CN107597087B - ZrO2Polycrystalline ceramic foam catalyst, method for the production thereof and use thereof - Google Patents
ZrO2Polycrystalline ceramic foam catalyst, method for the production thereof and use thereof Download PDFInfo
- Publication number
- CN107597087B CN107597087B CN201710798322.9A CN201710798322A CN107597087B CN 107597087 B CN107597087 B CN 107597087B CN 201710798322 A CN201710798322 A CN 201710798322A CN 107597087 B CN107597087 B CN 107597087B
- Authority
- CN
- China
- Prior art keywords
- zro
- catalyst
- biodiesel
- foamed ceramic
- polycrystalline
- 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.)
- Active
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
Abstract
The invention discloses ZrO2The polycrystalline foamed ceramic catalyst comprises Zr, Al and Ti elements, wherein the molar ratio of Zr to Al to Ti is 5: 2.2-3.5: 0.2. the invention also discloses ZrO2Preparation method of polycrystalline foamed ceramic catalyst by using ZrOCl2·8H2O、AlCl3And TiCl4And (4) participating in the reaction. The invention also discloses ZrO2Use of a catalyst for polycrystalline ceramic foam, ZrO prepared by reacting ZrO2The polycrystalline foam ceramic catalyst is used for catalyzing glycerin esterification to reduce the acid value of biodiesel, the biodiesel is used as a reaction raw material, and ZrO2The polycrystalline foamed ceramic is used as a catalyst, and the biodiesel byproduct glycerin is used as an esterifying agent to carry out esterification reaction. The method is efficient, clean, green and environment-friendly, and free fatty acid in the biodiesel is converted into fatty glyceride through esterification reaction of the fatty acid and the biodiesel byproduct glycerol, so that the purpose of reducing the acid value is achieved.
Description
Technical Field
The invention relates to a ZrO2A polycrystalline foamed ceramic catalyst, a preparation method and application thereof, belonging to the technical field of biomass energy.
Background
At present, biodiesel produced by esterification and ester exchange methods often contains a certain amount of free fatty acid due to incomplete reaction, process residues, product hydrolysis and the like. These fatty acids not only increase engine deposits and increase fuel pump plunger wear, but also can cause fuel injector head and combustion chamber carbon deposits, reduce diesel engine power and increase wear on the cylinder piston assembly. Meanwhile, the free acid also increases the corrosivity of fuel oil, causes emulsification of blended diesel oil and increases the probability of putrefaction and deterioration, and further causes damage to an engine due to corrosion of metal components and swelling of rubber pipelines. Therefore, in order to reduce the influence of free acid on an engine and improve the service performance of a biodiesel product, the biodiesel standard is continuously updated 3 times in 2007, 2014 and 2015 in China, and the acid value of the biodiesel is reduced from not higher than 0.8 mg KOH/g to not higher than 0.5 mg KOH/g.
However, the alkali widely used in the biodiesel industry today neutralizes the free acids in biodiesel, converts them to fatty acid salts, and then removes them by water washing. Not only produces a large amount of waste water, increases environmental protection pressure and input in the production process, and the product is often emulsified by the generated fatty acid salt, so that methanol and water are not easy to stratify, and the byproduct glycerol is difficult to recover, thereby affecting the product quality, increasing the production pressure of downstream refining processes, and reducing the product yield. In addition, strong alkali such as sodium hydroxide and potassium hydroxide used in the alkali washing process has serious corrosion to equipment. The operation is complicated, the reaction process and the production period are prolonged because a large amount of water is needed for washing for many times to remove the added alkaline substances, and the introduction of a large amount of water increases the pressure of water separation in the later period, so that the production process is prolonged. Because the water in the product can accelerate the conversion of fatty acid methyl ester to free acid, the oxidation stability of the product is influenced, the breeding of microorganisms is promoted, the decomposition and the deterioration of the product are accelerated, and the storage and the application of the biodiesel are influenced.
