure.
5. A composite solid base catalyst for preparing biodiesel by a glycerol-free method, which is prepared by the method of any one of claims 1 to 4.
6. The use of the composite solid base catalyst for preparing biodiesel according to the glycerol-free method of claim 5 in the preparation of biodiesel.
7. The use according to claim 6, comprising the steps of:
mixing oil and fat, methanol and dimethyl carbonate, and adding the composite solid base catalyst for preparing the biodiesel by the glycerol-free method according to claim 5 for reaction, wherein: the mass ratio of the grease, the methanol and the dimethyl carbonate is 1:5-10: 1-3.
8. The use of claim 6 or 7, wherein: the dosage of the composite solid base catalyst is 1-15% of the amount of the grease substances.
9. The use of claim 7, wherein: the grease, the methanol, the dimethyl carbonate and the composite solid base catalyst react under the reflux condition for 1-6 hours.
10. Use according to claim 9, wherein the reaction time is selected from 2 to 6 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410640235.7A CN105642266B (en) | 2014-11-13 | 2014-11-13 | Composite solid base catalyst for preparing biodiesel by glycerol-free method and preparation method thereof |
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| CN201410640235.7A CN105642266B (en) | 2014-11-13 | 2014-11-13 | Composite solid base catalyst for preparing biodiesel by glycerol-free method and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531916A (en) * | 2009-04-21 | 2009-09-16 | 合肥工业大学 | Solid alkali catalytic method for preparing biological diesel oil |
| CN102061224A (en) * | 2010-10-11 | 2011-05-18 | 西安石油大学 | Method for preparing biodiesel by catalysis of modified calcium oxide |
| CN103436369A (en) * | 2013-09-04 | 2013-12-11 | 西安石油大学 | Method for synchronously preparing biodiesel and glycerol carbonate under acceleration action of methanol |
-
2014
- 2014-11-13 CN CN201410640235.7A patent/CN105642266B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531916A (en) * | 2009-04-21 | 2009-09-16 | 合肥工业大学 | Solid alkali catalytic method for preparing biological diesel oil |
| CN102061224A (en) * | 2010-10-11 | 2011-05-18 | 西安石油大学 | Method for preparing biodiesel by catalysis of modified calcium oxide |
| CN103436369A (en) * | 2013-09-04 | 2013-12-11 | 西安石油大学 | Method for synchronously preparing biodiesel and glycerol carbonate under acceleration action of methanol |
Non-Patent Citations (1)
| Title |
|---|
| 纳米K2CO3/CaO催化大豆油制备生物柴油;张秋云等;《化学工程》;20110430;第39卷(第4期);第1.2节、第2.1.3节、第1.3节、第3节、第2.2节 * |
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