CN106268859A - A kind of natural gas and auto tail gas processes catalyst and preparation method thereof - Google Patents
A kind of natural gas and auto tail gas processes catalyst and preparation method thereof Download PDFInfo
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- CN106268859A CN106268859A CN201610652048.XA CN201610652048A CN106268859A CN 106268859 A CN106268859 A CN 106268859A CN 201610652048 A CN201610652048 A CN 201610652048A CN 106268859 A CN106268859 A CN 106268859A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000003345 natural gas Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000007789 gas Substances 0.000 title claims abstract description 16
- 230000008569 process Effects 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 107
- 239000011248 coating agent Substances 0.000 claims abstract description 96
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 15
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 12
- 239000010410 layer Substances 0.000 claims abstract description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010970 precious metal Substances 0.000 claims abstract description 5
- 239000011247 coating layer Substances 0.000 claims abstract description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 39
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 239000007767 bonding agent Substances 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910018879 Pt—Pd Inorganic materials 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000008199 coating composition Substances 0.000 claims description 2
- 239000010953 base metal Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000012423 maintenance Methods 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- 229910052878 cordierite Inorganic materials 0.000 description 5
- 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 description 5
- 239000000306 component Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000002940 palladium Chemical class 0.000 description 3
- 150000003057 platinum Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- B01J35/56—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1021—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1023—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20753—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/902—Multilayered catalyst
- B01D2255/9022—Two layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/018—Natural gas engines
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of catalyst being applicable to lean burn natural gas vehicle maintenance service and preparation method thereof.Catalyst is by carrier and is coated in supported catalyst coating and forms, and coating is the A coating coated successively and B coating two-layer catalyst coat；A coating is nickel, cobalt improved aluminum oxide coating layer, and B coating is cerium, zirconium, the alumina load noble coatings of lanthanum modification.Catalyst the first coating of the present invention is base metal coating, and cost is less than noble coatings, and can play catalytic action under high temperature, high gas flow rate, processes the methane in tail gas；Second coating is noble coatings, and in its coating, precious metal concentration is higher, it is possible to play the effect of low temperature ignition.Catalyst preparation process condition of the present invention is easy to control, practical.Using base metal active component, under the conditions of identical noble metal dosage, this catalyst performance is obviously improved.
Description
Technical field
The invention belongs to catalyst preparation technical field, especially belong to natural gas purification catalyst preparation technical field, relate to
And a kind of catalyst being applicable to lean burn natural gas vehicle maintenance service and preparation method thereof.
Background technology
The most urgent along with the energy and environmental problem, in order to protect environment, save the energy, people are to motor-vehicle tail-gas
Emission control proposes higher requirement.China starts to perform natural gas engine state five discharge standard on January 1st, 2013.China
Natural gas relatively horn of plenty, a lot of city buses and taxi all use natural gas as fuel, add that natural gas is as one
The development energy, also can be widely used in fuel for motor vehicle in the future.Therefore, strengthen Research on Post-processing Techniques and control the natural gas tailstock
Gas discharge is imperative, is particularly important as the core component catalyst in post-processing technology.Relative to gasoline car, natural
The development of gas car catalyst technology is in development, and in recent years due to the adjustment of energy resource structure, natural gas vehicle catalyst technology develops.
Chinese patent (CN200810225539.1) uses and catalysis material is milled to certain particle size, impregnates noble metal, dries
Powder is obtained, then ball milling slurrying after dry, roasting.Slurry is coated on ceramic honeycomb carrier, is urged after drying, roasting
Agent.This method for preparing catalyst is simple, belongs to single layer coating, along with adding of discharge standard is tight, it is difficult to meet Abgasgesetz and want
Ask.
Chinese patent (ZL201310110465.8) discloses the system of a kind of high-performance lean-burn type natural gas automotive catalyst
Preparation Method, with cordierite honeycomb ceramic as carrier, with activated alumina and all kinds of salt assitant as coating, with Gui JinshuPt &Pd be
Catalyst activity component, prepares the catalyst of a kind of efficiently catalyzing and oxidizing methane by change coating formula and coating processes.Its
Take all kinds of salt assitant to be dissolved in deionized water, add a certain proportion of activated alumina, stirring ball-milling, after controlling serosity parameter be
Prepare coating slurry, according to the carrying method that Pt, Pd metal is different, precious metal salt is joined in slurry in batches, stir
After cordierite honeycomb ceramic carrier be impregnated in slurry, dried high-temperature roasting i.e. obtains this catalyst.