In order to solve various problems in the traditional process for reducing the acid value of the biodiesel by alkali neutralization and water washing, CN101289627A utilizes weak alkaline substances such as ethanolamine, diethanolamine and the like to reduce the acid value of the biodiesel, and the problems of corrosion and emulsification in the reaction process are solved by generating insoluble amide with free acid. However, the amide substance is too slow in the reaction due to the slow settling speed, so that the amide substance cannot be completely removed by settling separation, and the color of the biodiesel is often deepened due to the residue, thereby affecting the product quality. And the used settling agents such as ethanolamine and the like are expensive, and insoluble amide precipitates need to be treated after reaction, so that the production flow is increased, and the reduction of the production cost is not facilitated.
CN102234567A fully mixes inorganic strong base and biodiesel to react, neutralizes redundant fatty acid, adds inorganic calcium salt solution to convert alkali metal soap after neutralization into water-insoluble calcium soap, and finally separates out the alkali metal soap through operations such as centrifugation and water washing. The method has the advantages that the problem that alkali metal soap is easy to emulsify in the process of washing with water is solved by using inorganic calcium salt, but strong alkali used by the method still has strong corrosion to equipment, and the problem of environmental pollution caused by washing with water cannot be solved. Meanwhile, the introduced calcium ions easily cause the calcium ions of the product to exceed the standard, thereby influencing the quality of the product.
CN104232307A uses alkaline anion exchange resin as solid alkali absorbent to perform neutralization reaction with fatty acid in biodiesel and absorb and remove fatty acid in the biodiesel, and the method can reduce the acid value of the biodiesel to below 0.1 mg KOH/g at the minimum, does not corrode equipment and has no emulsification phenomenon. However, the basic ion exchange resin used in this method requires pretreatment before use, and after each use, it is subjected to a complicated regeneration procedure before reuse. And the regeneration operation can be completed only by using strong acid, strong alkali and a large amount of water washing, so that the problem of environmental pollution caused by water washing in the production process is not thoroughly solved.
CN101230309A as ZrO2And TiO2As a carrier, chlorosulfonic acid is loaded to prepare solid super acid for reducing the acid value of the biodiesel. The method successfully solves the problems of corrosivity, environmental pollution and the like existing in the traditional alkali washing and neutralizing process, and can reduce the acid value of the biodiesel to 0.4 mg KOH/g. However, the acid value of the product is reduced to the national standard by repeating the acid reduction twice, the operation process is complicated, and the used supported catalyst has the problems of easy loss of active components, poor mechanical strength, short service life and the like.
CN103013676A adopts sulfuric acid, phosphoric acid, tungstosilicic acid and ionic liquid as catalysts, and can reduce the acid value of the biodiesel with high acid value to below 0.8 mg KOH/g under the conditions that the reaction temperature is 70-220 ℃ and the reaction pressure is 0.2-3 MPa. However, the reaction product is black in color and scorched, which is unfavorable for the product quality and the service performance. The whole reaction can be carried out under the catalysis conditions of certain pressure, sulfuric acid, phosphoric acid and the like, the requirement on equipment manufacturing is high, the production cost is not reduced, and the problem of reaction corrosion is not solved.
Therefore, the technology has certain problems in the process of reducing the acid value of the biodiesel product. In fact, as long as alkaline substances are used, the problems of corrosion, emulsification, wastewater pollution and the like in the biodiesel deacidification process cannot be thoroughly solved by strong alkali or weak alkali. The supported solid acid deacidification process has no various problems in the traditional alkali washing and neutralizing processes, but the process is still immature, and particularly has a plurality of problems which are not solved, such as component loss, complex preparation, high price and the like. The product obtained by the technology can meet the national standard requirement if only the product property is used for measurement. However, in the face of increasingly serious environmental pollution and continuously improved environmental protection standards, it is necessary to develop an efficient, clean and environment-friendly biodiesel acid reduction technology.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide ZrO2The polycrystalline foamed ceramic catalyst, the preparation method and the application thereof convert free fatty acid in the biodiesel into fatty glyceride through esterification reaction of the fatty acid and the biodiesel byproduct glycerol so as to achieve the purpose of reducing the acid value.
