CN105107508B - A kind of coal bed gas sulfur-tolerance deoxidation integral catalyzer and preparation method thereof - Google Patents
A kind of coal bed gas sulfur-tolerance deoxidation integral catalyzer and preparation method thereof Download PDFInfo
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- CN105107508B CN105107508B CN201510429836.8A CN201510429836A CN105107508B CN 105107508 B CN105107508 B CN 105107508B CN 201510429836 A CN201510429836 A CN 201510429836A CN 105107508 B CN105107508 B CN 105107508B
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- 239000003245 coal Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- 239000000919 ceramic Substances 0.000 claims abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 18
- 239000011593 sulfur Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000010953 base metal Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 54
- 239000007789 gas Substances 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 241000264877 Hippospongia communis Species 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000002309 gasification Methods 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000004073 vulcanization Methods 0.000 claims description 7
- 230000001413 cellular effect Effects 0.000 claims description 6
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052878 cordierite Inorganic materials 0.000 claims description 4
- 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 group [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 description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000006477 desulfuration reaction Methods 0.000 abstract description 2
- 230000023556 desulfurization Effects 0.000 abstract description 2
- 231100000572 poisoning Toxicity 0.000 abstract description 2
- 230000000607 poisoning effect Effects 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000007605 air drying Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 239000008246 gaseous mixture Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
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- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 238000001556 precipitation Methods 0.000 description 2
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- 238000011084 recovery Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- 101100084903 Botryococcus braunii SSL-1 gene Proteins 0.000 description 1
- 101100111707 Botryococcus braunii SSL-2 gene Proteins 0.000 description 1
- 101100437785 Botryococcus braunii SSL-3 gene Proteins 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
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Abstract
The present invention relates to a kind of coal bed gas sulfur-tolerance deoxidation integral catalyzers and preparation method thereof, the catalyst, which by catalyst carrier loads active component oxide/catalyst carrier compound that the oxide of nonmetallic active component obtains, to carry out full cure by the oxide of nonmetallic active component through vulcanizing treatment and obtains, wherein the catalyst carrier is by the γ Al that are applied on ceramic honeycomb carrier and ceramic honeycomb carrier2O3Tie coat forms；The nonmetallic active component is two or more the mixture in Co, Mo, Mn, Fe, Zn.The present invention is using base metal as active component, it is at low cost, and the catalyst prepared use in coal bed gas will not be inactivated by sulfur poisoning, stability is good, therefore is handled using during its catalytic deoxidation without reduction activation, and coal bed gas carries out desulfurization process without advance, simplify technique, the catalyst shape is regular, adapts to the characteristics of coal seam throughput is big, pressure head is low, bed pressure drop is small, easy to use.
Description
Technical field
The present invention relates to catalyst technical fields, and in particular to a kind of coal bed gas sulfur-tolerance deoxidation integral catalyzer and its system
Preparation Method.
Background technology
Coal bed gas is formed during plant changes to coal, its primary attachment is in coal micropore surface or deposits
In the gap in coal seam；Coal bed gas also has a small amount of ethane, carbon dioxide, nitrogen, helium, hydrogen, vulcanization based on methane
Hydrogen etc..The methane emission that China generates in coal production process accounts for the 21.9% of global total release, but recycles
Rate is extremely low.In China, the utilization rate of annual coal bed gas is less than 10%, and there are about 20,000,000,000 m3CBM Drainage be put into air, and
The greenhouse effects of methane are 21 times of carbon dioxide, and the destruction to ozone layer is 7 times of carbon dioxide.Therefore, substantial amounts of coal seam
Gas directly discharge is the significant wastage to the valuable energy, can also be threatened to environment for human survival, it is necessary to be recycled.
The coal bed gas of China's extraction typically contains the oxygen of volume fraction 2-12%, and the aerial explosion limit of methane only has under normal pressure
5-15%, and with the increase of pressure, explosion limit expands, if being directly enriched with methane from the coal bed gas of extraction, there will be
The danger of explosion.Therefore, before methane recovery utilizes, it is necessary to which, to coal bed gas deoxidation processing, exploitation sulfur-tolerance deoxidation catalyst is to close
Key technology, it is of great significance for the recycling of coal bed gas.
