CN109603869B - Phosphoric acid modified cerium oxide catalyst and preparation method and application thereof - Google Patents
Phosphoric acid modified cerium oxide catalyst and preparation method and application thereof Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
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- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
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Abstract
The invention relates to the technical field of air pollution control, and discloses a phosphoric acid modified cerium oxide catalyst and a preparation method and application thereof. The preparation method comprises the following steps: (1) soaking cerium oxide in a phosphoric acid solution, filtering the cerium oxide, washing the cerium oxide to be neutral, and drying the cerium oxide; (2) and calcining the dried cerium oxide at 100-400 ℃ for 1-4 hours to obtain the phosphoric acid modified cerium oxide catalyst. The catalyst prepared by the preparation method can be used for catalytic oxidation degradation of chlorine-containing volatile organic compounds, has high catalytic activity, strong chlorine poisoning resistance, sulfur poisoning resistance and water resistance, long catalytic life, is not easy to generate toxic byproducts when the chlorine-containing volatile organic compounds are catalytically oxidized, and has no secondary pollution.
Description
Technical Field
The invention relates to the technical field of air pollution control, in particular to a cerium oxide catalyst modified by phosphoric acid and a preparation method and application thereof.
Background
The chlorine-containing volatile organic compounds are one of organic compounds, such as chlorobenzene, dichlorobenzene, trichloroethylene and the like, are common reagents in industrial production processes, and are discharged into the environment in the form of waste water or waste gas. Most of chlorine-containing volatile organic compounds have lasting environment and high toxicity, can exist in atmospheric environment or water environment for a long time, and are enriched in organisms through food chains to cause carcinogenic, teratogenic and mutagenic effects. The organic compounds containing chlorine generally have toxicity, and 65 and 129 preferentially controlled black lists are selected from 7 ten thousand compounds by the U.S. environmental protection agency based on the toxicity of the compounds, the possibility of natural degradation, the probability of occurrence in water and other factors, wherein 7 polychlorinated biphenyls and related compounds exist. On the black list, the most serious pollutants for the environmental pollution of China comprise 1 polychlorinated biphenyl, 4 chlorobenzene and 10 halogenated hydrocarbons. It follows that the pollution of organic chlorides is quite common and serious, and therefore the disposal of organic chlorides is an important work content for the current environmental protection.
Chlorine-containing volatile organic compounds can be roughly divided into two main groups: the first is low molecular weight organic chloride mainly comprising trichloromethane, carbon tetrachloride, dichloroethane, trichloroethylene, trichloroethane, tetrachloroethylene, chlorobenzene and the like; the second is polymeric chloride, including polychlorinated biphenyl furan, dioxin, and the like. Most of these compounds come from organic solvents in industrial applications, fire extinguishing agents, intermediates for thermal conducting fluids and chemical products, and by-products of the power industry. Their concentrations in industrial waste gas or incineration plants vary greatly, the former typically being between 200 and 2000ppm and the latter usually being less than 1ng/m3. The chlorine-containing volatile organic compounds emitted by the organization can be collected and treated to effectively reduce the content of the tail gas. As a last line of defense, the development and application of the high-efficiency end treatment technology is the focus of research at present. In recent years, low-temperature plasma technology and membrane separation technology have been completely open in the treatment of low-concentration organic exhaust gas, and photocatalytic technology has been further developed. The control technology commonly used at present mainly comprises a thermal combustion method, a catalytic combustion method, an adsorption method, an absorption method, a condensation method and the like, and the removal efficiency of the control technology is usually related to the import concentration. On the basis of ensuring the removal efficiency, the prior art has advantages and disadvantages by combining the aspects of investment cost, applicable working conditions, operation safety and the like. The catalytic combustion technology is one of the most promising technologies by virtue of the characteristics of high treatment efficiency, low energy consumption, recoverable heat power and no secondary pollution.