In order to solve the above technical problems, the present invention provides ZrO2The polycrystalline foamed ceramic catalyst is characterized by comprising Zr, Al and Ti elements, wherein the molar ratio of Zr to Al to Ti is 5: 2.2-3.5: 0.2.
further, the Zr compound is ZrOCl2•8H2O or ZrO2The compound of Al is AlCl3Or Al2O3The compound of Ti is TiCl4Or TiO2。
The invention also provides ZrO2The preparation method of the polycrystalline foamed ceramic catalyst is characterized by comprising the following steps:
step by step ZrOCl2•8H2O、AlCl3And TiCl4Dissolved in deionized water to prepare the product with the concentration of 20-40%Precipitating mother liquor, and then slowly adding ethanol solution containing 10-13 g/L of template agent and precipitating agent into the precipitation mother liquor, wherein the precipitating agent and ZrOCl2•8H2The molar ratio of O is 1: 1-3: 1, and Y with the mass fraction of 5-10% is added and dissolved simultaneously2O3Heating the concentrated nitric acid until the pH value is 2-3 to 80-100 ℃ under vigorous stirring, and keeping the temperature for 12-24 hours; after the reaction is finished, adjusting the pH to 2-3 by using dilute nitric acid, and crystallizing for 6-12 hours at the temperature of 40-60 ℃; after crystallization, vacuum filtration is carried out, and deionized water is washed until no Cl is contained-1Washing with absolute ethyl alcohol for 2-3 times, and vacuum drying in a vacuum drying oven at 80-120 ℃ for 12-24 hours; putting the dried solid matter into a ball mill, grinding the solid matter into powder, adding 20-30 wt% of pore-forming agent, and continuing grinding until the solid matter is fully mixed; and taking out the mixed powder and 5-10 wt% of lubricant, putting the mixed powder and the lubricant into a wet mixing granulator, adding a binder for granulation, controlling the particle size to be 1-2 mm, putting the granulated catalyst precursor into a vacuum drying oven, drying for 6-8 h at 80-100 ℃, taking out, and putting into a muffle furnace, and roasting for 4-6 h at 500-600 ℃ to obtain the required catalyst.
Further, the template agent is one or more of CTAB, DBS, TW-80, ethylenediamine and n-butylamine.
Further, the precipitant is one or more of urea, potassium carbonate, potassium hydroxide, ammonia water, sodium carbonate, sodium hydroxide, ammonium carbonate, ammonium hydroxide, potassium bicarbonate and sodium bicarbonate.
Further, the pore-forming agent is one or more of ammonium bicarbonate, polyethylene glycol, ethylene oxide, alkyl cellulose, cellulose methyl ether polyallyl alcohol and amine.
Further, the lubricant is one or more of sesbania powder, paraffin, stearic acid, glycerol, lubricating oil and polyacrylamide.
Further, the binder is one or more of silica sol, methyl cellulose, starch, polyvinyl alcohol, aluminum sol, water glass and clay.
The invention also provides ZrO2Use of a catalyst for polycrystalline ceramic foams, characterized in that ZrO is treated with2Polycrystalline foamed ceramicsThe ceramic catalyst is used for catalyzing the esterification of glycerin to reduce the acid value of biodiesel, and specifically comprises the following steps: using biodiesel as reaction raw material, ZrO2Taking the polycrystalline foamed ceramic as a catalyst and taking the biodiesel byproduct glycerol as an esterifying agent to carry out esterification reaction; after the reaction is finished, the glycerin and the solid catalyst are centrifugally separated, and the upper layer liquid is rectified under reduced pressure to obtain a biodiesel product meeting the standard.
