CN101116822A - Non-uniform combustion catalyst and method for preparing the same - Google Patents
Non-uniform combustion catalyst and method for preparing the same Download PDFInfo
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- CN101116822A CN101116822A CNA2007102015425A CN200710201542A CN101116822A CN 101116822 A CN101116822 A CN 101116822A CN A2007102015425 A CNA2007102015425 A CN A2007102015425A CN 200710201542 A CN200710201542 A CN 200710201542A CN 101116822 A CN101116822 A CN 101116822A
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Abstract
The present invention discloses a non-uniformly distributed combustion catalyst and the preparation method thereof. The present invention belongs to the catalyst field, and in particular relates to the catalytic combustion catalyst product and the production method. The technical problem solved by the present invention is to provide the catalyst product with non-uniformly distributed active components and the preparation method. Another objective of the present invention is to apply the catalyst with non-uniformly distributed active components to the catalytic combustion reaction of methanol, methane and natural gas. The active components of the catalyst consist of one species or a plurality of species in palladium oxide, rhodium oxide, platinum oxide, cobalt oxide, nickel oxide and chromium oxide, and the active components are non-uniformly distributed in the catalyst in an eggshell-shape, of which the content occupies the 0.01-5 percent of the catalyst weight; the weight of an alumina carries occupies 95-99.99 percent. The present invention can decrease the combustion point of fuel, and can make the active component of precious metals utilized with high efficiency.
Description
Technical field
The invention belongs to catalyst field, particularly catalyst for catalytic combustion product and production method thereof.
Background technology
The catalyst great majority of present industrial use belong to loaded catalyst, and its active component mainly adopts noble metal, for example palladium or platinum etc., and its active component almost is to be uniformly distributed in the catalyst.In recent years, the many catalyst with non-uniform distribution of evidence are compared with even catalyst, have better activity, selectivity and longer life-span.
Chinese patent 01133374.X adopts noble metal active component Pt to be distributed in the method for honeycomb ceramic carrier coating outer surface with infusion process by the organic acid competitive Adsorption, and the coating of honeycomb ceramic carrier is formed and is by weight percentage: active A l
2O
320%～80%, TiO
210%～40%, CeO
25%～30%, ZrO
25%～20%, the noble metal loading is that every liter of catalyst contains 0.5～4.0gPt.This invention catalyst can be used for the purified treatment that all kinds contain combustible component waste gas.
Chinese patent 200310119324.9 discloses solid solution catalyst of a kind of methane catalytic combustion and preparation method thereof.This catalyst is cerium oxide, the cobalt oxide solid solution catalyst that adopts the preparation of burning urea method.The catalyst activity component is cerium oxide, cobalt oxide.The catalyst of this invention is used for methane catalytic combustion reaction, is under 49 the condition in air and methane volume ratio, can be at 395～570 ℃ with the complete catalytic combustion of methane.This catalyst has with low cost, and the preparation method is simple, the advantage of easy operating, but that shortcoming is the ignition and the completing combustion temperature of methane is higher.
Chinese patent 86103200 discloses a kind of honeycomb combustion catalyst of non-precious metal, and it is first carrier with silicate material, is second carrier with coating of metal oxides, is catalytic active component with the mixture of metal oxide and rare-earth oxide.This invention earlier a kind of carrier impregnation in applying liquid, carry out drying and roasting then, said dipping, drying and roasting need carry out twice, form second carrier after dipping, drying and the roasting for the first time, adhere to catalytic active component after dipping, drying and the roasting for the second time.
Chinese patent CN1736604A discloses a kind of egg shell type metal catalyst and its production and application.This catalyst is to be the eggshell type metal supported catalyst of carrier with the hollow silicon dioxide, and described hollow silicon dioxide carrier is the mesoporous material with certain wall thickness and certain pore size.With catalyst weight percentage is benchmark, and its composition is 0.1%～5.0% noble metal and/or 5.0%～40.0% transition metal, 0～0.5% base metal co-catalyst, 60.0%～99.0% hollow silicon dioxide carrier.Adopt infusion process or original position load method to be prepared into egg shell type metal catalyst.This catalyst has the good metal dispersiveness, and the particle diameter of metallic particles is less, is dispersed in outer surface, inner surface and the duct of hollow silicon dioxide carrier, effectively reduces the catalyst cost, has favorable industrial application prospect.Such egg shell type metal catalyst can be used for catalysis CO, CO
2Hydrogenation preparing lower carbon number hydrocarbons and alcohol can also be used for reactions such as selective hydrogenations such as alkene, alkynes and saturated hydrogenation.
