CN110075831A - A kind of iridium loaded catalyst and preparation method thereof for low-concentration methane catalysis burning - Google Patents
A kind of iridium loaded catalyst and preparation method thereof for low-concentration methane catalysis burning Download PDFInfo
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- CN110075831A CN110075831A CN201910450305.5A CN201910450305A CN110075831A CN 110075831 A CN110075831 A CN 110075831A CN 201910450305 A CN201910450305 A CN 201910450305A CN 110075831 A CN110075831 A CN 110075831A
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- low
- catalyst
- iridium
- concentration methane
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 30
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000002485 combustion reaction Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000010970 precious metal Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- -1 iridium metals Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000007084 catalytic combustion reaction Methods 0.000 abstract description 7
- 238000011109 contamination Methods 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011261 inert gas Chemical group 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of iridium loaded catalysts and preparation method thereof for low-concentration methane catalysis burning, belong to organic gaseous contamination object catalysis combustion field.Catalyst is by noble metal Ir, oxide and titania support composition.It is in terms of 100% by the weight of catalyst, the weight percent of precious metal iridium is 0.1 ~ 10.0%.The catalyst obtains the catalyst of carried noble metal ingredient by the precursor solution of the dipping precious metal iridium on titania support after drying, and roasting or the calcination process in hydrogen atmosphere in air atmosphere are obtained for low-concentration methane combustion catalyst.With other for compared with methane catalytic combustion catalyst, catalyst of the present invention to have the characteristics that preparation method is simple, low temperature active is high and stability is good, easy to promote and utilize.
Description
Technical field
The invention belongs to organic gaseous contamination objects to be catalyzed combustion field, specifically, being related to a kind of for low-concentration methane
It is catalyzed the iridium loaded catalyst and preparation method thereof of burning.
Background technique
In recent years, " environment " and " energy " problem is got worse, have become restrict human kind sustainable development it is important because
One of element.Natural gas is a kind of clean energy resource, but main component methane is also a kind of greenhouse gases.Therefore, the row of methane is controlled
Uncombusted methane is put and eliminates to have great importance.Catalysis burning has initiation temperature low, and reaction rate is fast, treatment effeciency
The advantages that high and applied widely is one of the important technology for controlling low-concentration methane discharge.
Palladium-based catalyst is that present methane catalytic combustion studies most commonly used noble metal catalyst.Patent
CN105457653A constructs functional layer by high-temp in-situ reaction to strengthen the interaction between palladium noble metal and carrier, and raising is urged
The performance of agent；Rare earth oxide auxiliary agent, alkali or alkaline earth metal is added using tin oxide as carrier in patent CN104923224A
Promote the activity and stability of palladium-based catalyst.Although palladium-based catalyst has obtained largely grinding in methane catalytic combustion field
Study carefully, but that there are still noble metal utilisations is low, low temperature active is insufficient, stability is poor and the technical problems such as high-speed low efficiency.2017
Year, Weave team (Science, 2017,356:299-303) utilizes the research method of model surface chemistry, theoretically
Confirm IrO2 (110) to the preferable low temperature active of methane activation.However, iridium base high-efficiency methane catalyst for catalytic combustion yet there are no
Report.Hu Pan waits (chemical journal, 2011,69:2080-2084) report Ir/ZrO quietly2Methyl hydride catalyzed performance, but it is remote not
And the catalytic performance (ACS Catalysis, 2017,7,1615-1625) of palladium catalyst reported in the literature.
Summary of the invention
For above-mentioned methyl hydride combustion catalyst problem encountered, the purpose of the present invention is to solve conventional load type is expensive
The disadvantages of metallic catalyst stability is poor, at high cost, and especially low temperature active is insufficient, it is simple to provide a kind of preparation process, price
It is cheap, it is suitble to the iridium based catalyst of large-scale production, to obtain the methyl hydride catalyzed combustion with superior low temperature activity and stability
Burn catalyst.
In order to achieve the above-mentioned object of the invention, The technical solution adopted by the invention is as follows:
A kind of iridium loaded catalyst for low-concentration methane catalysis burning, by precious metal iridium, its oxide and titanium dioxide
Carrier composition.