Further, the acid value of the biodiesel is 5-20 mg KOH/g, the purity of the glycerol is more than 80%, the mass ratio of the biodiesel to the glycerol is 3: 1-5: 1, and the amount of the catalyst is 0.3-1.0 wt%; the reaction temperature of the esterification reaction is 180-220 ℃, the reaction time is 3-6 h, the stirring speed is 300-500 rpm/min, and the pressure is reduced to-0.03-0.1 MPa.
The invention achieves the following beneficial effects:
（1）ZrO2the polycrystalline foamed ceramic catalyst is prepared by combining a uniform precipitation method and a high-temperature ceramic method, and is prepared by roasting an active component hydroxide precursor and decomposing the generated AL by using the hydroxide precursor2O3And TiO2Ti of (A)4+And Al3+Iso-cation of ZrO2Zr in (1)4+The ions are displaced to form a displaced solid solution, the solid solution can effectively prevent the crystal form transformation through eutectoid decomposition in the rapid cooling process, thereby effectively avoiding the problems of material lack of uniformity and low specific surface area caused by high-temperature roasting in a high-temperature ceramic method, and ensuring the mutual dispersion of different phases and components of the multi-component bulk catalyst. Meanwhile, the obtained catalyst is a bulk catalyst, so that the problem of component loss cannot occur in the reaction process, and the long-term service life of the catalyst is ensured.
(2) The method reduces the acid value of the biodiesel, can avoid corrosion, emulsification and material loss caused by alkaline cleaning, simultaneously obtains the fatty glyceride with the same components as the raw materials for producing the biodiesel, is easy to separate from the product, and particularly can basically remove the generated triglyceride, thereby obviously improving the service performance of the biodiesel.
Detailed Description
The invention is further described below. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
The invention provides a ZrO2The polycrystalline foamed ceramic catalyst comprises Zr, Al and Ti elements, wherein the molar ratio of Zr to Al to Ti is 5: 2.2-3.5: 0.2.
wherein the compound of Zr is ZrOCl2•8H2O or ZrO2The compound of Al is AlCl3Or Al2O3The compound of Ti is TiCl4Or TiO2。
The invention also provides ZrO2A method of making a polycrystalline ceramic foam catalyst, comprising:
step by step ZrOCl2•8H2O、AlCl3And TiCl4(N zirconium: N aluminum: N titanium = 5: 2.2-3.5: 0.2) is dissolved in deionized water to prepare 20-40% precipitation mother liquor, then ethanol solution containing 10-13 g/L template agent (CTAB) and urea (N urea: zirconium oxychloride =1: 1-3: 1) with certain concentration is slowly added into the precipitation mother liquor, and Y with the mass fraction of 5-10% is dissolved in the ethanol solution in a flowing mode2O3Heating the concentrated nitric acid until the pH value is 2-3 to 80-100 ℃ under vigorous stirring, and keeping the temperature for 12-24 hours. After the reaction is finished, adjusting the pH value to 2-3 by using dilute nitric acid, and crystallizing for 6-12 hours at the temperature of 40-60 ℃. After crystallization, vacuum filtration is carried out, and deionized water is washed until no Cl is contained-1Washing with absolute ethyl alcohol for 2-3 times, and vacuum drying at 80-120 ℃ in a vacuum drying oven for 12-24 hours. And (3) putting the dried solid matter into a ball mill, grinding the solid matter into powder, adding 20-30 wt% of ammonium bicarbonate, and continuing grinding until the solid matter is fully mixed. Taking out the mixed powder and 5-10 wt% of polyacrylamide, putting the mixed powder and the polyacrylamide into a wet mixing granulator, adding silica sol for granulation, controlling the particle size to be 1-2 mm, putting the granulated catalyst precursor into a vacuum drying oven, drying for 6-8 h at 80-100 ℃, taking out, and putting into a muffle furnace, and roasting for 4-6 h at 500-600 ℃ to obtain the required catalyst.
The invention also provides ZrO2The application of the polycrystalline foamed ceramic catalyst for catalyzing glycerol esterification to reduce the acid value of biodiesel is shown in the following specific examples.
