CN107497499A - A kind of monoblock type tufted alumina load catalyst and its application - Google Patents
A kind of monoblock type tufted alumina load catalyst and its application Download PDFInfo
- Publication number
- CN107497499A CN107497499A CN201710729336.5A CN201710729336A CN107497499A CN 107497499 A CN107497499 A CN 107497499A CN 201710729336 A CN201710729336 A CN 201710729336A CN 107497499 A CN107497499 A CN 107497499A
- Authority
- CN
- China
- Prior art keywords
- tufted
- monoblock type
- coating
- alumina
- porous ceramic
- Prior art date
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 239000000919 ceramic Substances 0.000 claims abstract description 87
- 239000011159 matrix material Substances 0.000 claims abstract description 72
- 239000011248 coating agent Substances 0.000 claims abstract description 60
- 238000000576 coating method Methods 0.000 claims abstract description 60
- 239000000243 solution Substances 0.000 claims description 54
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 35
- 241000264877 Hippospongia communis Species 0.000 claims description 29
- 238000010276 construction Methods 0.000 claims description 29
- 229910052878 cordierite Inorganic materials 0.000 claims description 26
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 26
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 230000003197 catalytic effect Effects 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000008246 gaseous mixture Substances 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 6
- 238000006057 reforming reaction Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229910010293 ceramic material Inorganic materials 0.000 claims description 5
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229910052573 porcelain Inorganic materials 0.000 claims description 5
- 229910052594 sapphire Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003929 acidic solution Substances 0.000 claims description 3
- 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 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims description 3
- 238000002407 reforming Methods 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 52
- 238000006243 chemical reaction Methods 0.000 description 47
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 46
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 40
- 239000007789 gas Substances 0.000 description 32
- 241000365446 Cordierites Species 0.000 description 26
- 239000011247 coating layer Substances 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- 239000007787 solid Substances 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 20
- 229910052782 aluminium Inorganic materials 0.000 description 14
- 238000001833 catalytic reforming Methods 0.000 description 13
- 238000007654 immersion Methods 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- -1 aluminum ions Chemical class 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910001593 boehmite Inorganic materials 0.000 description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 239000011609 ammonium molybdate Substances 0.000 description 5
- 229940010552 ammonium molybdate Drugs 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 241000256844 Apis mellifera Species 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 238000001935 peptisation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910009112 xH2O Inorganic materials 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- 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
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B01J35/615—
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a kind of monoblock type tufted alumina load catalyst and its application.The carrier includes hierarchical aluminium oxide coating and monolithic porous ceramic matrix；The hierarchical aluminium oxide coating is the micron order nanocluster that the blade for having thickness to be nanometer is piled into, in flower-like structure.
Description
Technical field
The present invention relates to material manufacture and Application in Chemical Engineering field, and in particular to monoblock type tufted alumina load catalyst and
Its catalytic applications.
Background technology
Monolithic construction carrier is a kind of with macro-size, the block formula catalyst carrier of compound with regular structure, inner homogeneous
The fluid passage of certain size is dispersed with, has resistance to mass tranfer small, mass-transfer efficiency is high, the advantages that being easy to assembly and disassembly.It is loaded
Manufactured monolithic construction catalyst has been widely used at the purification of vehicle exhaust and industrial waste gas after catalytic active component
The fields such as reason, catalysis burning.But monolithic construction carrier is mostly high temperature sintering body, such as cordierite honeycomb ceramic, α-Al2O3Bubble
, there is the drawbacks of specific surface area is small in foam ceramics etc., be highly detrimental to the scattered of catalytic active component.
Hierarchy activated alumina has the construction unit and micron and the overall pattern of scale above of nanoscale, energy
Coupling effect and cooperative effect occur on micro-nano yardstick, while making activated alumina that there is bigger serface, can also
Produce some special performances.But when using hierarchy activated alumina as during a kind of coating of monolithic construction carrier,
Its original pattern can not be often kept, so as to which hierarchy can not be made to play respective advantage with monolithic construction.
Therefore, this area is there is an urgent need to provide with excellent resistance to elevated temperatures, and specific surface area it is big can supported catalyst
The monolithic construction carrier of agent.
The content of the invention
A kind of the present invention is intended to provide catalyst with monolithic construction.
In the first aspect of the present invention, there is provided a kind of monoblock type tufted alumina support, the carrier include classification and tied
Structure aluminum oxide coating layer and monolithic porous ceramic matrix；The hierarchical aluminium oxide coating is the blade heap for having thickness to be nanometer
The micron order nanocluster of product, in flower-like structure.