Coal bed gas purification method of deoxidation mainly has two classes：Physical partition method, including low-temperature deep separation, pressure-variable adsorption and film
Separation；Combustion method, including coke combustion deoxidizing and catalysis combustion deoxidizing.Sky is mixed in the low concentration coal-bed gas of general underground extraction
Gas, for oxygen concentration up to 10% or so, physical partition method some in purification and separation process contains methane in flue gas leading is discharged,
And operation with high pressure is undergone, therefore can be in a certain stage in the range of burning and the explosion limit of methane, so as to which there are huge
Big security risk.Therefore, it is a kind of safe and reliable method of deoxidation using catalyst deoxidation.
The catalyst generally used in coal bed gas at present is graininess, it is impossible to meet that coal seam throughput is big, pressure head is low, pressure drop
The characteristics of small.Chinese patent CN1342516A discloses a kind of manganese deoxidier and preparation method thereof, before the deoxidier use
Hydrogen reducing is needed, adds processing step, expends hydrogen source.Chinese patent CN101664679A and CN101613627A are disclosed respectively
A kind of coal bed gas deoxidation catalyst and a kind of catalytic deoxidation process of oxygen-contained coal bed gas, catalyst activity component used are expensive
Metal, and not resistant to sulfur need reduction to make its activity recovery during use.
In view of the above deficiency in relation to coal bed gas deoxidation catalyst, exploitation is a kind of for coal bed gas property feature, with non-
Noble metal will be a kind of selection well for the resistant to sulfur integral catalyzer of active component, have very big market prospects.
The content of the invention
The technical problems to be solved by the invention are for above-mentioned deficiency in the prior art, provide a kind of Sulfur tolerance
It is good, it is active component suitable for integral catalyzer of coal bed gas deoxidation and preparation method thereof using base metal.
In order to solve the above technical problems, technical solution provided by the invention is：
A kind of coal bed gas sulfur-tolerance deoxidation integral catalyzer is provided, it is to load base metal activearm by catalyst carrier
Point the obtained active component oxide/catalyst carrier compound of oxide through vulcanizing treatment by base metal active component
Oxide carries out full cure and obtains, wherein the catalyst carrier on ceramic honeycomb carrier and ceramic honeycomb carrier by applying
γ-Al2O3Tie coat forms；
The base metal active component is two or more the mixture in Co, Mo, Mn, Fe, Zn；
The vulcanizing treatment carries out sulphur for active component oxide/catalyst carrier compound is placed in sulfur-bearing atmosphere
Change is handled, and 200-400 DEG C of curing temperature, the sulfur-bearing atmosphere is by N2、H2And the CS of gasification2Composition, wherein N2With H2Volume
Than for 1-3:1, CS2Quality and N2And H2The ratio of the two total volume is 0.2-0.3g/400mL.
By said program, the ceramic honeycomb carrier is cordierite honeycomb ceramic, mullite ceramic honey comb or aluminium oxide bee
Nest ceramics；
By said program, the oxide mass of active component in the active component oxide/catalyst carrier compound
Content is 8-16%, and the mass content of γ-Al2O3 tie coats is 6-12%.
The preparation method step of coal bed gas sulfur-tolerance deoxidation integral catalyzer of the present invention is as follows：
1) catalyst carrier is prepared：Ceramic honeycomb carrier is immersed in tie coat slurry, takes out, blows off after fully impregnating
Leftover slurry, then catalyst carrier is obtained through drying, 650-750 DEG C of roasting 1-4h, repeatedly impregnated as needed in preparation process,
Blow leftover slurry, drying, calcination steps off so that ceramic honeycomb carrier weightening 8-18wt%；
2) active component slurry is prepared：The soluble-salt of active component is dissolved in water and obtains solution, it, will after adding in alkali reaction
The oxide of active component is obtained after gained washing of precipitate, drying, 400-550 DEG C of roasting 1-4h, then is configured to active component slurry
Material；Or the carbonate of active component or oxalates mixed pyrolysis are obtained into the oxide of active component, then it is configured to active component
Slurry；Or the oxide of active component is directly configured to active component slurry；
3) active component oxide/catalyst carrier compound is prepared：Catalyst carrier obtained by step 1) is immersed into step
2) in gained active component slurry, taken out after fully impregnating, blow leftover slurry off, then obtained through drying, 650-750 DEG C of roasting 1-4h
To active component oxide/catalyst carrier compound；
4) coal bed gas sulfur-tolerance deoxidation integral catalyzer is prepared：Active component oxide/catalyst obtained by step 3) is carried
Body compound, which is placed in sulfur-bearing atmosphere, carries out vulcanizing treatment, and vulcanizing treatment is completed to obtain the catalysis of coal bed gas sulfur-tolerance deoxidation monoblock type
Agent.