Example 1:
adding biodiesel (acid value 20mg KOH/g) and biodiesel byproduct glycerol (content 85%) into a 5L glass reaction kettle according to the mass ratio of 3:1, starting a stirrer, setting the rotating speed to 350rpm/min, and weighing ZrO 0.3% of oil weight2And slowly adding the polycrystalline foamed ceramic catalyst into the reaction kettle. Switching on a vacuum pump, setting the temperature of a constant-temperature oil bath kettle at 220 ℃ after the vacuum pressure of the device is stabilized at-0.1 MPa and stirring uniformly, opening a low-temperature condensing device until the temperature of materials in the reaction kettle rises to 220 ℃, stabilizing the reaction for 6 hours, centrifugally separating the catalyst, standing and layering the obtained product, taking an upper methyl ester layer, and determining that the acid value is 0.3 mg KOH/g and the esterification rate is 98.5%. The upper layer of light yellow liquid enters a vacuum rectification device, and monoglyceride, diglyceride and triglyceride generated by the reaction and mixed trace glycerol are separated and removed, so that the refined biodiesel product can be obtained.
Example 2:
adding biodiesel (acid value 20mg KOH/g) and biodiesel byproduct glycerol (content 85%) into a 5L glass reaction kettle according to a mass ratio of 4:1, starting a stirrer, setting the rotating speed to be 500rpm/min, and weighing ZrO 1.0% of oil weight2And slowly adding the polycrystalline foamed ceramic catalyst into the reaction kettle. Switching on a vacuum pump, setting the temperature of a constant-temperature oil bath kettle at 220 ℃ after the vacuum pressure of the device is stabilized at-0.1 MPa and stirring uniformly, opening a low-temperature condensing device until the temperature of materials in the reaction kettle rises to 220 ℃, stabilizing the reaction for 6 hours, centrifugally separating the catalyst, standing and layering the obtained product, taking an upper methyl ester layer, and determining that the acid value is 0.1 mg KOH/g and the esterification rate is 99.5%. The upper layer of light yellow liquid enters a vacuum rectification device, and monoglyceride, diglyceride and triglyceride generated by the reaction and mixed trace glycerol are separated and removed, so that the refined biodiesel product can be obtained.
Example 3:
biodiesel (acid value 10mg KOH/g) and biodiesel by-product glycerol (content 90%) according to the mass ratio of 51 adding a 5L glass reaction kettle, starting a stirrer, setting the rotating speed to be 400rpm/min, and then weighing ZrO 0.8 percent of oil weight2And slowly adding the polycrystalline foamed ceramic catalyst into the reaction kettle. Switching on a vacuum pump, setting the temperature of a constant-temperature oil bath kettle to 200 ℃ after the vacuum pressure of the device is stabilized at-0.9 MPa and stirring uniformly, opening a low-temperature condensing device until the temperature of materials in the reaction kettle rises to 200 ℃, stabilizing the reaction for 5 hours, centrifugally separating the catalyst, standing and layering the obtained product, taking an upper methyl ester layer, and determining that the acid value is 0.4 mg KOH/g and the esterification rate is 96.0%. The upper layer of light yellow liquid enters a vacuum rectification device, and monoglyceride, diglyceride and triglyceride generated by the reaction and mixed trace glycerol are separated and removed, so that the refined biodiesel product can be obtained.