In the above-mentioned iridium loaded catalyst for low-concentration methane catalysis burning, the weight of catalyst is expensive in terms of 100%
For metal Ir based on precious metal element weight, the weight percent of noble metal Ir is 0.1 ~ 10%.
The preparation method of the above-mentioned iridium loaded catalyst for low-concentration methane catalysis burning, comprising the following steps:
(1) iridium metals precursor solution is supported on titania support, preferably equi-volume impregnating；
(2) by step (1) made sample in air dry after in air atmosphere roasting or in hydrogen atmosphere calcining or
Person first roasts in air atmosphere and calcines in hydrogen atmosphere again, and the iridium support type for obtaining being catalyzed burning for low-concentration methane is urged
Agent.
In the above preparation method, the precursor solution of step (1) the noble metal Ir is aqueous solution of chloraurate, also optional
With its aqueous chloride solution.
In the above preparation method, the drying temperature is 80 ~ 120 DEG C, and drying time is 1 ~ 24 h；The sky
Gas atmosphere maturing temperature is 500 ~ 900 DEG C, and calcining time is 1 ~ 24 h；Calcination temperature is 350 ~ 900 DEG C in hydrogen atmosphere, is forged
The burning time be 1 ~ 24 h, preferably 1 ~ 6 hour.
In the above preparation method, air atmosphere can also be mixed by the different proportion that oxygen and inert gas form as needed
Gas is closed to replace；Hydrogen atmosphere can be pure hydrogen atmosphere, can also be mixed as needed by the different proportion that hydrogen and inert gas form
Gas is closed to replace.
Titania support described in above-mentioned preparation method, directly selection business anatase or rutile structure two
Titan oxide particles, the titanium dioxide of the different-shape obtained by other methods also can be selected as carrier.
Above-mentioned titanium dichloride load iridium catalyst is used in low-concentration methane catalyst combustion reaction, can be direct by forming
It uses, can also be applied by being supported on business monolithic substrate.
Compared with prior art, the iridium loaded catalyst prepared by the present invention for low-concentration methane catalysis burning, tool
Have the characteristics that composition and preparation method are simple, at low cost, low temperature active is high and stability is good, it is easy to promote and utilize.
Specific embodiment
The present invention will be further explained with reference to the examples below, but protection scope of the present invention is not limited to implement
Range shown in example.
Embodiment 1:
For the iridium loaded catalyst of low-concentration methane catalysis burning, the catalyst by noble metal Ir, oxide and
TiO2Carrier composition.The mineral phase structure of the carrier is Anatase.It is the weight percent of Ir in terms of 100% by the weight of catalyst
Than being 1%.With equi-volume impregnating, will be impregnated on carrier containing the desired amount of chloro-iridic acid precursor solution, in air atmosphere
In, dry 12 h under the conditions of 100 DEG C, then in air atmosphere, 500 DEG C of 2 h of roasting, heating rate is 10 DEG C/min.
Finally, in pure H2400 DEG C of 1 h of roasting in atmosphere, heating rate are 10 DEG C/min, and methane catalytic combustion catalyst is made.
Embodiment 2:
For the iridium loaded catalyst of low-concentration methane catalysis burning, the catalyst by noble metal Ir, oxide and
TiO2Carrier composition.The mineral phase structure of the carrier is Rutile Type.It is the weight percent of Ir in terms of 100% by the weight of catalyst
Than being 5%.With equi-volume impregnating, will be impregnated on carrier containing the desired amount of chloro-iridic acid precursor solution, 80 DEG C of air gas
24 h are dried in atmosphere, 5 h are roasted in 800 DEG C of air atmospheres, and heating rate is 10 DEG C/min.Obtained methane catalytic combustion is urged
Agent.
Embodiment 3:
For the iridium loaded catalyst of low-concentration methane catalysis burning, the catalyst by noble metal Ir, oxide and and
TiO2Carrier composition.The mineral phase structure of the carrier is Anatase.It is the weight percent of Ir in terms of 100% by the weight of catalyst
Than being 1%.With equi-volume impregnating, will be impregnated on carrier containing the desired amount of iridium chloride precursor solution, 120 DEG C of air gas
It is dried overnight in atmosphere, H2500 DEG C of 2 h of roasting in atmosphere, heating rate are 10 DEG C/min, and methane catalytic combustion catalysis is made
Agent.