By said program, the preparation method of step 1) the tie coat slurry is：By γ-Al2O3Or in boehmite
It is one or two kinds of add in salpeter solutions, add water reconciliation and obtain tie coat slurry, tie coat slurry solid content is 15-
25%, nitric acid content is 1-5wt% in tie coat slurry.
By said program, the preparation method of step 2) the active component slurry is：The oxide of active component is added in
Salpeter solution and water carry out wet ball-milling, ball milling fully afterwards with nitre acid for adjusting pH value to 4-5 to obtain the final product, active component slurry solid content
For 20-25%.
The beneficial effects of the present invention are：
Coal bed gas sulfur-tolerance deoxidation integral catalyzer provided by the invention is used to that during coal bed gas deoxidation reduction work need not to be carried out
Change is handled, and deoxy activity is high, and stability is good, and its Sulfur tolerance is good, will not be inactivated by the sulfur poisoning in coal bed gas, coal bed gas need not
Carry out desulfurization process in advance directly can carry out deoxidation with the catalyst, in addition, it is using base metal as active component, cost
It is low, and the catalyst is integral catalyzer, is suitable for the characteristics of coal seam throughput is big, pressure head is low, bed pressure drop is small, user
Just.
Description of the drawings
Catalyst described in integral catalyzer vulcanizing treatment devices and embodiment 5 of the Fig. 1 prepared by the embodiment of the present invention 1
Performance testing device schematic diagram.
Wherein：1- mass flowmenters；2- gasification burners；3- precision metering pumps；4-CS2Slot；5- reacting furnaces；6- steam separates
Device；7- analyzers.
Specific embodiment
For those skilled in the art is made to more fully understand technical scheme, the present invention is made below in conjunction with the accompanying drawings into
One step is described in detail.
Embodiment 1
The preparation of coal bed gas sulfur-tolerance deoxidation integral catalyzer, step are as follows：
1) by 20g γ-Al2O3(nitric acid and water are by volume in addition 10mL salpeter solutions after being mixed with 2g boehmites
1:6 are mixed to get), it adds 70mL water and reconciles into tie coat slurry, 5.32g cellular aluminas ceramics are immersed into tie coat
It in slurry, takes out after five minutes, then leftover slurry is blown off with compressed air, subsequent 120 DEG C of heated-air dryings, and in 700 DEG C of roastings
2 obtain catalyst carrier, cellular alumina ceramics weightening 0.91g (weightening 14.6%) when small；
2) by 50gFe (NO3)3·9H2O and 38.9gCo (NO3)2·6H2O is dissolved in 240mL water, and Na is added dropwise2CO3Solution
(concentration 0.5mol/L), 40 DEG C, titration end-point pH=8.0 of controlling reaction temperature, filtering reacting liquid, gained precipitation are washed with water
2 times, with after dry at 120 DEG C, and in 400 DEG C roast 1-2 it is small when obtain oxide powder, the oxide powder obtained
19g adds in 10mL salpeter solutions (nitric acid and water by volume 1:6 are mixed to get) and 45mL water carry out wet ball-milling, ball milling 2 is small
Shi Houyong salpeter solutions (nitric acid and water by volume 1:6 are mixed to get) and water pH value to 4-5, obtain 40mL active components slurry
Material；
3) catalyst carrier obtained by step 1) is immersed in active component slurry obtained by step 2), taken out after five minutes, with pressure
Contracting air blows additional size off, and with 120 DEG C of heated-air dryings, integral catalyzer is obtained with when 650 DEG C of roastings 2 are small, whole
The oxide mass content of active component is 15.6% in formula catalyst, and the mass content of tie coat is 11.8%；
4) integral catalyzer obtained by step 3) is placed in sulfur-bearing atmosphere and carries out vulcanizing treatment, specific method is：It will be whole
Body formula catalyst is placed in reacting furnace 5, by N2And H2Gaseous mixture (N2With H2Volume ratio be 1:1) with the flow of 400mL/min
Input gasification burner 2, CS2CS in slot 42Vapour in gasification burner 2 is squeezed into the flow of 0.2-0.3g/min also by precision metering pump 3
Change, gaseous mixture is formed in gasification burner 2, gaseous mixture is inputted reacting furnace 5 carries out vulcanizing treatment to integral catalyzer, at vulcanization