The key problem to be solved in the first place is to improve the service life of the catalyst. Although some transition metal oxides such as manganese oxide, cerium oxide, etc. show better activity in catalytic combustion of chlorine-containing organic matters, these transition metal oxides can even achieve the same catalytic activity as noble metals, but the problem of catalyst chloridization poisoning cannot be avoided. Chlorine adsorbed on the surface of the catalyst can form chlorine-oxygen compounds or chlorides with metal ions, so that the number of active centers of the catalyst is reduced or the redox performance of the active centers is influenced, and the activity of the catalyst is inhibited. In addition, this process also increases the environmental risk of generating highly toxic polychlorinated byproducts, particularly dioxins.
Chinese patent publication No. CN108295852A discloses a Ce-Zr catalyst for catalytic oxidation of chlorine-containing volatile organic compounds, especially a Ru/CeZrOxThe catalyst can realize better activity and conversion rate at lower temperature. Due to the use of Ru, the catalyst cost is high.
Chinese patent publication No. CN103962134A discloses a method for eliminating chlorinated aromatic hydrocarbons by burning, in which cerium oxide nanorods, nanocubes and nano octahedrons are used as carriers to load noble metal (Ru) ruthenium as a catalyst, and reaction exhaust gas is absorbed by dilute alkali solution. The method has high catalytic activity, no secondary pollutant is generated in the reaction, and the catalyst cost is higher due to the use of Ru.
Chinese patent publication No. CN10389425A discloses a catalyst for polychlorinated aromatic hydrocarbon combustion, which is Fe, Ni, Cr, Bi or Mn doped cobaltosic oxide. The catalyst has high catalytic activity and strong chlorine poisoning resistance, but has a fragile structure, and cannot be applied to waste gas treatment at a high airspeed.
Chinese patent publication No. CN103962127A discloses a catalyst for burning chlorinated aromatic hydrocarbon, which is Sr, Ce, Mg, Al, Fe, Co, Ni, Cu doped LaMnO with perovskite structure3. The catalyst has the advantages of simple preparation, low cost, good thermal stability, low catalytic activity and easy low-temperature chlorine poisoning.
The existing catalyst for catalytic oxidation of the chlorine-containing volatile organic compounds has poor water resistance and sulfur resistance, has high requirements on the water content and the sulfur content of the flue gas containing the chlorine-containing volatile organic compounds, and needs to dehydrate and desulfurize the flue gas before catalytic oxidation degradation.
Disclosure of Invention
The prepared catalyst can be used for catalytic oxidation degradation of chlorine-containing volatile organic compounds, has high catalytic activity, strong chlorine poisoning resistance, sulfur poisoning resistance and water resistance and long catalytic life, does not easily generate toxic byproducts when the chlorine-containing volatile organic compounds are catalytically oxidized, and does not have secondary pollution.
The specific technical scheme is as follows:
a preparation method of a phosphoric acid modified cerium oxide catalyst comprises the following steps:
(1) soaking cerium oxide in a phosphoric acid solution, filtering the cerium oxide, washing the cerium oxide to be neutral, and drying the cerium oxide;
(2) and calcining the dried cerium oxide at 100-400 ℃ for 1-4 hours to obtain the phosphoric acid modified cerium oxide catalyst.
The preparation method of the invention is characterized in that cerium oxide is soaked in phosphoric acid solution, characteristic phosphate groups (which can be converted into trihydroxy phosphate groups in the presence of water vapor) are introduced on the surface of the catalyst, and chlorine-containing volatile organic compounds can be effectively dechlorinated in the presence of oxygen and water, so that the desorption of chlorine on the surface of the catalyst is promoted, the catalyst is prevented from being poisoned by chlorine, meanwhile, water in flue gas has a promoting effect on the catalytic oxidation process, and the catalyst has better sulfur resistance on the surface of experimental data.
The load of phosphorus in the catalyst has an important influence on the catalytic activity of the catalyst, when the load of phosphorus is lower, the influence on the chlorine resistance, sulfur resistance and water resistance of the catalyst is smaller, the increment of the catalytic activity is not obvious, and when the load of phosphorus is higher, the catalytic activity of the catalyst is reduced, so the load of phosphorus needs to be controlled.
Preferably, the phosphorus loading amount in the cerium oxide catalyst is 0.1-5% in percentage by mass of phosphorus element.
More preferably, the phosphorus loading amount in the cerium oxide catalyst is 0.3-1% by mass of phosphorus element.
