CN102626640B - Monolithic catalyst for low temperature oxidation of methane and preparation thereof - Google Patents
Monolithic catalyst for low temperature oxidation of methane and preparation thereof Download PDFInfo
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- CN102626640B CN102626640B CN2012100803754A CN201210080375A CN102626640B CN 102626640 B CN102626640 B CN 102626640B CN 2012100803754 A CN2012100803754 A CN 2012100803754A CN 201210080375 A CN201210080375 A CN 201210080375A CN 102626640 B CN102626640 B CN 102626640B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 title abstract description 31
- 230000003647 oxidation Effects 0.000 title abstract description 11
- 239000011651 chromium Substances 0.000 claims abstract description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000919 ceramic Substances 0.000 claims abstract description 16
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 16
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical group [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- 229910000684 Cobalt-chrome Inorganic materials 0.000 claims abstract description 9
- 239000010952 cobalt-chrome Substances 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 239000006255 coating slurry Substances 0.000 claims abstract description 4
- 238000007598 dipping method Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- 239000010970 precious metal Substances 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910001430 chromium ion Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 16
- 239000003345 natural gas Substances 0.000 abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 230000010718 Oxidation Activity Effects 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000011572 manganese Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000009938 salting Methods 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- -1 methane hydro carbons Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910002555 FeNi Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
A monolithic catalyst for low temperature oxidation of methane comprises cordierite honeycomb ceramic carrier and a coating thereon. The coating has an expression of Pd / CoxCry-M / Al2O3, wherein Pd is noble metal palladium; CoxCry is cobalt chromium compound oxide, and a molar ratio of cobalt to chromium is between 0.001-100; M represents one or more doped metal selected from cerium, zirconium, iron, lanthanum, nickel and manganese, and a dopping amount (molar ratio) of M to (Co+Cr+M) is less than 0.10; and Al2O3 is gamma-Al2O3 with high thermal stability. The preparation method includes the following steps: step one, preparing the composite metal oxide CoxCry-M; step two, preparing the coating slurry; step three, dipping; step four, drying and calcining to obtain the monolithic catalyst. The catalyst of the invention can be used in methane purification of natural gas and vehicle tail gas and has good methane oxidation activity and thermal stability.
Description
Technical field
The invention belongs to the environment-friendly engineering technical field, relate to the processing of methane in natural gas and auto tail gas, particularly a kind of integral catalyzer and preparation thereof for the reaction of methane low-temperature oxidation.
Background technology
The demand of environment and energy security aspect is just promoting gas combustion automobile (NGVs) and is worldwide developing rapidly.Data according to international gas combustion automobile association show, calendar year 2001 so far in world wide combustion gas automobile pollution average growth rate per annum reach 24%, and expect the year two thousand twenty and reach 6,500 ten thousand.China's 16 cleaning vehicle emphasis Model Cities (area) gas-fueled vehicles (CNG and LNG) recoverable amount was over 600,000 in 2010.
Along with gas-fueled vehicles developing rapidly worldwide, the environmental problem that gas-fueled vehicles produce also causes people's concern gradually, and this is mainly the methane of its exhaust emissions.In natural gas and auto tail gas HC, being unburned methane more than 80%, is the hydro carbons of C1～C4 more than 95% in remaining non-methane hydro carbons (NMHC); And in tail-gas from gasoline automobiles, methane only accounts for 5～8%, main component is the hydrocarbon of C4～C8; The methane of natural gas vehicle exhaust emissions increases, and discharge rate is 10 times of gasoline car; And methane is the most difficult oxidized hydro carbons, so the natural gas vehicle tai-gas clean-up catalyst must have higher transformation efficiency to methane.
At present, the main active of catalytic cleaner is the noble metals such as Pt, Pd and Rh, and noble metal is that wherein Pd will be far above other metallic catalysts to the clean-up effect of methane especially.Yet because noble metal is expensive, resource-constrained, greatly restricted cost and the large-scale application of catalyst.Therefore, reduce the consumption of noble metal, even develop non-precious metal catalyst is study hotspot both domestic and external always.It is generally acknowledged, the transition metals such as Co, Cr, Mn, Cu, Ni all have higher methane oxidation ability, all can think the active component of potential methane oxidation.