Example 4:
adding biodiesel (acid value 5mg KOH/g) and biodiesel byproduct glycerol (content 90%) into a 5L glass reaction kettle according to the mass ratio of 3:1, starting a stirrer, setting the rotating speed to be 500rpm/min, and weighing ZrO 0.3% of oil weight2And slowly adding the polycrystalline foamed ceramic catalyst into the reaction kettle. Switching on a vacuum pump, setting the temperature of a constant-temperature oil bath kettle at 180 ℃ after the vacuum pressure of the device is stabilized at-0.1 MPa and stirring uniformly, opening a low-temperature condensing device until the temperature of materials in the reaction kettle rises to 180 ℃, stabilizing the reaction for 4 hours, centrifugally separating the catalyst, standing and layering the obtained product, taking an upper methyl ester layer, and determining that the acid value is 0.2 mg KOH/g and the esterification rate is 96%. The upper layer of light yellow liquid enters a vacuum rectification device, and monoglyceride, diglyceride and triglyceride generated by the reaction and mixed trace glycerol are separated and removed, so that the refined biodiesel product can be obtained.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (6)
1. ZrO2The preparation method of the polycrystalline foamed ceramic catalyst is characterized by comprising the following steps:
step by step ZrOCl2•8H2O、AlCl3And TiCl4Dissolving the precipitate in deionized water to prepare 20-40% of precipitation mother liquor, and slowly adding ethanol solution containing 10-13 g/L of template agent and precipitant into the precipitation mother liquor, wherein the precipitant and ZrOCl2•8H2The molar ratio of O is 1: 1-3: 1, and Y with the mass fraction of 5-10% is added and dissolved simultaneously2O3Heating the concentrated nitric acid until the pH value is 2-3 to 80-100 ℃ under vigorous stirring, and keeping the temperature for 12-24 hours; after the reaction is finished, adjusting the pH to 2-3 by using dilute nitric acid, and crystallizing for 6-12 hours at the temperature of 40-60 ℃; after crystallization, vacuum filtration is carried out, and deionized water is washed until no Cl is contained-1Washing with absolute ethyl alcohol for 2-3 times, and vacuum drying in a vacuum drying oven at 80-120 ℃ for 12-24 hours; putting the dried solid matter into a ball mill, grinding the solid matter into powder, adding 20-30 wt% of pore-forming agent, and continuing grinding until the solid matter is fully mixed; and taking out the mixed powder and 5-10 wt% of lubricant, putting the mixed powder and the lubricant into a wet mixing granulator, adding a binder for granulation, controlling the particle size to be 1-2 mm, putting the granulated catalyst precursor into a vacuum drying oven, drying for 6-8 h at 80-100 ℃, taking out, and putting into a muffle furnace, and roasting for 4-6 h at 500-600 ℃ to obtain the required catalyst.
2. ZrO according to claim 12The preparation method of the polycrystalline foamed ceramic catalyst is characterized in that the template agent is one or more of CTAB, DBS, TW-80, ethylenediamine and n-butylamine.
3. ZrO according to claim 12The preparation method of the polycrystalline foamed ceramic catalyst is characterized in that the precipitator is one or more of urea, potassium carbonate, potassium hydroxide, ammonia water, sodium carbonate, sodium hydroxide, ammonium carbonate, ammonium hydroxide, potassium bicarbonate and sodium bicarbonate.
4. ZrO according to claim 12The preparation method of the polycrystalline foamed ceramic catalyst is characterized in that the pore-forming agent is ammonium bicarbonate, polyethylene glycol and ethylene oxideOne or more of alkane, alkyl cellulose, cellulose methyl ether polypropylene alcohol and amine.
5. ZrO according to claim 12The preparation method of the polycrystalline foamed ceramic catalyst is characterized in that the lubricant is one or more of sesbania powder, paraffin, stearic acid, glycerol, lubricating oil and polyacrylamide.