For with γ-Al
2O
3Be carrier, support active component non-uniform Distribution in noble metal and the catalyst, be used for the catalyst that methyl alcohol and combustion of natural gas use and yet there are no report.
Summary of the invention:
The technical problem that the present invention solves provides catalyst prod of active component non-uniform Distribution and preparation method thereof.
Another object of the present invention is that the catalyst with prepared active component non-uniform Distribution is applied in the catalyst combustion reaction of methyl alcohol, methane, natural gas etc.
A kind of catalyst that is used for catalytic combustion of active component non-uniform Distribution, wherein one or more form the catalyst activity component by palladium oxide, rhodium oxide, platinum oxide, cobalt oxide, nickel oxide, chromium oxide, and active component is the eggshell type non-uniform Distribution in catalyst, its content accounts for 0.01%～5% of catalyst weight, and the weight of alumina support is 95%～99.99%;
Catalyst provided by the present invention, this Preparation of catalysts method is: with a kind of metal active constituent or several metal active constituent with the metal salt solution form by precipitating reagent method, pre-preg competitive Adsorption method, flood competitive Adsorption method or colloid method altogether active component supported in γ-Al
2O
3On the carrier, make catalyst prod by dry, roasting.
Catalyst of the present invention is with γ-Al
2O
3Be carrier, metal oxide is an active component, and active component is eggshell type and distributes in catalyst.γ-Al
2O
3Diameter is between 1-4mm.
Catalyst provided by the present invention is by the metal oxide component that accounts for catalyst weight 0.01%～5% with to account for catalyst weight be that 95%～99.99% alumina support is formed.
(1) precipitating reagent method
(1) one or more metal salt solution and alkaline solution of preparation palladium, rhodium, platinum, cobalt, nickel, chromium;
(2) a certain amount of alumina globule be impregnated in the above-mentioned alkaline solution after oven dry, dip time is 1-3h;
(3) alumina globule after will flooding is put into oven for drying;
(4) alumina globule after will drying impregnated in above-mentioned one or more metal salt solutions, and dip time is 10-60min;
(5) alumina globule after will flooding is put into the Muffle furnace roasting.
(2) pre-preg competitive Adsorption method
(1) one or more metal salt solution and oxalic acid solution of preparation palladium, rhodium, platinum, cobalt, nickel, chromium;
(2) alumina globule after a certain amount of oven dry be impregnated in the above-mentioned oxalic acid solution, dip time is 5-20min;
(3) alumina globule after will flooding places 100-180 ℃ of baking oven to dry 5-40min;
(4) alumina globule after will drying impregnated in the mixed liquor of above-mentioned a kind of metal salt solution or several metal salt solutions, and dip time is 5-20min;
(5) alumina globule after will flooding places baking oven dry;
(6) dried alumina globule is placed the Muffle furnace roasting that heats up.
(3) flood the competitive Adsorption method altogether
(1) one or more metal salt solution and citric acid solution of preparation palladium, rhodium, platinum, cobalt, nickel, chromium;
(2) two or more metal salt solutions are mixed;
(3) alumina globule after a certain amount of oven dry be impregnated in the above-mentioned solution, dip time is 10-30min;
(4) alumina globule after will flooding is put into the Muffle furnace roasting that heats up.
(4) colloid method
(1) one or more metal salt solution and alkaline solution of preparation palladium, rhodium, platinum, cobalt, nickel, chromium;
(2) in metal salt solution, add the Arabic gum of 0.8%-8%, and mix;
(3) regulate above-mentioned pH value of solution value to 7～8 with alkaline solution;
(4) above-mentioned solution is boiled under condition of stirring, be burgundy to liquid till;
(5) alumina globule after a certain amount of oven dry be impregnated in above-mentioned one or more the metal salt colloid, dip time is 10-50min;
(6) bead behind the above-mentioned dipping is placed baking oven dry;
(7) dried bead is placed Muffle furnace, through the intensification roasting.
Catalyst provided by the present invention is characterized in that in this Preparation of catalysts process, and the baking temperature after the dipping active component is 60 ℃～180 ℃, and time 2-6 hour, baking temperature can be selected 80 ℃～120 ℃; Sintering temperature is 200 ℃～1000 ℃, preferred 500 ℃～800 ℃, and roasting 2-5h.
Catalyst prod provided by the invention is in dipping process, and the pH value of maceration extract is controlled between 5～7.