In another preference, the hierarchical aluminium oxide coating is growth in situ on monolithic porous ceramic matrix
Coating.
In another preference, the specific surface area of the coating is 50-150m2/g；The tortuosity of the coating is
1.0-3.5 preferably 1.0-3.0.
In another preference, the monolithic porous ceramic matrix is selected from cordierite honeycomb ceramic, α-Al2O3Foam is made pottery
Porcelain, mullite ceramic honey comb.
In another preference, the weight ratio of the hierarchical aluminium oxide coating and monolithic porous ceramic matrix is 1:
100-1: 3；Preferably 1: 50-1: 5.
In the second aspect of the present invention, there is provided a kind of monoblock type tufted carrying alumina provided by the invention as described above
The preparation method of body, methods described include step：
(1) handle, cool down, treat in high temperature furnace after monolithic porous ceramic matrix is pre-processed in an acidic solution
With；The acid solution is nitric acid, hydrochloric acid or oxalic acid；
(2) alcohol-water that the stand-by monolithic porous ceramic matrix that step (1) obtains is put into aluminum nitrate and urea mixes
Close in solution, kept at 160-180 DEG C 1-24 hours, cooling, washing, obtain being combined with tufted alumina precursor after drying
The monolithic porous ceramic material of (i.e. boehmite) coating；With
(3) after the material that step (2) obtains being soaked into 1-10 minutes in the concentrated sulfuric acid (weight concentration 98%), in 800-
1200 DEG C of roasting 1-24 hours, monoblock type tufted alumina support provided by the invention as described above is obtained after cooling.
In another preference, acid solution weight concentration described in step (1) is 20%-50%；The pretreatment temperature
Spend for 30-95 DEG C.
In another preference, aluminum ions molar concentration is 0.1-10mol/L in step (2) described mixed solution；Institute
The volume ratio for stating mixed solution and monolithic porous ceramic matrix is 5:1-50:1.
In the third aspect of the present invention, there is provided a kind of monoblock type tufted carrying alumina provided by the invention as described above
The purposes of body, carrier as monolithic construction catalyst or for obtaining monolithic construction catalyst.
In the fourth aspect of the present invention, there is provided a kind of monolithic construction catalyst, the catalyst are by as described above
Monoblock type tufted alumina support supporting catalytic active component provided by the invention.
In another preference, with the gross weight meter of catalyst, the weight of the catalytic active component (on the basis of metal)
Amount percentage is 1%-30%.
In another preference, the catalytic active component is selected from W, Mo or Mg single metal oxide or sulfide,
Or W-Mo, W-Mg or Mo-Mg bimetallic oxide or sulfide.
In the fifth aspect of the present invention, there is provided a kind of monolithic construction catalyst provided by the invention as described above
Purposes.
In another preference, reacted for the purified treatment of vehicle exhaust and industrial waste gas, high-temperature catalytic.
In the sixth aspect of the present invention, there is provided a kind of methane hydrogen sulfide catalystic reforming method, described method include step
Suddenly：Make containing CH4、H2S and N2Gaseous mixture by being filled with monolithic construction catalyst provided by the invention as described above
Fixed bed reactors carry out catalytic reforming reaction.
In another preference, H in the gaseous mixture2S volume fractions are 1%-30%, CH4With H2S volume ratios are 10:1-
1:10, remaining is N2。
In another preference, the catalytic reforming reaction temperature is 600-1000 DEG C, gas space velocity 10000-
50000h-1。
Accordingly, the invention provides with excellent resistance to elevated temperatures, and specific surface area it is big can supported catalyst it is whole
Body formula structure carrier.
Brief description of the drawings
Fig. 1 shows the outward appearance of monolithic porous ceramic matrix；Wherein,
A is cordierite honeycomb ceramic, and B is Alpha-alumina foamed ceramics.
Fig. 2 is shown in cordierite honeycomb ceramic with being made after tufted aluminum oxide is respectively coated on Alpha-alumina foamed ceramics
Monoblock type tufted alumina support；Wherein,
A is using cordierite honeycomb ceramic as monoblock type tufted alumina support made of matrix (scale is 0.5 millimeter), a
It is the microscopic appearance (scale is 5 microns) of wherein tufted aluminum oxide,
B is using Alpha-alumina foamed ceramics as monoblock type tufted alumina support made of matrix (scale is 1 millimeter), b
It is the microscopic appearance of wherein tufted aluminum oxide (scale is 5 microns).