(the Studies in Surface Science and Catalysis such as J.R.Paredes, 2002,144,427) a kind of Co-Cr spinel oxide prepared by coprecipitation is disclosed, this oxide is used for to methane oxidation, found that it has extraordinary catalytic performance to methane oxidation, and have good sulfur resistance.
Doping can change catalyst character in a certain respect, and such as activity, stability, anti-poisoning capability etc. is a kind of important research means in catalyst formulation research.The present inventor had once reported the Co-Cr bi-metal oxide catalyst of the cerium doping prepared by coprecipitation, and found that appropriate cerium doping has effectively improved Catalytic methane oxidation active (Catal.Today, 2011,175,216).Yet above-mentioned research all is based on metal oxide, and the specific area less of oxide, this has just limited its application in practice.Metal oxide supported, on certain carrier, can overcome above-mentioned shortcoming.
Russian Patent SU410806-A (1974) discloses a kind of SiO for combustion of methane
2The Cr-Co bimetallic catalyst supported, change Cr in catalyst
2O
3, Co
3O
4The mass ratio shared with carrier is respectively: 35～42,20～23 and 35～45.Work as Cr
2O
3And Co
3O
4Mass ratio when 0.3～1.8-2.2, can improve activity and the stability of catalyst.
D.Fino etc. (Catal.Today, 2006,117,559) have prepared CoCr with urea combustion (SCS)
2O
4Integral catalyzer, purify the material of preparation for CNG tail gas methane.Its preparation process is as follows: first with the synthetic γ-Al of urea combustion original position on honeycomb ceramic carrier
2O
3, synthetic CoCr on above-mentioned carrier then uses the same method
2O
4, then use infusion process carried noble metal Pd, γ-Al
2O
3, CoCr
2O
4With the Pd mass ratio be 100: 15: 1, after Overheating Treatment, make the CNG vehicle tai-gas clean-up catalyst.Although urea combustion is easy and simple to handle, without roasting, there is potential explosion danger in this reaction, and can discharge NO in course of reaction
xDeng pernicious gas.
Chinese patent CN102039146A discloses a kind of for natural gas engine exhaust gas purification catalyst and preparation method thereof, this catalyst by carrier, be coated in the coating on carrier and the catalytic active component that loads on coating forms.The active component of this catalyst comprises compound transition metal oxide MnO
x-MO
x(M=Co, Sn, Fe), CoO
x-MO
x(Mn, Sn, Fe), SnO
x-MO
x(Mn, Co, Fe), FeO
x-MO
xA kind of in (M=Mn, Co, Sn) or one or more, or transition metal-complex rare-earth oxidate containing valuable metal M-Ce (M=Mn, Co, Ni, Fe, Sn, Cu).。
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of integral catalyzer and preparation thereof for the reaction of methane low-temperature oxidation, it can be used for the catalytic purification of natural gas and auto tail gas methane, and has higher stability.
To achieve these goals, the technical solution used in the present invention is:
A kind of integral catalyzer for methane low-temperature oxidation reaction, be comprised of cordierite honeycomb ceramic carrier and the coating that is coated on carrier, and the expression formula of described coating is Pd/CoxCry-M/Al
2O
3, in formula, Pd is precious metal palladium; CoxCry is cobalt chromium composite oxides, and wherein cobalt chromium mol ratio is between 0.001～100; M is the metal of doping, and M is one or more in cerium, zirconium, lanthanum, iron, nickel, manganese, and when being two or more, ratio is any therebetween, and doping (mol ratio) M: (Co+Cr+M)<0.10; Al
2O
3For having the γ-Al of high thermal stability
2O
3.
The mesh order number of described cordierite honeycomb ceramic carrier is 300～600 orders.
Cobalt chromium mol ratio x: y=1: 2 in described CoxCry
The time, the catalyst activity optimum.
The weight of described coating accounts for 20～40% of honeycomb substrate weight, and in coating, the percentage by weight of each component is Pd: CoxCry-M: Al
2O
3=70～100: 10～20: 0.2～1.