Catalyst provided by the present invention adopting colloid method and precipitating reagent legal system to be equipped with that employed precipitating reagent is an alkaline solution in the process of catalyst, comprises Na
2CO
3, NaHCO
3, ammoniacal liquor, NaOH, KOH or other alkaline solutions, the concentration of alkaline solution is 0.05～5mol/L.
Catalyst provided by the present invention is a precious metal salt solution in this catalyst employed active component in preparation process, refer to palladium, rhodium, platinum, cobalt, nickel, chromium etc. wherein one or more hydrochloric acid be that solution or nitric acid are that solution or sulfuric acid are solution, RhCl for example
3, PdCl
2, chromic nitrate, cobaltous sulfate, and chloroplatinic acid (H
2PtCl
6.6H
2O) solution, and solution concentration is 0.005mol/～3mol/L.
Activated alumina is γ-Al among the present invention
2O
3Bead.
Beneficial effect
Use the evaluation result of this catalyst to show: the firing point comparison of gas is according to reducing 60-90 ℃, and the conversion ratio of gas is 60-80%.The present invention can reduce the firing point of fuel, and the noble metal active component is efficiently utilized.
The specific embodiment
For the present invention is described better, further specify the present invention below in conjunction with embodiment and Comparative Examples, but scope of the present invention is not limited only to these embodiment.
Used part material is as follows in the example of the present invention: spherical γ-Al
2O
3, oxalic acid, citric acid, maleic acid, NaOH, palladium bichloride, oxyammonia platinum, hydrochloric acid, Na
2CO
3, NaHCO
3, ammoniacal liquor, chromic nitrate, cobaltous sulfate, deionized water.
Embodiment 1
Preparation rhodium sulfate, platinum nitrate, cobalt chloride, nickel nitrate, chromium sulfate solution, concentration is 0.02mol/L solution, prepares the Na of 0.1mol/L simultaneously
2CO
3Solution impregnated in Na with the alumina globule after the oven dry
2CO
3In the solution, dip time is 60 minutes, with the alumina globule behind the above-mentioned dipping in baking oven 160 ℃ dry 5 minutes down; With the γ-Al after the oven dry
2O
3Bead impregnated in the metal salt solution of above-mentioned equal-volume mixing, and dip time is 10 minutes, and controlling the pH value of solution value with hydrochloric acid and NaOH in the dipping process is 7; Alumina globule behind the dipping is taken out through 80 ℃ of dry 4h; With dried γ-A1
2O
3500 ℃ of roasting 4h of bead make catalyst.Metal oxide weight accounts for 5% in the catalyst.
Embodiment 2
Radium chloride is made into the solution that concentration is 3mol/L; Prepare the Na of 1mol/L simultaneously
2CO
3Solution impregnated in NaHCO with the alumina globule after the oven dry
3In the solution, dip time is 80 minutes, with the alumina globule behind the above-mentioned dipping in baking oven 120 ℃ dry 5 minutes down; Alumina globule after the oven dry be impregnated in the metal salt solution of above-mentioned equal-volume mixing, dip time is 20 minutes, and controlling the pH value of solution value with hydrochloric acid and NaOH in the dipping process is 6; Alumina globule behind the dipping is taken out through 100 ℃ of dry 4h; 600 ℃ of roasting 3h make catalyst with dried alumina globule.Metal oxide weight accounts for 2% in the catalyst.
Embodiment 3
It is 0.005mol/L solution that nickel chloride is made into concentration, and chromic nitrate, cobaltous sulfate are made into the solution of 0.1mol/L, and three kinds of solution arbitrarily than mixing, are prepared the Na of 1.2mol/L simultaneously
2CO
3Solution impregnated in Na with the alumina globule after the oven dry
2CO
3In the solution, dip time is 80 minutes, with the alumina globule behind the above-mentioned dipping in baking oven 100 ℃ dry 5 minutes down; Alumina globule after the oven dry be impregnated in the metal salt solution of above-mentioned mixing, and dip time is 20 minutes, and controlling the pH value of solution value with hydrochloric acid and NaOH in the dipping process is 6; Alumina globule behind the dipping is taken out through 100 ℃ of dry 4h; 600 ℃ of roasting 3h make catalyst with dried alumina globule.Metal oxide weight accounts for 1% in the catalyst.
Claims (9)
1. non-uniform combustion catalyst, carrier is an aluminium oxide, it is characterized in that wherein one or more form active component by palladium oxide, rhodium oxide, platinum oxide, cobalt oxide, nickel oxide, chromium oxide.
2. non-uniform combustion catalyst according to claim 1 is characterized in that described catalyst activity constituent content accounts for 0.01%～5% of catalyst weight.