Fig. 3 is that the Electronic Speculum of the integral alumina material floating coat of tufted alumina powder coating prepared by comparative example 2 is shone
Piece.
Embodiment
The in-depth study by extensive, inventor make tufted alumina growth monolithic porous using appropriate method
On ceramic matrix surface, the pattern of raw material is maintained, while the specific surface area of matrix is improved, there is resistance to elevated temperatures
The advantages that good；Tufted aluminum oxide coating layer also has open pore passage structure on micro-nano yardstick, is spread when being handled for fluid
Resistance is small.
Further, integral catalyzer will be made after above-mentioned carrier loaded catalytic active component in inventor, applied to sulphur
During methane high-temperature catalytic reforming reaction in the presence of change hydrogen, there is catalytic activity height, service life length, and gas treatment amount
The advantages that big, there is good industrial applications prospect.
On this basis, the present invention is completed.
Monoblock type tufted alumina support
As used in the present invention, " hierarchical aluminium oxide " or " tufted aluminum oxide " is interchangeable, all referring to one kind by
The powder particle material with micro-meter scale that nano alumina particles rule accumulation is formed.It is preferred that the hierarchy oxygen
Change the micron order nanocluster that aluminium is piled into by thickness for the blade of nanometer, in flower-like structure.
As used in the present invention, " monolithic porous ceramic matrix " or " monoblock type ceramic matrix " is interchangeable, and is all
Refer to the one kind prepared using quality raw materials such as emergy, carborundum, cordierites as major ingredient, through overmolding and special high-sintering process
Porous ceramic materials with large aperture, high apparent porosity.
Monoblock type tufted alumina support provided by the invention is by monolithic porous ceramic matrix and hierarchical aluminium oxide
Coating is formed, and described hierarchical aluminium oxide coating has the tufted structure of micro-nano yardstick, i.e., by numerous length in micron
Yardstick, diameter or thickness share one or more fulcrums in the fiber fines or blade of nanoscale and assemble the structure to be formed.Its
The visible accompanying drawing 2 of electron scanning micrograph.
The specific surface area of hierarchical aluminium oxide coating is 50- in monoblock type tufted alumina support provided by the invention
150m2/ g, preferably 60m2/ more than g；The tortuosity of the coating is 1.0-3.5, preferably 1.0-3.0.
Hierarchical aluminium oxide coating and monoblock type ceramic matrix in monoblock type tufted alumina support provided by the invention
Weight ratio be 1:100-1:3, preferably 1:50-1:5.Coating amount is too low, and such as less than 1%, then coating is equivalently employed without, is applied
Layer amount too high 1:3, higher than 33%, then easily cause channel blockage.
Above-mentioned monolithic porous ceramic matrix generally has cordierite honeycomb ceramic and α-Al2O3The major class of foamed ceramics two, is making pottery
It is evenly distributed inside porcelain basal body there is many and the duct with macro-scale, the hole density of ceramic honey comb is generally 200-
600 hole numbers/square inch (psi), the hole density of foamed ceramics is 20-60 hole numbers/inch (ppi).
There is provided monoblock type tufted aluminum oxide is prepared using growth in situ mode combination high-temperature calcination in the present invention
Carrier.Specific steps include：
The first step, monolithic porous ceramic matrix is pre-processed in an acidic solution, washing carries out high temperature after drying
Roasting, obtains pretreated monolithic porous ceramic matrix；
Second step, pretreated monolithic porous ceramic matrix is immersed in a solution, 1-24 is kept at 160-180 DEG C
Cool down, dry after hour, obtain being combined with the monolithic porous ceramic material of tufted alumina precursor (i.e. boehmite) coating；
The solution is the alcohol-water mixed solution of aluminum nitrate and urea；
3rd step, the monolithic porous ceramic material for being combined with tufted alumina precursor (i.e. boehmite) coating that will be obtained
Material is calcined 1-24 hours in the concentrated sulfuric acid (weight concentration 98%) at 800-1200 DEG C after immersion 1-10 minutes, obtain entirety
Formula tufted alumina support.
In the above-mentioned first step, the acid solution is one kind in nitric acid, hydrochloric acid or oxalic acid, and acid solution weight concentration is
20%-50%.
In one embodiment of the invention, the pretreatment temperature in the above-mentioned first step is 30-95 DEG C, and processing time is
1-24 hours.