The present invention also provides a kind of preparation method of described integral catalyzer, comprises the steps:
Step 1, the preparation of composite metal oxide CoxCry-M: the cobalt ions (Co of preparation solubility
2+) and chromium ion (Cr
3+) mixed solution or the cobalt ions (Co of solubility
2+), chromium ion (Cr
3+) and doped metal ion M
N+Mixed solution, n+ is the valence state of doping metals, [Co
2+]+[Cr
3+]=1～2mol/L or [Co
2+]+[Cr
3+]+[M
N+]=1～2mol/L; With the ammonia spirit of 10wt.%, regulate mixed solution pH 7～9.5, then under agitation aging; Vacuum filtration is then dried under 100～120 ℃, then 450～600 ℃ of lower roastings, more than 2 hours or 2 hours, make the cobalt chromic composite metal oxide CoxCry-M of doping metals;
Step 2, the preparation of coating paste: in proportion by γ-Al
2O
3With CoxCry-M, mix, form mixture, then add deionized water, stir and obtain suspension, regulate the addition of deionized water, make the solid content of suspension between 30～40%; By the suspension ball milling, control granularity D90 and be less than 50 μ m, obtain slurries; Then adding in proportion the Pd mass fraction is 10% Pd (NO
3)
2Solution, 3～7, obtain required coating paste with nitric acid or vinegar acid for adjusting pH;
Step 3, dipping: cordierite honeycomb ceramic carrier be impregnated in coating paste prepared by step 2, at the uniform velocity pull out, blow stifled;
Step 4, dry and roasting: by the cordierite honeycomb ceramic carrier after step 3 applying coating slurry after under 100～120 ℃, drying, repeating step three again, coated weight to cordierite honeycomb ceramic carrier reaches 20～40%, then, 450～700 ℃ of roastings 2～5 hours, obtain integral catalyzer.
When in step 1, doping metals M was cerium, lanthanum, iron, nickel, zirconium, metal salt solution was its nitrate, and when doping metals M was manganese, metal salt solution was manganese acetate.
In step 1, metal salt solution cobalt and chromium are its nitrate.
In step 2, adding Pd (NO
3)
2The time, directly join in the slurries of coating, together with slurries, be coated on the cordierite honeycomb carrier.
In step 2, adding Pd (NO
3)
2The time, first the slurries of coating are coated on the cordierite honeycomb carrier, then by Pd (NO
3)
2The solution incipient impregnation is to the surface of composite metal oxide CoxCry-M in step 1.
In step 3, when honeycomb ceramic carrier impregnated in slurries, stopped 1～3 second, then the speed with per second 30～60mm at the uniform velocity proposes.
Compared with prior art, molecular sieve catalyst of the present invention has good catalytic oxidation ability to natural gas and auto tail gas methane, and water resistant steam, sulfur poisoning-resistant ability are better, have the adaptable advantage of adverse circumstances.Simultaneously, abundant, with low cost by the catalyst raw material that the present invention makes, possess application prospect.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further details.
Embodiment mono-
By 25.648g Co (NO
3)
26H
2O and 70.536g Cr (NO
3)
39H
2O is dissolved in the 200mL deionized water, obtains the cobalt chromium salt solution, wherein [Co
2+]: [Cr
3+]=1: 2, [Co
2+]+[Cr
3+]=1.32mol/L; Under vigorous stirring, with the ammonia spirit of 10wt.%, dropwise drip above-mentioned salting liquid, until pH of mixed=9.0 are then under agitation aging; Vacuum filtration, and, with deionized water washing 3 times, then under 110 ℃, dry, then 500 ℃ of lower roastings 2 hours, make composite metal oxide Co
1Cr
2
By 50g γ-Al
2O
3With 5.5g oxide Co
1Cr
2Put into beaker, add the 140g deionized water, at room temperature stir 0.5h; By this suspension ball milling, control granularity D
90=30 μ m, obtain slurries; Then add 8.5g Pd (NO
3)
2(mass fraction of Pd is 10%), wherein the addition of Pd accounts for 1.5% of catalyst coat weight, finally uses the nitre acid for adjusting pH 4, obtains coating paste;
400 orders, the cordierite honeycomb ceramic carrier of Φ 83 * 60 impregnated in this coating paste, stopped 2 seconds, at the uniform velocity pull out, then use air purge, the cordierite honeycomb ceramic carrier of step applying coating slurry was dried 1 hour at 110 ℃, repeat above-mentioned dipping, baking step, coated weight to cordierite honeycomb ceramic carrier reaches 30%, then 600 ℃ of roastings 4 hours, obtains integral catalyzer.
Embodiment bis-
The preparation method is with embodiment 1, and different is to add 4.5g Pd (NO
3)
2(mass fraction of Pd is about 10%), wherein the addition of Pd accounts for 0.8% of catalyst coat weight, obtains catalyst 2 of the present invention.
Embodiment tri-
The preparation method is with embodiment 1, and different is in salting liquid, by 49.791g Co (NO
3)
26H
2O and 34.230g Cr (NO
3)
39H
2O is dissolved in the 200mL deionized water, obtains the cobalt chromium salt solution, wherein [Co
2+]: [Cr
3+]=2: 1, obtain catalyst 3 of the present invention.
Embodiment tetra-
The preparation method is with embodiment 1, and different is in salting liquid, by 24.370g Co (NO
3)
26H
2O and 67.015g Cr (NO
3)
39H
2O is dissolved in the 200mL deionized water, obtains the cobalt chromium salt solution, wherein [Co
2+]: [Cr
3+]=1: 2, and add 5.741g Ce (NO
3)
36H
2O, make [Ce
3+]/([Co
2+]+[Cr
3+]+[Ce
3+])=0.05, obtain catalyst 4 of the present invention.
The catalyst activity test is carried out in the stainless steel fixed bed reactors.Before advancing reactor, methane, oxygen and nitrogen fully mix in blender.Analog gas in the catalyst activity evaluation experimental forms (volume fraction): CH
40.5%, O
210%, N
2For molecular balance gas, the total flow of gas is 150mL/min, and corresponding reaction velocity (GHSV) is 40,000h
-1Reaction pressure is normal pressure; Reactor is as in a temperature control electric furnace, and reaction temperature is 200～500 ℃.By online chromatography analysis product, catalyst activity means with methane conversion (%).The simulated experiment result is as follows:
Embodiment five
The preparation method is with embodiment 1, and different is in salting liquid, by 24.370g Co (NO
3)
26H
2O and 67.015g Cr (NO
3)
39H
2O is dissolved in the 200mL deionized water, obtains the cobalt chromium salt solution, wherein [Co
2+]: [Cr
3+]=1: 2, and add 4.178g La (NO
3)
36H
2O, make [La
3+]/([Co
2+]+[Cr
3+]+[La
3+])=0.05, obtain catalyst P d/Co of the present invention
1Cr
2-La/Al
2O
3.
Embodiment six
The preparation method is with embodiment 1, and different is in salting liquid, by 24.370g Co (NO
3)
26H
2O and 67.015g Cr (NO
3)
39H
2O is dissolved in the 200mL deionized water, obtains the cobalt chromium salt solution, wherein [Co
2+]: [Cr
3+]=1: 2, and add 3.240g C
4H
6MnO
44H
2O, make [Mn
2+]/([Co
2+]+[Cr
3+]+[Mn
2+])=0.05, obtain catalyst P d/Co of the present invention
1Cr
2-Mn/Al
2O
3.
Embodiment seven
The preparation method is with embodiment 1, and different is in salting liquid, by 24.370g Co (NO
3)
26H
2O and 67.015g Cr (NO
3)
39H
2O is dissolved in the 200mL deionized water, obtains the cobalt chromium salt solution, wherein [Co
2+]: [Cr
3+]=1: 2, and add 2.671g Fe (NO
3)
39H
2O and 1.922g Ni (NO
3)
26H
2O, wherein [Fe
3+]: [Ni
2+]=1: 1, make ([Fe
3+]+[Ni
2+])/([Co
2+]+[Cr
3+]+[Fe
3+]+[Ni
2+])=0.05, obtain catalyst P d/Co of the present invention
1Cr
2-FeNi/Al
2O
3.