When the phosphorus loading is controlled to be 0.3-1%, the catalyst not only has higher catalytic activity, but also has excellent chlorine resistance, sulfur resistance and water resistance.
Preferably, in the step (1), the concentration of the phosphoric acid solution is 10-200 g/L, and the molar ratio of cerium oxide to phosphoric acid is 1: 0.05-1; more preferably, the molar ratio of the cerium oxide to the phosphoric acid is 1: 0.05-0.2.
Preferably, in the step (1), the soaking temperature of the cerium oxide is 10-80 ℃, and the soaking time is 0.5-3 h; further preferably, in the step (1), the soaking temperature of the cerium oxide is 10-40 ℃, and the soaking time is 0.5-1 h.
And (2) soaking, cooling, filtering and washing the precipitate in the step (1) to obtain a light yellow precipitate.
In the step (2), the calcination may be performed in a nitrogen or air atmosphere.
The calcination temperature of the catalyst is too high, so that a form with good catalytic performance cannot be obtained, and the catalytic efficiency is reduced; the calcination temperature is too low to obtain a catalyst having the desired composition.
Preferably, in the step (2), the calcination temperature is 200-300 ℃.
The catalyst calcination time is not easy to be too long, and the calcination time is too long, so that the catalyst crystal lattice is collapsed, and the specific surface area is reduced.
Preferably, in the step (2), the calcination time is 1-2 h.
The invention also provides an application of the phosphoric acid modified cerium oxide catalyst in catalytic oxidative degradation of chlorine-containing volatile organic compounds, which comprises the following steps:
reacting flue gas containing chlorine-containing volatile organic compounds and water vapor under the action of the cerium oxide catalyst;
in the flue gas, the volume fraction of the water vapor is 0.1-5%;
the reaction temperature is 100-300 ℃.
Preferably, the mass fraction of the water vapor in the flue gas is 0.5-2%.
The content of the water vapor in the flue gas is properly increased, the catalytic oxidation efficiency of the catalyst on the chlorine-containing volatile organic compounds is improved, when the content of the water vapor is 0.5-2%, the catalyst shows the best chlorobenzene removal efficiency, and when the content of the water vapor is increased to 5%, the catalyst still shows good catalytic activity.
Preferably, the reaction temperature is 200-300 ℃.
The cerium oxide catalyst has good oxidation efficiency on chlorine-containing volatile organic compounds in a medium-low temperature region of 100-300 ℃, and particularly has the best catalytic efficiency in a temperature region of 200-300 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method is simple in preparation process, low in cost and suitable for large-scale production;
(2) phosphoric acid-treated CeO of the present invention2Catalyst, fully utilizes CeO2Due to Ce4+/Ce3+The catalyst has good oxygen storage and release performance and oxygen mobility, and the capability of hydrolyzing and dechlorinating chlorine-containing organic matters by phosphate radicals, so that the catalyst can stably convert chlorine-containing volatile organic pollutants into H for a long time in industrial waste gas and flue gas environments2O、CO2And HCl, realize dechlorination at low temperature, water-resistant, chlorine-resistant performance is better;
(3) experimental data show that the catalyst has better sulfur resistance;
(4) the catalyst of the invention takes low-cost cerium oxide as an active material, and phosphoric acid is used for treatment, so that the service life of the catalyst is greatly prolonged, toxic byproducts generated in the catalytic reaction process are inhibited, and secondary pollution is avoided.
Drawings
FIG. 1 is a graph of SS NMR characterization results for the catalyst prepared in example 1;
FIG. 2 is a graph of the results of in situ infrared characterization of the catalyst prepared in example 1.
Detailed Description
Example 1
Preparing a catalyst:
(1) cerium oxide powder and phosphoric acid (concentration of phosphoric acid solution is 1mol/L) are mixed according to a molar ratio of 1:0.05, the mixture reacts for 0.5h at 30 ℃, and the obtained mixture is cooled, stood and washed to obtain yellow cerium oxide precipitate.
(2) And washing the obtained mixture to be neutral, drying, and calcining at 200 ℃ for 1h in an air atmosphere to obtain the catalyst.
The phosphorus loading of the prepared catalyst was 0.7%.