Catalyst described in 200 mg embodiment 1-4 is taken respectively, is placed in tubular fixed-bed reactor and is tested, and is reacted
Gas continue through it is tubular fixed-bed, reaction velocity be 30000 ml g-1 h-1, the group of gas is passed through as methane: oxygen: nitrogen
Gas=1:20:79(volume fraction).Activity evaluation is as shown in table 1.
1 catalyst activity evaluation result of table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| The temperature that methane conversion is 10% | 260 ℃ | 350℃ | 250 ℃ |
| The temperature that conversion ratio is 99% | 320 ℃ | 800 DEG C of > | 320 ℃ |
| Methane conversion at a temperature of conversion ratio is 99%, after the reaction of 50 h continuitys | ~99% | - | - |
Claims (6)
1. a kind of iridium loaded catalyst and preparation method thereof for low-concentration methane catalysis burning, which is characterized in that by expensive
Metal Ir, oxide and titania support composition.
2. a kind of iridium loaded catalyst and its preparation side for low-concentration methane catalysis burning as described in claim 1
Method, which is characterized in that by the weight of catalyst be 100% in terms of, noble metal Ir is based on precious metal element weight, the weight of noble metal Ir
Measuring percentage is 0.1 ~ 10%.
3. a kind of preparation method of iridium loaded catalyst for low-concentration methane catalysis burning described in claim 1,
It is characterized in that, includes the following steps:
(1) iridium metals precursor solution is supported on titania support, preferably equi-volume impregnating；
(2) by step (1) made sample in air dry after in air atmosphere roasting or in hydrogen atmosphere calcining or
Person first roasts in air atmosphere and calcines in hydrogen atmosphere again, and the iridium support type for obtaining being catalyzed burning for low-concentration methane is urged
Agent.
4. a kind of preparation method of the iridium loaded catalyst for low-concentration methane catalysis burning according to claim 3,
It is characterized in that, the precursor solution of step (1) the noble metal Ir is aqueous solution of chloraurate, it is water-soluble that its chloride also can be selected
Liquid.
5. a kind of preparation side of iridium loaded catalyst for low-concentration methane catalysis burning according to claim 3
Method, which is characterized in that the drying temperature is 80 ~ 120 DEG C, and drying time is 1 ~ 24 h；The air atmosphere roasts temperature
Degree is 500 ~ 900 DEG C, and calcining time is 1 ~ 24 h；Calcination temperature is 350 ~ 900 DEG C in hydrogen atmosphere, and the time is 1 ~ 24 h,
It is preferred that 1 ~ 6 hour.
6. a kind of iridium loaded catalyst for low-concentration methane catalysis burning described in claim 1 is urged in low-concentration methane
Change the application in combustion reaction.
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| CN201910450305.5A CN110075831B (en) | 2019-05-28 | 2019-05-28 | Iridium supported catalyst for catalytic combustion of low-concentration methane and preparation method thereof |
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| CN201910450305.5A CN110075831B (en) | 2019-05-28 | 2019-05-28 | Iridium supported catalyst for catalytic combustion of low-concentration methane and preparation method thereof |
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| CN110075831A true CN110075831A (en) | 2019-08-02 |
| CN110075831B CN110075831B (en) | 2022-07-15 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111029599A (en) * | 2019-08-28 | 2020-04-17 | 深圳市通用氢能科技有限公司 | Anti-reversal catalyst for fuel cell and preparation method thereof |
| CN111686723A (en) * | 2020-06-17 | 2020-09-22 | 中山大学 | Iridium-containing bimetallic catalyst for catalytic combustion of methane and preparation method thereof |
| CN113117699A (en) * | 2021-04-19 | 2021-07-16 | 福州大学 | Sulfate radical modified iridium-based methane combustion catalyst, and preparation and application thereof |
| CN114618484A (en) * | 2022-04-15 | 2022-06-14 | 福州大学 | Supported iridium-based catalyst and preparation method thereof |
| CN114653367A (en) * | 2022-03-11 | 2022-06-24 | 青岛大学 | Preparation and application of iridium-supported catalyst with different carriers |
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| CN114618484A (en) * | 2022-04-15 | 2022-06-14 | 福州大学 | Supported iridium-based catalyst and preparation method thereof |
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