Chinese patent (ZL201210466258.1) discloses a kind of integral catalyzer, is made up of carrier and coating；Institute
Stating coating is double-decker, and wherein ground floor is applied directly on carrier by aluminium oxide and auxiliary agent；The second layer is by aluminium oxide, auxiliary agent
Being coated in ground floor coating with mesoporous material, described mesoporous material is made up of one or more meso pore characteristics catalyst.Above-mentioned
Catalyst is non-precious metal catalyst, and catalyst performance is relatively low, it is difficult to meet the tightest discharge standard requirement.
Summary of the invention
The present invention discloses a kind of catalyst being applicable to the process of lean burn natural gas tail gas according to the deficiencies in the prior art
And preparation method thereof.Method difference prepared by the present invention and tradition CNG catalyst is to use layered coating, and ground floor uses
Nickel, cobalt improved aluminum oxide coating layer, the second layer uses the alumina load noble coatings that cerium, zirconium, lanthanum etc. are modified, and the present invention obtains
Obtained the lean-burn CNG catalyst of a kind of excellent performance.
The present invention is achieved through the following technical solutions:
Present invention firstly provides a kind of natural gas and auto tail gas and process catalyst, described catalyst is by carrier and is coated in
Supported catalyst coating forms, it is characterised in that: described coating is the A coating coated successively and B coating two-layer catalyst
Coating；A coating is nickel, cobalt improved aluminum oxide coating layer, and B coating is cerium, zirconium, the alumina load noble coatings of lanthanum modification.
Described coating A is carried on γ-Al by one or both in Ni, Co2O3Composition, wherein the percentage by weight of Ni is born
Carrying capacity is 1%～20%, and the weight percent loadings of Co is 2%～8%: when Ni Yu Co loads simultaneously, its weight percent
Than load total amount≤20%.
Described coating B is by cerium, zirconium, the γ-Al of lanthanum modification2O3Carried noble metal forms, the wherein weight percent of cerium, zirconium, lanthanum
It is 0～20% than consumption；In coating B, noble metal is Pd or Pt-Pd, wherein the percentage by weight consumption of Pd or Pt-Pd be 1%～
20%.
Present invention also offers the preparation method of above-mentioned catalyst, comprise the following steps:
(1), form according to the catalyst of above-mentioned coating A, weigh corresponding γ-Al2O3Powder；
(2), weighing required Ni, Co salt according to above-mentioned coating A catalyst composition, add suitable quantity of water, amount of water is (1)
0.9～1.0 times of middle material water absorption, mix homogeneously；
(3), step (1) gained powder is added in the solution of step (2)；Being stirred until homogeneous rapidly, standing time >=1 is little
Time, 80 DEG C are vacuum dried 2 hours, calcine 2 hours for 1000 DEG C, obtain the modified alumina powder of a kind of Ni, Co；
(4), by powder and other of step (3) gained needing the mixture adding component to add bonding agent, ball milling is uniform
By the time the slurry of coating A；A coating paste is coated on carrier, is dried 2 hours through 120 DEG C, calcines 2 hours for 600 DEG C, obtains A and be coated with
Layer catalyst.
(5), form according to the catalyst of above-mentioned coating B, weigh corresponding γ-Al2O3Powder；And according to the method for step (2)
Ce, Zr, La solution required for configuration.
(6), the γ-Al that step (5) is obtained2O3Powder and solution stir rapidly, standing time >=1 hour, and 80 DEG C true
Empty dry 8 hours, calcine 2 hours for 600 DEG C, obtain the modified alumina powder of a kind of Ce, Zr, La；
(7), according to the requirement of coating B weighing precious metals pd or Pd, Pt solution, add suitable quantity of water, amount of water is powder in (6)
0.9～1.0 times of material water absorption, mix homogeneously.Standing time >=1 hour, 80 DEG C are vacuum dried 2 hours, and 600 DEG C of calcinings 2 are little
Time, obtain the noble metal powder of coating B；
(8), by powder and other of step (7) gained needing the mixture adding component to add bonding agent, ball milling is uniform
By the time the slurry of coating B；
(9), by the slurry of coating B be coated on that step (4) obtains containing on coating A catalyst, be dried 2 through 120 DEG C little
Time, calcine 2 hours, obtain described catalyst for 600 DEG C.
The present invention is when preparing described catalyst, first according to design it needs to be determined that coating A, the coated weight of coating B and urge
Agent noble metal dosage.According to design it needs to be determined that the γ-Al of coating A2O3, the consumption of Co and Ni, wherein Co and Ni is solvable
Property salt, such as nitrate cobalt etc..Noble metal dosage according to catalyst determines modified aluminas and the noble metal dosage of coating B.This
Invention catalyst, when coating, first coats A coating, after 600 DEG C of roastings are stable, is coated with B coating.Its purpose is to allow your gold
Belong to layer to separate with base metal layer, each play catalytic action.