As shown in fig. 1, the presence of phosphate groups on the surface of cerium oxide was confirmed by SS NMR characterization. Subsequent in situ infrared characterization is shown in fig. 2, which also demonstrates the presence of P-O and P ═ O on the surface of the phosphoric acid treated ceria. The test shows that the main existing form of phosphoric acid on the surface of the catalyst after phosphoric acid treatment is dihydroxyphosphate radical.
Example 2
Preparing a catalyst:
(1) mixing cerium oxide powder and phosphoric acid in the molar ratio of 1 to 0.05, reacting at 80 deg.c for 0.5 hr, cooling the mixture, standing and washing to obtain yellow cerium oxide precipitate.
(2) And washing the obtained mixture to be neutral, drying, and calcining at 200 ℃ for 1h in an air atmosphere to obtain the catalyst.
The phosphorus loading of the prepared catalyst was 0.4%.
Example 3
Preparing a catalyst:
(1) mixing cerium oxide powder and phosphoric acid in a molar ratio of 1:0.05, reacting at 30 ℃ for 0.5h, cooling the obtained mixture, standing and washing to obtain yellow cerium oxide precipitate.
(2) And washing the obtained mixture to be neutral, drying, and calcining at 300 ℃ for 2h in an air atmosphere to obtain the catalyst.
The phosphorus loading of the prepared catalyst was 0.7%.
Example 4
Preparing a catalyst:
(1) mixing cerium oxide powder with phosphoric acid in a ratio of 1: 0.2 mol ratio, reacting for 1h at 30 ℃, cooling, standing and washing the obtained mixture to obtain yellow cerium oxide precipitate.
(2) And washing the obtained mixture to be neutral, drying, and calcining at 200 ℃ for 1h in an air atmosphere to obtain the catalyst.
The phosphorus loading of the prepared catalyst was 1.2%.
Example 5
Preparing a catalyst:
(1) mixing cerium oxide powder with phosphoric acid in a ratio of 1: 0.2 mol ratio, reacting for 1h at 30 ℃, cooling, standing and washing the obtained mixture to obtain yellow cerium oxide precipitate.
(2) And washing the obtained mixture to be neutral, drying, and calcining at 300 ℃ for 2h in an air atmosphere to obtain the catalyst.
The phosphorus loading of the prepared catalyst was 1.2%.
Comparative example 1
And calcining the cerium oxide powder for 2h at 300 ℃ under an air atmosphere to obtain the catalyst.
Application example 1
The chlorobenzene is catalytically oxidized by the catalyst prepared in the above 5 examples, which specifically comprises the following steps:
the activity test is carried out on a fixed bed reactor, the loading amount of the catalyst is 1.0g, and the granularity is 40-60 meshes. The initial gas concentrations were: 1000ppm of chlorobenzene, [ O ]2]＝10％，[H2O]＝0.2％，N2As carrier gas, GHSV (gas space velocity) ═ 10000h-1. The reaction temperature is measured at 100 deg.C, 150 deg.C, 200 deg.C, 225 deg.C, 250 deg.C, 300 deg.C, and the test data of 1h reaction is detailed in Table 1.
TABLE 1 catalytic Oxidation efficiency/% of catalyst to chlorobenzene
The experimental results in table 1 show that the catalysts prepared by the method of the present invention have good oxidation efficiency to chlorobenzene in the medium and low temperature range of 150-300 ℃, and particularly, the catalysts prepared in examples 1 and 3 have catalytic efficiency of more than 90% in the temperature range of 200-300 ℃. Therefore, the catalyst is very suitable for catalytic oxidation of chlorobenzene under medium-low temperature flue gas.
Application example 2
The following experiments were carried out on a fixed bed reactor with a catalyst loading of 1g and a particle size of 40-60 mesh. The initial gas concentrations were: 1000ppm of chlorobenzene, [ O ]2]＝10％，[H2O]＝0.5％，N2As carrier gas, GHSV (gas space velocity) ═ 10000h-1. The reaction temperature is measured at 100 deg.C, 150 deg.C, 200 deg.C, 225 deg.C, 250 deg.C, 300 deg.C, and the test data of 1h reaction is detailed in Table 2.
TABLE 2H2Effect of O (0.5%) on the catalytic Oxidation efficiency of Chlorobenzene%
Application example 3
The following experiments were carried out on a fixed bed reactor with a catalyst loading of 1g and a particle size of 40-60 mesh. The initial gas concentrations were: 1000ppm of chlorobenzene, [ O ]2]＝10％，[H2O]＝2％，N2As carrier gas, GHSV (gas space velocity) ═ 10000h-1. The reaction temperature is measured at 100 deg.C, 150 deg.C, 200 deg.C, 225 deg.C, 250 deg.C, 300 deg.C, and the test data of 1h reaction is detailed in Table 3.
TABLE 3H2Effect of O (2%) on the catalytic Oxidation efficiency of chlorobenzene%
Application example 4
The following experiments were carried out on a fixed bed reactor with a catalyst loading of 1g and a particle size of 40-60 mesh. The initial gas concentrations were: 1000ppm of chlorobenzene, [ O ]2]＝10％，[H2O]＝5％，N2As carrier gas, GHSV (gas space velocity) ═ 10000h-1. The reaction temperature is measured at 100 deg.C, 150 deg.C, 200 deg.C, 225 deg.C, 250 deg.C, 300 deg.C, and the test data of 1h reaction is detailed in Table 4.
TABLE 4H2Catalytic oxidation efficiency of O (5%) p-chlorobenzeneInfluence of/assay
As shown in the experimental results of tables 1 to 4, the H content in the flue gas is properly increased2The content of O and the catalytic oxidation efficiency of the catalyst to chlorobenzene are still improved, and the best chlorobenzene removal efficiency is shown when the water passing amount is 0.2-2%. When the water content is increased to 5%, the catalyst still shows good activity, and the catalytic efficiency is more than 85% at 300 ℃. Therefore, the catalyst can make full use of H in the flue gas2O, greatly promotes the catalytic oxidation of chlorobenzene.
In the comparative example 1, the catalytic oxidation efficiency of the catalyst not modified by phosphoric acid to chlorobenzene is better when the moisture content in the flue gas is lower at 200-300 ℃, but the catalytic oxidation efficiency of the catalyst to chlorobenzene is rapidly reduced along with the increase of the moisture content in the flue gas, which indicates that the water resistance of the cerium oxide catalyst not modified by phosphoric acid is poorer.
Application example 5
Stability test of catalytic oxidation of chlorobenzene by catalyst
The following experiments were carried out on a fixed bed reactor with a catalyst loading of 1g and a particle size of 40-60 mesh. The initial gas concentrations were: 1000ppm of chlorobenzene, [ O ]2]＝10％，[H2O]＝0.5％，N2As carrier gas, GHSV (gas space velocity) ═ 10000h-1. The reaction temperature is measured to be 300 ℃ and N2For carrier gas, the test data are detailed in table 5.
TABLE 5 stability/% (test temperature 300 ℃ C.) of catalyst
As can be seen from Table 5, the catalyst of the present invention has almost no influence on the oxidation activity of chlorobenzene after the chlorobenzene is treated for several hours (containing a certain amount of water vapor), and the catalyst of the present invention has good chlorine poisoning resistance and can stably operate for a long time.
The catalyst of comparative example 1 which is not modified by phosphoric acid has poor stability and is easy to be poisoned by chlorine to lose catalytic activity.
Application example 6
Sulfur resistance test of catalytic oxidation chlorobenzene by catalyst
The following experiments were carried out on a fixed bed reactor with a catalyst loading of 1g and a particle size of 40-60 mesh. The initial gas concentrations were: 1000ppm of chlorobenzene, [ O ]2]＝10％，[H2O]＝0.5％，[SO2]＝50ppm，N2As carrier gas, GHSV (gas space velocity) ═ 10000h-1. The reaction temperature is measured to be 300 ℃ and N2For carrier gas, the test data are detailed in table 6.
TABLE 6 Sulfur resistance Activity of catalyst/% (test temperature 300 ℃ C.)
As can be seen from Table 6, the catalyst of the present invention is in SO2After the catalyst is treated for several hours, the chlorobenzene oxidation activity is hardly influenced, and the catalyst has stronger adaptability to smoke components and is suitable for smoke with various compositions.
The catalyst of comparative example 1 which is not modified by phosphoric acid has poor stability and is easy to lose catalytic activity due to chlorine poisoning and sulfur poisoning.
The above-mentioned embodiments are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.
Claims (7)
1. A method for catalytic oxidative degradation of chlorine-containing volatile organic compounds is characterized by comprising the following steps:
reacting flue gas containing chlorine-containing volatile organic compounds and water vapor under the action of a cerium oxide catalyst;
in the flue gas, the volume fraction of the water vapor is 0.1-5%;
the reaction temperature is 100-300 ℃;
the preparation method of the cerium oxide catalyst comprises the following steps:
(1) soaking cerium oxide in a phosphoric acid solution, filtering the cerium oxide, washing the cerium oxide to be neutral, and drying the cerium oxide;
(2) calcining the dried cerium oxide at 100-400 ℃ for 1-4 hours to obtain a phosphoric acid modified cerium oxide catalyst;
the cerium oxide catalyst contains 0.3-1% of phosphorus in percentage by mass.
2. The method for catalytic oxidative degradation of chlorine-containing volatile organic compounds according to claim 1, wherein in the step (1), the concentration of the phosphoric acid solution is 10-200 g/L, and the molar ratio of cerium oxide to phosphoric acid is 1: 0.05-1.
3. The method for catalytic oxidative degradation of chlorine-containing volatile organic compounds according to claim 1 or 2, wherein in the step (1), the cerium oxide is soaked at 10-80 ℃ for 0.5-3 h.
4. The method for catalytic oxidative degradation of chlorine-containing volatile organic compounds according to claim 1, wherein in the step (2), the calcination temperature is 200-300 ℃.
5. The method for catalytic oxidative degradation of chlorine-containing volatile organic compounds according to claim 4, wherein in the step (2), the calcination time is 1-2 h.
6. The method for catalytic oxidative degradation of chlorine-containing volatile organic compounds according to claim 1, wherein the mass fraction of water vapor in the flue gas is 0.5-2%.
7. The method for catalytic oxidative degradation of chlorine-containing volatile organic compounds according to claim 1, wherein the reaction temperature is 200-300 ℃.
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| CN111001297A (en) * | 2019-12-25 | 2020-04-14 | 浙江大学 | Process and device for degrading chlorine-containing volatile organic compounds in two stages of hydrolysis and oxidation |
| CN111330606A (en) * | 2020-04-14 | 2020-06-26 | 浙江大学 | Catalyst for efficiently degrading chlorine-containing organic waste gas at low temperature and preparation method and application thereof |
| CN113713820A (en) * | 2021-07-31 | 2021-11-30 | 中国计量大学 | Cerium-cobalt-based acid modified catalyst for catalytic oxidation of chlorine-containing volatile organic compounds and preparation method thereof |
| CN114534752A (en) * | 2022-01-25 | 2022-05-27 | 北京工业大学 | Catalyst for catalytic combustion of dichloromethane and toluene mixture and preparation method thereof |
| CN115970722B (en) * | 2023-03-21 | 2023-05-16 | 山东迅达化工集团有限公司 | Low-temperature combustion catalyst with organic chlorine hydrolysis function and application thereof in purification treatment of gas flow containing water vapor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7157071B2 (en) * | 2004-06-30 | 2007-01-02 | Council Of Scientitic And Industrial Research | Process for preparing hydrogen peroxide |
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| Title |
|---|
| "PRODUCTION OF ETHYLENE FROM ETHANOL DEHYDRATION OVER H3PO4-MODIFIED CERIUM OXIDE CATALYSTS";Soo Ling Chong et al.;《Malaysian Journal of Analytical Sciences》;20171231;第839-848页 * |
| Soo Ling Chong et al.."PRODUCTION OF ETHYLENE FROM ETHANOL DEHYDRATION OVER H3PO4-MODIFIED CERIUM OXIDE CATALYSTS".《Malaysian Journal of Analytical Sciences》.2017,第839-848. * |
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| WO2020151577A1 (en) | 2020-07-30 |
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