Science and engineering skill is：When vulcanization 5 is small at 230 DEG C of initial temperature, then be warming up to 400 DEG C continue vulcanization 15 it is small when.Integral catalyzer
Vulcanizing treatment schematic device as shown in Figure 1, vulcanizing treatment complete i.e. obtain coal bed gas sulfur-tolerance deoxidation integral catalyzer, be denoted as
SSL-1。
Embodiment 2
The preparation of coal bed gas sulfur-tolerance deoxidation integral catalyzer, step are as follows：
1) by 20g γ-Al2O3It is added in after being mixed with 2g boehmites in 10mL salpeter solutions, adds the reconciliation of 70mL water
Into tie coat slurry, nitric acid content is 5wt% in tie coat slurry, and 6.43g cordierite honeycomb ceramics are immersed transition applies
It in layer slurry, takes out after five minutes, then leftover slurry is blown off with compressed air, subsequent 120 DEG C of heated-air dryings, and in 700 DEG C of roastings
Burn 2 it is small when obtain catalyst carrier, cordierite honeycomb ceramic weightening 0.67g (weightening 9.4%)；
2) by 19.84gMnCO3、15.43gZnCO3With 6.13g (NH4)6Mo7O24·4H2O mixing and ball millings 2h is after 450 DEG C
Roasting 2h obtains oxide powder, and the oxide powder 17g obtained adds in 10mL salpeter solutions and 60mL water carries out wet type ball
Mill, when ball milling 2 is small after with salpeter solution adjust pH value to 4-5, obtain 50mL active component slurries；
3) catalyst carrier obtained by step 1) is immersed in active component slurry obtained by step 2), taken out after five minutes, with pressure
Contracting air blows additional size off, and with 120 DEG C of heated-air dryings, integral catalyzer is obtained with when 500 DEG C of roastings 2 are small, whole
The oxide mass content of active component is 8.6% in formula catalyst, and the mass content of tie coat is 6.4%；
4) integral catalyzer obtained by step 3) is placed in sulfur-bearing atmosphere and carries out vulcanizing treatment, processing method and embodiment
1 is similar, the difference is that N2And H2Gaseous mixture in N2With H2Volume ratio be 3:1, vulcanizing treatment technique is：In initial temperature
When vulcanization 8 is small at 230 DEG C of degree, then be warming up to 400 DEG C continue vulcanization 12 it is small when, vulcanizing treatment is completed to obtain coal bed gas resistant to sulfur and take off
Oxygen integral catalyzer, is denoted as SSL-2.
Embodiment 3
The preparation of coal bed gas sulfur-tolerance deoxidation integral catalyzer, step are as follows：
1) 30.71g boehmites is taken to add in 10mL salpeter solutions, 100mL water is added and reconciles into tie coat slurry
Expect, nitric acid content is 1wt% in tie coat slurry, 5.32g cellular aluminas ceramics is immersed in tie coat slurry, 5 points
It is taken out after clock, then leftover slurry is blown off with compressed air, subsequent 120 DEG C of heated-air dryings, and when 700 DEG C of roastings 2 are small, then weigh
Multiple this impregnates, blows leftover slurry, drying, calcination steps off once, obtains catalyst carrier so that cellular alumina ceramics weightening
1.12g (weightening 17.3%)；
2) by 50gFe (NO3)3·9H2O and 38.9gCo (NO3)2·6H2O is dissolved in 240mL water, and Na is added dropwise2CO3Solution
(concentration 0.5mol/L), 40 DEG C, titration end-point pH=8.0 of controlling reaction temperature, filtering reacting liquid, gained precipitation are washed with water
2 times, with after dry at 120 DEG C, and in 400 DEG C roast 1-2 it is small when obtain oxide powder, the oxide powder that will be obtained
19g adds in 15mL salpeter solutions and 45mL water and carries out wet ball-milling, when ball milling 2 is small after with salpeter solution adjust pH value to 4-5, obtain
To 55mL active component slurries；
3) catalyst carrier obtained by step 1) is immersed in active component slurry obtained by step 2), taken out after five minutes, with pressure
Contracting air blows additional size off, and with 120 DEG C of heated-air dryings, integral catalyzer is obtained with when 500 DEG C of roastings 2 are small, whole
The oxide mass content of active component is 10.5% in formula catalyst, and the mass content of tie coat is 7.8%；
4) integral catalyzer obtained by step 3) is placed in sulfur-bearing atmosphere and carries out vulcanizing treatment, processing method and embodiment
1 is identical, and vulcanizing treatment is completed to obtain coal bed gas sulfur-tolerance deoxidation integral catalyzer, is denoted as SSL-3.