Claims (5)
1. preparation method for the integral catalyzer of methane low-temperature oxidation reaction, described integral catalyzer is comprised of cordierite honeycomb ceramic carrier and the coating that is coated on carrier, and the expression formula of described coating is Pd/CoxCry-M/Al
2O
3, in formula, Pd is precious metal palladium; CoxCry is cobalt chromium composite oxides, and wherein cobalt chromium mol ratio is between 0.001～100; M is the metal of doping, and M is more than one in cerium, zirconium, lanthanum, iron, nickel, manganese, and when being two or more, ratio is any therebetween, and with molar ratio computing, doping M:(Co+Cr+M)<0.10; Al
2O
3For having the γ-Al of high thermal stability
2O
3
It is characterized in that, comprise the steps:
Step 1, the preparation of composite metal oxide CoxCry-M: cobalt ions, chromium ion and the doped metal ion M of preparation solubility
N+Mixed solution, n+ is the valence state of doping metals, [Co
2+]+[Cr
3+]+[M
N+]=1～2mol/L; With the ammonia spirit of 10wt.%, regulate mixed solution pH 7～9.5, then under agitation aging; Vacuum filtration is then dried under 100～120 ℃, then 450～600 ℃ of lower roastings, more than 2 hours or 2 hours, make the cobalt chromic composite metal oxide CoxCry-M of doping metals;
Step 2, the preparation of coating paste: in proportion by γ-Al
2O
3With CoxCry-M, mix, form mixture, then add deionized water, stir and obtain suspension, regulate the addition of deionized water, make the solid content of suspension between 30～40%; By the suspension ball milling, control granularity D90 and be less than 50 μ m, obtain slurries; Then adding in proportion the Pd mass fraction is 10% Pd (NO
3)
2Solution, 3～7, obtain required coating paste with nitric acid or vinegar acid for adjusting pH;
Step 3, dipping: cordierite honeycomb ceramic carrier be impregnated in coating paste prepared by step 2, at the uniform velocity pull out, blow stifled;
Step 4, dry and roasting: by the cordierite honeycomb ceramic carrier after step 3 applying coating slurry after under 100～120 ℃, drying, repeating step three again, coated weight to cordierite honeycomb ceramic carrier reaches 20～40%, then, 450～700 ℃ of roastings 2～5 hours, obtain integral catalyzer.
2. preparation method according to claim 1, is characterized in that, when in step 1, doping metals M was cerium, lanthanum, iron, nickel, zirconium, metal salt solution was its nitrate, and when doping metals M was manganese, metal salt solution was manganese acetate.
3. preparation method according to claim 1, is characterized in that, in step 1, cobalt and chromium all add with its nitrate form.
4. preparation method according to claim 1, is characterized in that, in step 2, adding Pd (NO
3)
2The time, directly join in the slurries of coating, together with slurries, be coated on the cordierite honeycomb carrier.
5. preparation method according to claim 1, is characterized in that, in step 3, when honeycomb ceramic carrier impregnated in slurries, stopped 1～3 second, and then the speed with per second 30～60mm at the uniform velocity proposes.
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| CN107376935B (en) * | 2017-07-19 | 2020-05-26 | 上海化工研究院有限公司 | Monolithic catalyst for CO normal-temperature catalytic oxidation and preparation method thereof |
| CN107899570A (en) * | 2017-11-28 | 2018-04-13 | 秦皇岛天大环保研究院有限公司 | Integral catalyzer for super low concentration methyl hydride combustion and preparation method thereof |
| CN109985661A (en) * | 2019-04-29 | 2019-07-09 | 无锡威孚环保催化剂有限公司 | Catalyst and preparation method based on purification of volatile organic pollutant |
| CN110180533B (en) * | 2019-05-09 | 2020-09-11 | 华中科技大学 | KxMn-containing alloy8O16Catalyst synthesis method and application |
| CN110882686B (en) * | 2019-12-18 | 2023-01-10 | 西南石油大学 | Monolithic catalyst for preparing dimethyl carbonate by direct synthesis method, preparation method and direct synthesis method of dimethyl carbonate |
| CN114345361A (en) * | 2022-01-18 | 2022-04-15 | 晋江鹭安能源有限公司 | With CeO2Method for preparing carrier-supported transition metal oxide-supported catalyst body |
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