In one embodiment of the invention, the above-mentioned first step is also included the monolithic porous ceramics by pretreatment
It is washed with deionized after matrix to solution in neutrality, ceramic matrix is put into high temperature furnace after drying and is warming up to 1200 DEG C of processing
It is 6 hours, stand-by after cooling.
In above-mentioned second step, the mol ratio of aluminum nitrate and urea in the alcohol-water mixed solution of the aluminum nitrate and urea
For 1:4-1:20, it is preferred that being 1:5-1:15, the volume ratio of ethanol and water is 20:1-4:1, it is preferred that being 15:1-5:1, mix
It is 0.1-10mol/L to close aluminum ions molar concentration in solution.
In above-mentioned second step, the alcohol-water mixed solution of the aluminum nitrate and urea with it is pretreated monolithic porous
The volume ratio of ceramic matrix is 5:1-50:1.
In one embodiment of the invention, in above-mentioned second step, by pretreated monolithic porous ceramic matrix
Immerse in a solution, keep 1-24 hours after adjusting pH value to neutrality with ammoniacal liquor (weight concentration 25%) at 160-180 DEG C.
In one embodiment of the invention, in above-mentioned second step, by aluminum nitrate and the alcohol-water mixed solution of urea
Enter in high pressure water heating kettle, and immerse pretreated monolithic porous ceramic matrix, the temperature of water heating kettle is adjusted to 160-180 DEG C
Lower constant temperature 1-24 hours, the material of cooling is washed with deionized to filtrate in after neutral after terminating for hydro-thermal reaction, at 120 DEG C
Lower drying 12 hours, then obtain being combined with the monolithic porous ceramics of tufted alumina precursor (i.e. boehmite) coating after cooling down
Material.
Above-mentioned second step, the material that step (2) obtains is soaked into 1-10 minutes in the concentrated sulfuric acid (weight concentration 98%),
It is put into after taking-up in high temperature furnace and is warming up to 800-1200 DEG C of roasting 1-24 hour, described monoblock type tufted oxygen is obtained after cooling
Change Lu porous material.
The water-heat process of above-mentioned second step may be repeated, to meet hierarchical aluminium oxide coating and monolithic porous pottery
The weight of porcelain basal body than requirement.When coating amount is of a relatively high, the total surface area of monolithic substrate is larger, is advantageous to active component
Scattered and catalytic activity raising, but often a water-heat process is difficult to reach higher coating amount, so need repeatedly (such as but
It is not limited to, 2-3 times) repeat water-heat process.The number for repeating water-heat process depends on process conditions and coating demand.And from work
Journey practical term, need to weigh between coating amount and hydro-thermal number, because the increase of hydro-thermal number, it is meant that material cost of manufacture
Also increase.
The monoblock type tufted alumina support that the present invention adopts offer can be used for manufacture monolithic construction catalyst.
Monolithic construction catalyst
Monolithic construction catalyst provided by the invention is to urge the above-mentioned monoblock type tufted alumina support load provided
Agent, it is made up of monoblock type tufted alumina support with catalytic active component.
In one embodiment of the invention, with the gross weight meter of monolithic construction catalyst, wherein catalytic activity group
It is 1%-30%, preferably 2%-25% to divide the percentage by weight (on the basis of metal).
In one embodiment of the invention, there is provided monolithic construction catalyst described in catalytic active component be
W, Mo or Mg single metal oxide or sulfide, or W-Mo, W-Mg, Mo-Mg bimetallic oxide or sulfide.
The deposition of described catalytic active component, method well known in the art can be used, such as, but not limited to impregnates legal system
It is standby.Preparation process is as follows：
(i) by catalytic active component presoma, such as, but not limited to soluble nitrate, haloid, sulfate, mixed with water
Conjunction obtains the solution containing the presoma；
(ii) solution containing the presoma for obtaining step (i) is added drop-wise to monoblock type tufted oxygen provided by the invention
Change in alumina supporter, make matrix complete wetting, obtain sample；
(iii) 1-24h is calcined in 800-1200 DEG C of high temperature furnace after the sample drying for obtaining step (ii), after cooling
Obtain being loaded with the monolithic construction catalyst of active component.
Monolithic construction catalyst provided by the invention, especially suitable for high-temperature catalytic course of reaction, it is such as, but not limited to
Methyl hydride catalyzed reforming reaction process.