Embodiment 4
The preparation of coal bed gas sulfur-tolerance deoxidation integral catalyzer, step are as follows：
1) 30.71g γ-Al are taken2O3It adds in 10mL salpeter solutions, adds 60mL water and reconcile into tie coat slurry, mistake
It is 2wt% to cross nitric acid content in coating paste, and 7.65g mullites ceramic honey comb is immersed in tie coat slurry, is taken after five minutes
Go out, then leftover slurry is blown off with compressed air, subsequent 120 DEG C of heated-air dryings, and when 700 DEG C of roastings 2 are small, repeat this leaching
It steeps, blow leftover slurry, drying, calcination steps off once, obtain catalyst carrier so that cellular alumina ceramics weightening 0.74g
(weightening 8.8%)；
2) by 6gCoO, 10gMoO3And 14gFe2O315mL salpeter solutions are added in after mixing and 85mL water carries out wet ball-milling,
PH value is adjusted to 4-5 with salpeter solution and water after when ball milling 2 is small, obtains 70mL active component slurries；
3) catalyst carrier obtained by step 1) is immersed in active component slurry obtained by step 2), taken out after five minutes, with pressure
Contracting air blows additional size off, and with 120 DEG C of heated-air dryings, integral catalyzer is obtained with when 500 DEG C of roastings 2 are small, whole
The oxide mass content of active component is 9.5% in formula catalyst, and the mass content of tie coat is 6.6%；
4) integral catalyzer obtained by step 3) is placed in sulfur-bearing atmosphere and carries out vulcanizing treatment, processing method and embodiment
1 is identical, and vulcanizing treatment is completed to obtain coal bed gas sulfur-tolerance deoxidation integral catalyzer, is denoted as SSL-4.
Embodiment 5
Application of the sulfur-tolerance deoxidation integral catalyzer in coal bed gas deoxidation processing：
Test device is as shown in Figure 1, sulfur-tolerance deoxidation integral catalyzer is placed in reacting furnace 5, by unstripped gas input vaporization
Stove 2 is inputted after mixing in reacting furnace 5 in gasification burner 2, and residual gas is discharged after the separation of steam trap 6 after catalytic reaction,
Analyzer 7 is connected to test residual gas component and content with water steam analysis 6.Oxygen content is 1-5%, vulcanizes in unstripped gas
Hydrogen content is 50-200mg/M3, methane content 60-80%, carbon dioxide 10-30%, surplus is nitrogen, by mass flow
1 control gas flow of meter, simulation coal bed gas composition carry out the deoxy performance test of catalyst.
The active testing condition of catalyst is：Normal pressure -0.5MPa, 450-650 DEG C of reaction temperature, air speed 5000-10000h-1, Catalyst packing 35mL, the sample test time for 12 it is small when.
Coal bed gas sulfur-tolerance deoxidation integral catalyzer active testing process conditions prepared by embodiment 1-4 are shown in Table 1：
Table 1
During active testing it is every 2 it is small when survey an exit gas in oxygen content, obtain data and be shown in Table 2：
Table 2
From above-mentioned test result, catalyst deoxidation effect prepared by the embodiment of the present invention is good, through 12h catalytic deoxidations
It handles, oxygen content is down to 0.23-0.35% by initial 1.65-4.53% in coal bed gas, and catalyst does not go out under sulfur-bearing atmosphere
Now apparent deactivation phenomenom.