The catalyst of the present invention is double coated catalysts, and its ground floor is base metal coating, uses nickel, cobalt improved oxygen
Change aluminized coating；Its second coating is noble coatings, uses the metal-modified alumina load noble coatings such as cerium, zirconium, yttrium.
The advantage of catalyst of the present invention is: the first coating is base metal coating, and cost is less than noble coatings, and can be at height
Under gas flow rate warm, high, play catalytic action, process the methane in tail gas.Second coating is noble coatings, expensive in its coating
Metal concentration is higher, it is possible to play the effect of low temperature ignition.The present invention is characterized by: in the first coating, nickel, the interpolation of cobalt are wanted
In right amount, and the suitable catalyst of ratio of the first coating and the second coating just can embody preferable performance.
Catalyst preparation process condition of the present invention is easy to control, practical.Base metal active component Co and Ni is used to make
For A coating (bottom), B coating is coated on surface.Under the conditions of identical noble metal dosage, this catalyst performance is substantially carried
Rise.Experiment proves that catalyst performance of the present invention is excellent.
Accompanying drawing explanation
Fig. 1 is different loads amount catalyst CH4Activity data；
Fig. 2 is A, B layer difference coated weight catalyst CH4Activity data.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further described, and detailed description of the invention is further to the present invention
Illustrating, limit the present invention never in any form, technology same or like with the present invention is without departing from the scope of protection of the invention.
Comparative example:
Coated weight is prepared by 180g/l single coating catalyst
Weigh platinum salt solution and palladium salt solution (containing Pt0.2753g and Pd1.3768g) respectively, add in 80g deionized water,
Stir.By 98.35g γ-Al2O3Powder adds in platinum palladium solution, places 1 hour after stirring rapidly.Then 80 DEG C of vacuum
It is dried 8 hours, calcines 2 hours, obtain Pd-Pt/ γ-Al for 600 DEG C2O3Powder (for khaki powder).Khaki powder add viscous
Connect agent, be prepared as serosity, be coated in hole mesh number 400cell/in2, on volume 2.5ml cordierite ceramic honeycomb carrier, coating is done
Heavily going up carrying capacity is: 0.45g.Drying and roasting, being bullion content is 80g/ft3Platinum palladium catalyst.
Embodiment 1:
A coating is Ni/ γ-Al2O3, coated weight is 40g/l；B coating is 140g/l catalysis preparation
Weigh nickel nitrate (nickeliferous 5g), add in 80g deionized water, stir.By 95.00g γ-Al2O3Powder adds nitre
In acid nickel solution, place 1 hour after stirring rapidly.Then 80 DEG C are vacuum dried 8 hours, calcine 2 hours, obtain for 1000 DEG C
Ni/γ-Al2O3Powder.Ni/γ-Al2O3Powder adds bonding agent, is prepared as serosity, is coated in hole mesh number 400cell/in2, body
On long-pending 2.5ml cordierite ceramic honeycomb carrier, on dry coating weight, carrying capacity is: 0.1g.After drying roasting, obtain coating A1.Point
Another name takes platinum salt solution and palladium salt solution (containing Pt0.354g and Pd1.770g), adds in 80g deionized water, stirs.Will
97.876gγ-Al2O3Powder adds in platinum palladium solution, places 1 hour after stirring rapidly.Then 80 DEG C are vacuum dried 8 hours,
600 DEG C of roastings 2 hours, obtain Pd-Pt/ γ-Al2O3Powder (for khaki powder).Khaki powder adds bonding agent, preparation
Becoming serosity, be coated on A1, on dry coating weight, carrying capacity is: 0.35g.Drying and roasting, being bullion content is 80g/ft3Platinum palladium
Catalyst.
Above various types of materials, nitrate etc. are commercially available.
Embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6 are identical with the preparation process of embodiment 1, simply
The load capacity of Co, Ni in A coating is different.Its list of ingredients is as follows:
Testing result:
| Co load capacity | Li load capacity | |
| Embodiment 1 | 0 | 76.1 |
| Embodiment 2 | 0 | 71.4 |
| Embodiment 3 | 0 | 89.8 |
| Embodiment 4 | 3% | 0 |
| Embodiment 5 | 8% | 0 |
| Embodiment 6 | 10% | 8% |
Catalyst in above comparative example and embodiment is carried out active evaluation test.Experimental condition is as follows:
Simulation lean-combustion engine exhaust gas volume composition: methane: 1000ppm, carbon monoxide: 3000ppm, titanium dioxide
Carbon: 10%, nitric oxide: 1000ppm oxygen: 6.5%, nitrogen: Balance Air；Air speed: 60000h-1。
The different embodiment catalyst CH of table 14Activity data
| T50(℃) | T90(℃) | |
| Comparative example | 344 | 420 |
| Embodiment 1 | 337 | 388 |
| Embodiment 2 | 334 | 384 |
| Embodiment 3 | 332 | 388 |
| Embodiment 4 | 338 | 391 |
| Embodiment 5 | 337 | 389 |
| Embodiment 6 | 334 | 387 |
It is appreciated that from table 1:
By the change of coating, in the case of identical bullion content, the performance of the performance of double coated catalysts is better than single
Coating.
By changing A coating and the coated weight of B coating, specific embodiment is as follows:
Embodiment 7:
A coating is Ni/ γ-Al2O3, coated weight is 60g/l；B coating is 120g/l catalysis preparation
Weigh nickel nitrate (nickeliferous 5g), add in 80g deionized water, stir.By 95.00g γ-Al2O3Powder adds nitre
In acid nickel solution, place 1 hour after stirring rapidly.Then 80 DEG C are vacuum dried 8 hours, calcine 2 hours, obtain for 1000 DEG C
Ni/γ-Al2O3Powder.Ni/γ-Al2O3Powder adds bonding agent, is prepared as serosity, is coated in hole mesh number 400cell/in2, body
On long-pending 2.5ml cordierite ceramic honeycomb carrier, on dry coating weight, carrying capacity is: 0.15g.After drying roasting, obtain coating A1.Point
Another name takes platinum salt solution and palladium salt solution (containing Pt0.413g and Pd2.065g), adds in 80g deionized water, stirs.Will
97.522gγ-Al2O3Powder adds in platinum palladium solution, places 1 hour after stirring rapidly.Then 80 DEG C are vacuum dried 8 hours,
600 DEG C of roastings 2 hours, obtain Pd-Pt/ γ-Al2O3Powder (for khaki powder).Khaki powder adds bonding agent, preparation
Becoming serosity, be coated on A1, on dry coating weight, carrying capacity is: 0.30g.Drying and roasting, being bullion content is 80g/ft3Platinum palladium
Catalyst.
Embodiment 8, embodiment 9, embodiment 10 are identical with the preparation process of embodiment 7, at A coating coated weight the most not
With, B coating coated weight is also adjusted with A coating, and in B coating, noble metal total amount is identical.Its list of ingredients is as follows:
| A figure layer coated weight | B figure layer coated weight | |
| Embodiment 7 | 60g/l | 120g/l |
| Embodiment 8 | 80g/l | 100g/l |
| Embodiment 9 | 100g/l | 80g/l |
| Embodiment 10 | 80g/l | 60g/l |
Testing result:
Table 2A, B layer difference coated weight embodiment catalyst CH4Activity data
| T50(℃) | T90(℃) | |
| Comparative example | 344 | 420 |
| Embodiment 7 | 334 | 384 |
| Embodiment 8 | 328 | 380 |
| Embodiment 9 | 332 | 382 |
| Embodiment 10 | 335 | 384 |
It is appreciated that from table 2:
The performance of embodiment 7,8,9,10 is superior to comparative example, can obtain the catalyst that performance is good.
Fig. 1 is the CH4 conversion rate curve that employing table 1, the present invention of Fig. 2 employing table 2 data creating test detection.In figure,
Abscissa is temperature, unit: DEG C；Vertical coordinate is conversion ratio, unit: %.In figure, " 0 " is comparative example catalyst performance curve, " 1
～6 " it is respectively enforcement 1～the catalyst performance curve of embodiment 6；" 7～10 " are respectively enforcement 7～the catalyst of embodiment 10
Performance curve.
As can be drawn from Figure 1, at the high-temperature area of 380 DEG C～540 DEG C scopes, bottom uses non-noble metal Ni or Co modified
Coating, conversion ratio is apparently higher than not having bottom catalyst.Bottom uses non-noble metal catalyst coat, catalyst T90All exist
Less than 400 DEG C, and comparative example catalyst is at 420 DEG C.More 400～600 DEG C of vehicle conditions in conjunction with gas-fueled vehicles row's temperature.Use real
Execute example catalyst and the transformation ratio comparative example catalyst of CH4 is wanted high 5%～10%.This catalyst can well apply to natural gas
Vehicle maintenance service.