3. non-uniform combustion catalyst according to claim 1 and 2 is characterized in that described catalyst activity constituent content accounts for 0.1%～3% of catalyst weight.
4. a method for preparing catalyst according to claim 1 comprises the steps: one or more the salting liquid of metal of (1) preparation palladium, rhodium, platinum, cobalt, nickel, chromium; (2) a certain amount of alumina globule be impregnated in the alkaline solution after oven dry, dip time is 1-3h; (3) alumina globule after will flooding is put into oven for drying; (4) alumina globule after will drying impregnated in above-mentioned one or more mixed salt solutions, and dip time is 10-60min; (5) alumina globule after will flooding is put into the Muffle furnace roasting.
5. method for preparing catalyst according to claim 4 is characterized in that described metal salt solution is meant wherein one or more hydrochloric acid solution, salpeter solution or sulfuric acid solution of palladium, rhodium, platinum, cobalt, nickel, chromium.
6. method for preparing catalyst according to claim 4 is characterized in that the baking temperature after the described dipping active component is 60 ℃～180 ℃, time 2-6 hour; Sintering temperature is 200 ℃～1000 ℃, roasting time 2-5h.
7. method for preparing catalyst according to claim 4, the pH value that it is characterized in that described metal salt solution is 5～7.
8. method for preparing catalyst according to claim 4 is characterized in that described alkaline solution is a sodium carbonate, sodium acid carbonate, and ammoniacal liquor, NaOH, potassium hydroxide, the concentration of alkaline solution is 0.05～5mol/L.
9. method for preparing catalyst according to claim 4 is characterized in that described metal salt solution is RhCl
3, PdCl
2, chromic nitrate, cobaltous sulfate and chloroplatinic acid (H
2PtCl
6.6H
2O) solution, solution concentration are 0.005mol/L～3mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007102015425A CN101116822A (en) | 2007-08-30 | 2007-08-30 | Non-uniform combustion catalyst and method for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007102015425A CN101116822A (en) | 2007-08-30 | 2007-08-30 | Non-uniform combustion catalyst and method for preparing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101116822A true CN101116822A (en) | 2008-02-06 |
Family
ID=39053171
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007102015425A Pending CN101116822A (en) | 2007-08-30 | 2007-08-30 | Non-uniform combustion catalyst and method for preparing the same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890351B (en) * | 2009-05-21 | 2012-10-24 | 中国石油化工股份有限公司 | Eggshell type nickel-based catalyst |
| CN103510978A (en) * | 2013-10-23 | 2014-01-15 | 山东理工大学 | Combined oxidation bed for coal mine ventilation air preheating catalytic oxidation device |
| CN103769085A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of catalyst for catalytic combustion |
| CN111054389A (en) * | 2019-11-25 | 2020-04-24 | 李俊鸿 | Methanol low-temperature heating catalyst and preparation method thereof |
| CN114210340A (en) * | 2021-12-21 | 2022-03-22 | 商丘国龙新材料有限公司 | High-activity gas-phase synthesis dimethyl carbonate catalyst and preparation method and application thereof |
| CN114210325A (en) * | 2021-12-21 | 2022-03-22 | 商丘国龙新材料有限公司 | Catalyst for synthesizing dimethyl oxalate by gas-phase carbonylation and preparation method and application thereof |
-
2007
- 2007-08-30 CN CNA2007102015425A patent/CN101116822A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890351B (en) * | 2009-05-21 | 2012-10-24 | 中国石油化工股份有限公司 | Eggshell type nickel-based catalyst |
| CN103769085A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of catalyst for catalytic combustion |
| CN103510978A (en) * | 2013-10-23 | 2014-01-15 | 山东理工大学 | Combined oxidation bed for coal mine ventilation air preheating catalytic oxidation device |
| CN111054389A (en) * | 2019-11-25 | 2020-04-24 | 李俊鸿 | Methanol low-temperature heating catalyst and preparation method thereof |
| CN111054389B (en) * | 2019-11-25 | 2023-06-30 | 李俊鸿 | Methanol low-temperature heating catalyst and preparation method thereof |
| CN114210340A (en) * | 2021-12-21 | 2022-03-22 | 商丘国龙新材料有限公司 | High-activity gas-phase synthesis dimethyl carbonate catalyst and preparation method and application thereof |
| CN114210325A (en) * | 2021-12-21 | 2022-03-22 | 商丘国龙新材料有限公司 | Catalyst for synthesizing dimethyl oxalate by gas-phase carbonylation and preparation method and application thereof |
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