Claims (6)
1. a kind of coal bed gas sulfur-tolerance deoxidation integral catalyzer, which is characterized in that it is to load base metal by catalyst carrier
Active component oxide/catalyst carrier compound that the oxide of active component obtains is active by base metal through vulcanizing treatment
The oxide of component carries out full cure and obtains, wherein the catalyst carrier is by ceramic honeycomb carrier and ceramic honeycomb carrier
γ-the Al of upper coating2O3Tie coat forms；
The base metal active component is two or more the mixture in Co, Mo, Mn, Fe, Zn；
The vulcanizing treatment is that active component oxide/catalyst carrier compound is placed in sulfur-bearing atmosphere and is carried out at vulcanization
Reason, 200-400 DEG C of curing temperature, the sulfur-bearing atmosphere is by N2、H2And the CS of gasification2Composition, wherein N2With H2Volume ratio be
1-3:1, CS2Quality and N2And H2The ratio of the two total volume is 0.2-0.3g/400mL.
2. coal bed gas sulfur-tolerance deoxidation integral catalyzer according to claim 1, it is characterised in that：The active component oxygen
The oxide mass content of active component is 8-16%, γ-Al in compound/catalyst carrier compound2O3The quality of tie coat
Content is 6-12%.
3. coal bed gas sulfur-tolerance deoxidation integral catalyzer according to claim 1, it is characterised in that：The ceramic honeycomb carries
Body is cordierite honeycomb ceramic, mullite ceramic honey comb or cellular alumina are ceramic.
4. a kind of preparation method of any coal bed gas sulfur-tolerance deoxidation integral catalyzers of claim 1-3, feature exist
In step is as follows：
1）Prepare catalyst carrier：Ceramic honeycomb carrier is immersed in tie coat slurry, is taken out after fully impregnating, blows remnants off
Slurry, then catalyst carrier is obtained through drying, 650-750 DEG C of roasting 1-4h, it repeats to impregnate as needed in preparation process, blow off
Leftover slurry, drying, calcination steps so that ceramic honeycomb carrier weightening 8-18wt%；
2）Prepare active component slurry：The soluble-salt of active component is dissolved in water and obtains solution, after adding in alkali reaction, by gained
The oxide of active component is obtained after washing of precipitate, drying, 400-550 DEG C of roasting 1-4h, then is configured to active component slurry；Or
The carbonate of active component or oxalates mixed pyrolysis are obtained into the oxide of active component, then are configured to active component slurry；
Or the oxide of active component is directly configured to active component slurry；
3）Prepare active component oxide/catalyst carrier compound：By step 1）Gained catalyst carrier immerses step 2）Institute
It obtains in active component slurry, is taken out after fully impregnating, blow leftover slurry off, then lived through drying, 650-750 DEG C of roasting 1-4h
Property component oxide/catalyst carrier compound；
4）Prepare coal bed gas sulfur-tolerance deoxidation integral catalyzer：By step 3）Gained active component oxide/catalyst carrier
Conjunction object, which is placed in sulfur-bearing atmosphere, carries out vulcanizing treatment, and vulcanizing treatment is completed to obtain coal bed gas sulfur-tolerance deoxidation integral catalyzer.
5. the preparation method of coal bed gas sulfur-tolerance deoxidation integral catalyzer according to claim 4, it is characterised in that step
1）The preparation method of the tie coat slurry is：By γ-Al2O3Or one or both of boehmite addition nitric acid is molten
It in liquid, adds water reconciliation and obtains tie coat slurry, tie coat slurry solid content is 15-25%, nitric acid in tie coat slurry
Content is 1-5wt%.
6. the preparation method of coal bed gas sulfur-tolerance deoxidation integral catalyzer according to claim 4, it is characterised in that step
2）The preparation method of the active component slurry is：The oxide of active component is added in into salpeter solution and water carries out wet type ball
Mill, ball milling fully afterwards with nitre acid for adjusting pH value to 4-5 to obtain the final product, active component slurry solid content be 20-25%.
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Denomination of invention: A sulfur resistant deoxygenation integral catalyst for coalbed methane and its preparation method Granted publication date: 20180522 Pledgee: Yunongshang Financial Leasing Co.,Ltd. Pledgor: HAISO TECHNOLOGY Co.,Ltd. Registration number: Y2024980030801 |