Claims (4)
1. natural gas and auto tail gas processes a catalyst, and described catalyst is by carrier and is coated in supported catalyst coating
Composition, it is characterised in that: described coating is the A coating coated successively and B coating two-layer catalyst coat；A coating is that nickel, cobalt change
Property aluminum oxide coating layer, B coating is the alumina load noble coatings that cerium, zirconium, lanthanum are modified.
Natural gas and auto tail gas the most according to claim 1 processes catalyst, it is characterised in that: described coating A is by Ni, Co
In one or both be carried on γ-Al2O3Composition, wherein the weight percent loadings of Ni is 1%～20%, the weight of Co
Percent loadings is 2%～8%: when Ni Yu Co loads simultaneously, its percentage by weight load total amount≤20%.
Natural gas and auto tail gas the most according to claim 1 process catalyst, it is characterised in that: described coating B by cerium,
γ-the Al that zirconium, lanthanum are modified2O3Carried noble metal forms, and wherein cerium, zirconium, the percentage by weight consumption of lanthanum are 0～20%；Coating B
Middle noble metal is Pd or Pt-Pd, and wherein the percentage by weight consumption of Pd or Pt-Pd is 0.1%～20%.
4. a natural gas and auto tail gas processes method for preparing catalyst, it is characterised in that comprise the following steps:
Described catalyst components consumption consumption as described in any one of claim 1 to 5 prepares；
(1), form according to the catalyst of above-mentioned coating A, weigh corresponding γ-Al2O3Powder；
(2), weighing required Ni, Co salt according to above-mentioned coating A catalyst composition, add suitable quantity of water, amount of water is material in (1)
0.9～1.0 times of material water absorption, mix homogeneously；
(3), step (1) gained powder is added in the solution of step (2)；It is stirred until homogeneous rapidly, standing time >=1 hour,
80 DEG C are vacuum dried 2 hours, calcine 2 hours for 1000 DEG C, obtain the modified alumina powder of a kind of Ni, Co；
(4), by powder and other of step (3) gained needing the mixture adding component to add bonding agent, ball milling uniformly waits until
The slurry of coating A；A coating paste is coated on carrier, is dried 2 hours through 120 DEG C, calcines 2 hours, obtain A coating and urge for 600 DEG C
Agent.
(5), form according to the catalyst of above-mentioned coating B, weigh corresponding γ-Al2O3Powder；And configure according to the method for step (2)
Required Ce, Zr, La solution.
(6), the γ-Al that step (5) is obtained2O3Powder and solution stir rapidly, standing time >=1 hour, and 80 DEG C of vacuum are done
Dry 8 hours, calcine 2 hours for 600 DEG C, obtain the modified alumina powder of a kind of Ce, Zr, La；
(7), according to the requirement of coating B weighing precious metals pd or Pd, Pt solution, add suitable quantity of water, amount of water is that in (6), powder is inhaled
0.9～1.0 times of the water yield, mix homogeneously.Standing time >=1 hour, 80 DEG C are vacuum dried 2 hours, calcine 2 hours for 600 DEG C,
Noble metal powder to coating B；
(8), by powder and other of step (7) gained needing the mixture adding component to add bonding agent, ball milling uniformly waits until
The slurry of coating B；
(9), by the slurry of coating B be coated on that step (4) obtains containing on coating A catalyst, be dried 2 hours through 120 DEG C,
Calcine 2 hours, obtain described catalyst for 600 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108927168A (en) * | 2018-07-16 | 2018-12-04 | 山东艾泰克环保科技股份有限公司 | A kind of natural gas vehicle three-way catalyst and preparation method thereof |
| CN109174077A (en) * | 2018-10-17 | 2019-01-11 | 安徽菲扬新材料有限公司 | A kind of vehicle maintenance service catalyst and preparation method thereof |
| CN115382540A (en) * | 2022-07-29 | 2022-11-25 | 凯龙蓝烽新材料科技有限公司 | Preparation method of modified alumina carrier supported noble metal catalyst for lean burn CNG |
-
2016
- 2016-08-04 CN CN201610652048.XA patent/CN106268859A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108927168A (en) * | 2018-07-16 | 2018-12-04 | 山东艾泰克环保科技股份有限公司 | A kind of natural gas vehicle three-way catalyst and preparation method thereof |
| CN109174077A (en) * | 2018-10-17 | 2019-01-11 | 安徽菲扬新材料有限公司 | A kind of vehicle maintenance service catalyst and preparation method thereof |
| CN115382540A (en) * | 2022-07-29 | 2022-11-25 | 凯龙蓝烽新材料科技有限公司 | Preparation method of modified alumina carrier supported noble metal catalyst for lean burn CNG |
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