6. ZrO according to claim 12The preparation method of the polycrystalline foamed ceramic catalyst is characterized in that the binder is one or more of silica sol, methyl cellulose, starch, polyvinyl alcohol, aluminum sol, water glass and clay.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710798322.9A CN107597087B (en) | 2017-09-07 | 2017-09-07 | ZrO2Polycrystalline ceramic foam catalyst, method for the production thereof and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710798322.9A CN107597087B (en) | 2017-09-07 | 2017-09-07 | ZrO2Polycrystalline ceramic foam catalyst, method for the production thereof and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107597087A CN107597087A (en) | 2018-01-19 |
| CN107597087B true CN107597087B (en) | 2020-05-19 |
Family
ID=61062131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710798322.9A Active CN107597087B (en) | 2017-09-07 | 2017-09-07 | ZrO2Polycrystalline ceramic foam catalyst, method for the production thereof and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107597087B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116286196B (en) * | 2023-01-29 | 2024-03-05 | 浙江大学 | Method for catalytic conversion of algae oil by wrapping zirconium-based metal organic framework with acidic ionic liquid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269958A (en) * | 2008-05-08 | 2008-09-24 | 广东东方锆业科技股份有限公司 | Cerium stabilizing zirconium oxide structure ceramic material and preparation method thereof |
| CN103752297A (en) * | 2014-01-03 | 2014-04-30 | 南昌大学 | Zirconium-oxide catalyst for producing biodiesel, as well as preparation method and application of zirconium-oxide catalyst |
| CN103877958A (en) * | 2014-03-12 | 2014-06-25 | 南京大学昆山创新研究院 | Catalyst for preparing biodiesel and preparation method thereof as well as preparation process of biodiesel |
-
2017
- 2017-09-07 CN CN201710798322.9A patent/CN107597087B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269958A (en) * | 2008-05-08 | 2008-09-24 | 广东东方锆业科技股份有限公司 | Cerium stabilizing zirconium oxide structure ceramic material and preparation method thereof |
| CN103752297A (en) * | 2014-01-03 | 2014-04-30 | 南昌大学 | Zirconium-oxide catalyst for producing biodiesel, as well as preparation method and application of zirconium-oxide catalyst |
| CN103877958A (en) * | 2014-03-12 | 2014-06-25 | 南京大学昆山创新研究院 | Catalyst for preparing biodiesel and preparation method thereof as well as preparation process of biodiesel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107597087A (en) | 2018-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111500373B (en) | Preparation method of biodiesel | |
| CN105537003A (en) | Drainage oil type collophanite reverse flotation collecting agent and preparation method thereof | |
| CN105668650B (en) | The preparation method of low sodium cobaltosic oxide | |
| CN103739803A (en) | Synthesis method of imino methylated amino resin | |
| CN1824735A (en) | Preparation of curcas biological diesel oil by solid phase catalytic method | |
| CN107597087B (en) | ZrO2Polycrystalline ceramic foam catalyst, method for the production thereof and use thereof | |
| CN104107705A (en) | Solid base catalyst for preparing biodiesel | |
| CN106675699A (en) | Preparation method of ultra-overbased synthetic magnesium sulfonate | |
| CN105133035A (en) | Cleaning and decontaminating silicon wafer texturing agent and preparation method therefor | |
| CN1824734A (en) | Method of synthesizing biodiesel oil using fixed bed gaseous phase esterification reaction | |
| CN105002005A (en) | Ultrasonic automobile carbon removal cleaning agent and preparation method thereof | |
| JP2005015562A (en) | Method for producing fatty acid alkyl ester | |
| CN107723087A (en) | A kind of preparation method of biodiesel | |
| CN205275500U (en) | Epoxypropane system is produced to chloropharin metaplasia | |
| CN110229378B (en) | Crystallization drying process for recycling polyester bottle flakes | |
| CN103484258A (en) | Method for preparing biodiesel by using nano hydroxyapatite to catalyze triglyceride | |
| CN102391914A (en) | Method for preparing biodiesel by catalysis of rare-earth oxide mesoporous material | |
| CN102229864B (en) | Method for producing biodiesel with hogwash oil of high acid value | |
| CN106083585A (en) | A kind of method that dimethyl carbonate is prepared in indirect alcoholysis | |
| CN105133030A (en) | Long-acting silicon wafer texture-etchant and preparation method therefor | |
| CN1830550A (en) | Synthesis reaction catalyst for loading type alkali metal biodiesel oil | |
| CN220531190U (en) | Tail gas treatment device for chemical vapor deposition furnace | |
| CN103467289B (en) | A kind of preparation method of glycerine triacetate | |
| CN103691453A (en) | Preparation method for solid acid catalyst | |
| CN103657627A (en) | Activated carbon/CaZnO solid base catalyst for producing biodiesel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |