CN114345360A - With CeO2Method for preparing catalyst for carrier and loading transition metal oxide - Google Patents
With CeO2Method for preparing catalyst for carrier and loading transition metal oxide Download PDFInfo
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- CN114345360A CN114345360A CN202210050546.2A CN202210050546A CN114345360A CN 114345360 A CN114345360 A CN 114345360A CN 202210050546 A CN202210050546 A CN 202210050546A CN 114345360 A CN114345360 A CN 114345360A
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- metal oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 21
- 238000011068 loading method Methods 0.000 title abstract description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 36
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 17
- 238000007873 sieving Methods 0.000 claims description 15
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 92
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000032683 aging Effects 0.000 abstract description 3
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 239000003345 natural gas Substances 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000007084 catalytic combustion reaction Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- REHUGJYJIZPQAV-UHFFFAOYSA-N formaldehyde;methanol Chemical compound OC.O=C REHUGJYJIZPQAV-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/003—Additives for gaseous fuels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
- C10L2230/04—Catalyst added to fuel stream to improve a reaction
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- Combustion & Propulsion (AREA)
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Abstract
The invention relates to a CeO2A method for preparing a catalyst which is a carrier and supports a transition metal oxide. The catalyst is prepared by taking cerium oxide as a carrier and loading a transition metal oxide, and has the advantages of high catalytic activity on methane, high temperature resistance, strong aging resistance, water resistance and good poisoning resistanceThe efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst prepared from CeO2A method for preparing a catalyst which is a carrier and supports a transition metal oxide.
Background
With the development of economic society, energy shortage, environmental deterioration and the like become more and more serious, and people pay more and more attention. Methane is clean energy with abundant reserves and low price, the catalytic combustion of methane has the characteristics of high energy utilization rate and low pollution discharge, and the key point is the preparation of a catalyst with high activity and high stability.
Natural gas is one of three traditional fossil energy sources, and accounts for about 23% of the global energy consumption. Main of natural gasThe essential component is methane, which accounts for more than 95 percent. Natural gas has the highest hydrogen to carbon ratio and therefore the highest calorific value compared to other fuels, and is the highest calorific energy source among natural biological and fossil fuels (as shown in table 1). In addition, ash, CO, C0 from the combustion of natural gas2And SO. The indexes are far lower than coal and petroleum, the emission of carbon dioxide in the combustion process is low, and the contribution degree of the emitted carbon dioxide to the greenhouse effect is only 54 percent of that of the petroleum and 48 percent of that of the coal. Thus, natural gas is considered a clean, hydrogen-rich energy source, and is the preferred fuel in many countries.
TABLE 1
| Item | Wood material | Coal (coal) | Petroleum products | Natural gas |
| Total heat value/(KJ/kg) | 6300～8400 | 21000～30000 | 42000～46000 | 55000 |
| H/C (atomic ratio) | 1:10 | 1:1 | 2:1 | 4:1 |
The main component of natural gas is methane, so the utilization of natural gas is the utilization technology of methane. The most common utilization of methane is direct flame combustion, but the direct flame combustion requires a higher temperature, low energy utilization, and high temperature N2Will be mixed with O2Generating polluting gases such as NO. Therefore, as people continuously explore other utilization ways of methane, with the increasing attention and importance of people on the problems of energy shortage and environmental pollution, natural gas which is rich in reserves, low in price and considered as one of clean energy is currently concerned. The main component of natural gas is methane, if the natural gas is directly burnt by flame, high temperature can be generated, the energy utilization rate is low, and a large amount of harmful substances such as NOx, CO and the like can be generated to pollute the environment. In addition, methane gas can become thin when methane directly burns to a certain degree and thus can't continue direct combustion, causes very big partial waste, if directly discharge these methane that do not burn out in the atmosphere, the methane gas that the greenhouse effect is extremely strong can cause the influence to the environment again.
Currently, the main ways of using methane are: preparing C2 compound by methane coupling, preparing aromatic hydrocarbon by methane chlorination or ammoniation, preparing methanol (formaldehyde) by methane oxidation, preparing synthesis gas by methane reforming or partial oxidation and methane catalytic combustion. These applications can generally convert methane into a product with higher added value, thereby bringing about great economic, environmental and social benefits. Methane is an extremely stable compound, being the shortest carbon chain organic and having a tetrahedral configuration of carbon-oxygen bonds, and its activation usually requires very high temperatures. Furthermore, thermodynamic limitations prevent the use of methane, since some of the intermediates formed by the conversion of methane are unstable and tend to form Nitrogen Oxides (NO) at high temperaturesX) CO and other by-products and incomplete combustion utilization. Therefore, the key to methane utilization is methane activation, wherein methane catalytic combustion is a relatively common methane activation mode. The key point of catalytic combustion of methane is the catalyst, because the methane molecule is stable and difficult to activate, so a proper catalyst is designed and preparedThe efficiency of the catalytic combustion of methane can be improved. There are various catalysts for catalytic combustion of methane, and they are classified into noble metal catalysts and metal oxide catalysts according to the difference in active components.
At present, methane combustion catalysts used in methane catalytic combustion at home and abroad have many problems to be solved urgently, such as high activity, high price and poor thermal stability of the traditional noble metal catalyst; the transition metal oxide catalyst is low in cost, good in stability, but poor in activity. The noble metal catalyst is mainly Pd, Rh and the like, wherein the Pd catalyst has the best activity and is most researched and applied. Noble metals generally have high activity, but are poor in stability (service life), expensive in price, poor in sulfur toxicity resistance, relatively poor in thermal stability and easy to inactivate at high temperature, so that the application range of the noble metals is limited to a certain extent and is only applied to low-temperature heating devices such as household gas stoves, gas water heaters and the like and the environment.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides CeO2The catalyst prepared by the method has the advantages of high catalytic activity on methane, high temperature resistance, strong ageing resistance, water resistance and good poisoning resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
with CeO2A method for preparing a catalyst which is a carrier and supports a transition metal oxide, comprising the steps of:
(1) treating cerous nitrate hexahydrate at high temperature to obtain cerium oxide, tabletting, crushing and sieving to obtain 40-60 mesh cerium oxide for later use;
(2) adding a proper amount of deionized water into nitrate of transition metal and barium nitrate, and uniformly mixing to form a solution A;
(3) adding the spare cerium oxide into the solution A, uniformly stirring, drying, roasting, tabletting, crushing and sieving to obtain a 40-60-mesh sample A;
(4) and adding the sample A into a lanthanum nitrate solution, uniformly stirring, drying, roasting, tabletting, crushing, and sieving by a 40-60-mesh sieve to obtain the catalyst.
The cerium oxide is used as a carrier in the invention, because the cerium oxide not only can improve the performance of the catalyst, but also has high oxygen storage and release performance, the catalyst can work under rich-fuel and lean-fuel oxygen-rich conditions, and the catalytic efficiency is greatly improved.
The catalyst prepared by the invention well solves the main factors influencing the activity and the thermal stability of the catalyst, and is a methane combustion catalyst with high activity, high stability, water resistance and toxicity resistance.
The purity of the cerous nitrate hexahydrate in the invention is more than 99.9%, and the purity of the transition metal nitrate is more than 99.9%.
Further, the transition metal is one of copper, zinc, iron, cobalt and nickel.
Further, the high-temperature treatment of the cerous nitrate hexahydrate in the step (1) is specifically to raise the temperature from room temperature to 500-600 ℃ by a program and keep the temperature for 5.5-6.5 h.
Furthermore, the rate of temperature programming is 1.5-2.5 ℃/min.
Further, in the step (2), the mass of the transition metal nitrate is 0.8-1.2% of the mass of the cerium oxide, and the mass of the barium nitrate is 5-9% of the mass of the cerium oxide.
Further, in the step (3), the drying temperature is 90-110 ℃, the roasting temperature is 500-600 ℃, and the roasting time is 5.5-6.5 h.
Further, in the step (3), the drying temperature is 100 ℃, the roasting temperature is 550 ℃, and the roasting time is 6 hours.
Furthermore, the roasting temperature rise rate is 1.5-2.5 ℃/min.
Further, the heating rate of the roasting is 2 ℃/min.
Further, in the step (4), the drying temperature is 90-110 ℃, the roasting temperature is 500-600 ℃, and the roasting time is 5.5-6.5 h.
Further, in the step (4), the drying temperature is 100 ℃, the roasting temperature is 550 ℃, and the roasting time is 6 hours.
Further, the mass of lanthanum nitrate is 2-4% of the mass of cerium oxide.
The lanthanum nitrate solution is prepared by dissolving lanthanum nitrate in a proper amount of water to form a uniform solution, and the nitrate of the transition metal and the barium nitrate are added with a proper amount of water to form a uniform solution.
Furthermore, the roasting temperature rise rate is 1.5-2.5 ℃/min.
Compared with the prior art, the invention has the beneficial effects that:
the catalyst is prepared by taking cerium oxide as a carrier and loading a transition metal oxide, and has the advantages of high catalytic activity on methane, high temperature resistance, strong aging resistance, water resistance and good poisoning resistance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
This example uses CeO2A method for preparing a catalyst which is a carrier and supports a transition metal oxide, comprising the steps of:
(1) carrying out high-temperature treatment on cerium nitrate hexahydrate with the purity of more than 99.9%, wherein the high-temperature treatment is specifically to carry out temperature programming from room temperature to 350 ℃, and keep the temperature for 6.5 hours, the temperature programming rate is 1.5 ℃/min, so as to obtain cerium oxide, tabletting, crushing, and sieving so as to obtain 40-60-mesh cerium oxide for later use;
(2) adding a proper amount of deionized water into nickel nitrate and barium nitrate with the purity of more than 99.9 percent, and uniformly mixing to form a solution A, wherein the mass of the nickel nitrate is 0.8 percent of that of the cerium oxide, and the mass of the barium nitrate is 5 percent of that of the cerium oxide;
(3) adding the spare cerium oxide into the solution A, uniformly stirring, drying at 90 ℃, placing the dried substance into a muffle furnace for roasting, tabletting, crushing and sieving to obtain a 40-60-mesh sample A under the air atmosphere, wherein the heating rate is 1.5 ℃/min, the roasting temperature is 500 ℃, and the roasting time is 6.5 h;
(4) adding the sample A into a lanthanum nitrate solution, uniformly stirring, drying at 90 ℃ until the mass of lanthanum nitrate is 2% of that of cerium oxide, placing the dried substance into a muffle furnace for roasting, wherein the heating rate is 1.5 ℃/min, the roasting temperature is 500 ℃, the roasting time is 6.5h, tabletting, crushing, and sieving by a 40-60-mesh sieve to obtain the catalyst.
Example 2
This example uses CeO2A method for preparing a catalyst which is a carrier and supports a transition metal oxide, comprising the steps of:
(1) carrying out high-temperature treatment on cerium nitrate hexahydrate with the purity of more than 99.9%, wherein the high-temperature treatment is specifically to carry out temperature programming from room temperature to 425 ℃ and keep the temperature for 6 hours, the temperature programming rate is 2 ℃/min, obtaining cerium oxide, tabletting, crushing and sieving to obtain 40-60-mesh cerium oxide for later use;
(2) adding a proper amount of deionized water into copper nitrate and barium nitrate with the purity of more than 99.9%, and uniformly mixing to form a solution A, wherein the mass of nickel nitrate is 1% of that of cerium oxide, and the mass of barium nitrate is 7% of that of cerium oxide;
(3) adding the spare cerium oxide into the solution A, uniformly stirring, drying at 100 ℃, placing the dried substance into a muffle furnace for roasting, in the air atmosphere, heating at the rate of 2 ℃/min, at the roasting temperature of 550 ℃, for 6 hours, tabletting, crushing and sieving to obtain a 40-60 mesh sample A;
(4) adding the sample A into a lanthanum nitrate solution, uniformly stirring, drying at 90 ℃ until the mass of lanthanum nitrate is 3% of that of cerium oxide, roasting the dried substance in a muffle furnace at the temperature rise rate of 1.5 ℃/min and the roasting temperature of 500 ℃ for 6.5h in the air atmosphere, tabletting, crushing, and sieving by a 40-60-mesh sieve to obtain the catalyst.
Example 3
This example uses CeO2A method for preparing a catalyst which is a carrier and supports a transition metal oxide, comprising the steps of:
(1) carrying out high-temperature treatment on cerium nitrate hexahydrate with the purity of more than 99.9%, wherein the high-temperature treatment is specifically to heat the temperature from room temperature to 500 ℃ by a program and keep the temperature for 5.5 hours, the temperature programming rate is 2.5 ℃/min, obtaining cerium oxide, tabletting, crushing and sieving to obtain 40-60-mesh cerium oxide for later use;
(2) adding a proper amount of deionized water into zinc nitrate and barium nitrate with the purity of more than 99.9 percent, and uniformly mixing to form a solution A, wherein the mass of nickel nitrate is 1.2 percent of that of cerium oxide, and the mass of barium nitrate is 9 percent of that of cerium oxide;
(3) adding the spare cerium oxide into the solution A, uniformly stirring, drying at 110 ℃, placing the dried substance into a muffle furnace for roasting, wherein the heating rate is 2.5 ℃/min under the air atmosphere, the roasting temperature is 600 ℃, the roasting time is 5.5h, tabletting, crushing and sieving to obtain a sample A with 40-60 meshes;
(4) adding the sample A into a lanthanum nitrate solution, uniformly stirring, drying at 110 ℃, placing the dried substance into a muffle furnace for roasting, wherein the lanthanum nitrate is 4% of the cerium oxide by mass, the heating rate is 2.5 ℃/min, the roasting temperature is 600 ℃, the roasting time is 5.5h, tabletting, crushing, and sieving by a 40-60-mesh sieve to obtain the catalyst.
Test example 1 investigation of different calcination temperatures on the texture Properties of the catalyst and on the catalytic Activity for methane Combustion
A catalyst was prepared in the same manner as in example 2 except that the calcination temperature was changed in steps (3) and (4) in example 2, and the results of the performance test were shown in Table 2.
TABLE 2
Wherein a crystal grain size is calculated according to the scherrar formula (calculated as the (111) crystal plane of cerium oxide), and b crystal grain size is calculated according to the scherrar formula (calculated as the (200) crystal plane of cerium oxide).
As can be seen from Table 2, the catalyst has the largest specific surface area and the best catalytic activity at a calcination temperature of 550 ℃ in the invention.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. With CeO2A method for preparing a catalyst which is a carrier and supports a transition metal oxide, characterized by comprising the steps of:
(1) treating cerous nitrate hexahydrate at high temperature to obtain cerium oxide, tabletting, crushing and sieving to obtain 40-60 mesh cerium oxide for later use;
(2) adding a proper amount of deionized water into nitrate of transition metal and barium nitrate, and uniformly mixing to form a solution A;
(3) adding the spare cerium oxide into the solution A, uniformly stirring, drying, roasting, tabletting, crushing and sieving to obtain a 40-60-mesh sample A;
(4) and adding the sample A into a lanthanum nitrate solution, uniformly stirring, drying, roasting, tabletting, crushing, and sieving by a 40-60-mesh sieve to obtain the catalyst.
2. CeO according to claim 12The preparation method of the catalyst which is used as a carrier and is loaded with transition metal oxide is characterized in that the transition metal is one of copper, zinc, iron, cobalt and nickel.
3. CeO according to claim 12The preparation method of the catalyst which is used as a carrier and is loaded with transition metal oxide is characterized in that in the step (1), cerous nitrate hexahydrate has high temperatureThe treatment is specifically programmed from room temperature to 350-500 ℃ and kept for 5.5-6.5 h.
4. CeO according to claim 32A process for preparing a catalyst carrying transition metal oxide, characterized in that the rate of temperature programming is 1.5-2.5 ℃/min.
5. CeO according to claim 12The preparation method of the catalyst which is used as the carrier and is loaded with the transition metal oxide is characterized in that in the step (2), the mass of the transition metal nitrate is 0.8-1.2% of the mass of the cerium oxide, and the mass of the barium nitrate is 5-9% of the mass of the cerium oxide.
6. CeO according to claim 12The preparation method of the catalyst which is used as the carrier and is loaded with the transition metal oxide is characterized in that the drying temperature in the step (3) is 90-110 ℃, the roasting temperature is 500-600 ℃, and the roasting time is 5.5-6.5 h.
7. CeO according to claim 62The preparation method of the catalyst which is a carrier and loads transition metal oxide is characterized in that the roasting temperature rise rate is 1.5-2.5 ℃/min.
8. CeO according to claim 12The preparation method of the catalyst used as the carrier and loaded with the transition metal oxide is characterized in that the drying temperature in the step (4) is 90-110 ℃, the roasting temperature is 500-600 ℃, the roasting time is 5.5-6.5h, and preferably, the lanthanum nitrate accounts for 2-4% of the cerium oxide by mass.
9. CeO according to claim 82The preparation method of the catalyst which is a carrier and loads transition metal oxide is characterized in that the drying temperature in the step (4) is 100 ℃, the roasting temperature is 550 ℃, and the roasting time is 6 h.
10. Root of herbaceous plantA CeO according to claim 8 or 92The preparation method of the catalyst which is a carrier and loads transition metal oxide is characterized in that the roasting temperature rise rate is 1.5-2.5 ℃/min.
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