Described methane hydrogen sulfide catalytic reforming reaction process, including step：
CH will be contained4、H2S and N2Gaseous mixture, wherein H2S volume fractions are 1%-30%, CH4With H2S volume ratios are 10:
1-1:10, remaining is N2, by being filled with the fixed bed reactors of monolithic construction catalyst provided by the invention, it is catalyzed
Reforming reaction；It is described reaction temperature be 600-1000 DEG C, gas space velocity 10000-50000h-1, normal pressure (0.1-0.2MPa)
Under the conditions of carry out.
Wherein：
The features described above that the present invention mentions, or the feature that embodiment is mentioned can be in any combination.Disclosed in this case specification
All features can be used in combination with any combinations thing form, each feature disclosed in specification, can with it is any provide it is identical,
The alternative characteristics substitution of impartial or similar purpose.Therefore except there is special instruction, disclosed feature is only impartial or similar spy
The general example of sign.
Main advantages of the present invention are：
1st, monolithic construction catalyst provided by the invention monoblock type tufted alumina support provided by the present invention is with urging
Change active component to form, monoblock type tufted alumina support therein is by monolithic porous ceramic matrix and tufted aluminum oxide coating layer
Form, tufted aluminum oxide coating layer possesses the type looks feature of grading structure material, can play the general load of common aluminum oxide simultaneously
Body acts on and the coupling of micro-nano material acts synergistically, and not only pore passage structure opens, and inside diffusional resistance is small, moreover it is possible to is greatly improved
The resistance to elevated temperatures of aluminum oxide so that at reaction of the integral catalyzer obtained especially suitable for large flow fluid under high temperature
Reason.
2nd, monolithic construction catalyst provided by the invention is applied to methane hydrogen sulfide catalytic reforming reaction process, Neng Gouyou
Effect promotes methane conversion synchronous with hydrogen sulfide, and catalyst service life is grown.
The inside diffusional resistance of monoblock type tufted alumina support of the present invention is small, means that fluid applies in tufted aluminum oxide
Resistance when being spread in layer is small, and this is that pore passage structure opening is determined (see accompanying drawing 2a on micro-nano yardstick by tufted aluminum oxide
And 2b), its influence can be represented with tortuosity, and tortuosity is to be used to express solid material pore structure to diffusion process influence
An important engineering parameter【Fang Dingye, etc., using SPSRM determine ammonia synthesis catalyst tortuosity, Industrial Catalysis, 2001
Year, the phase page 61 of volume 9 the 4th】, tortuosity is smaller, then it represents that inside diffusional resistance is small.Described tortuosity can use the world
General SPSRM methods measure.
The resistance to elevated temperatures of monoblock type tufted alumina support of the present invention is good, means tufted aluminum oxide at high temperature
The specific surface area change of coating is little, remains to keep higher value, this aspect be by tufted aluminum oxide on micro-nano yardstick
What steric hindrance caused by structure Coupling determined, due to the presence of steric hindrance, aluminum oxide nanoparticle (blade) can be avoided
Cause specific surface area to be remarkably decreased because reuniting and sintering at high temperature, be that tufted is passed through by the preparation method of uniqueness on the other hand
The stabilization to aluminium oxide structure that aluminum oxide is brought with ceramic matrix strong bonded.Described specific surface area can use the world
General low-temperature physics determination of adsorption method, the ASAP2010 type low temperature N such as, but not limited to produced using Merck ＆ Co., Inc of the U.S.2Thing
Manage adsorption instrument measure.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.The experimental method of unreceipted actual conditions in the following example, generally according to conventional strip
Part or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise all percentage, ratio, ratio or number is pressed
Weight meter.The unit in percent weight in volume in the present invention is well-known to those skilled in the art, such as is referred to 100
The weight of solute in the solution of milliliter.Unless otherwise defined, all specialties used in text are ripe with this area with scientific words
It is identical to practice meaning known to personnel.In addition, any method similar or impartial to described content and material all can be applied to
In the inventive method.Preferable implementation described in text only presents a demonstration with material to be used.
The preparation of monoblock type tufted alumina support
Embodiment 1
The cordierite honeycomb ceramic for taking commercially available hole density to be 400psi, is cut into size 1.0cm × 1.0cm × 2.5cm
Matrix, weight 1.175g, be immersed in 50wt% salpeter solution, carry out pretreatment 24h at 30 DEG C, wash drying,
Then 6h is calcined at 1200 DEG C.Weigh aluminum nitrate (Al (NO3)3·9H2O) 0.1mol, urea 1.0mol are placed in beaker,
Deionized water and absolute ethyl alcohol are added at room temperature so that the volume ratio of ethanol and water is 20 in solution:1, aluminum ions mole dense
Spend for 4mol/L, stir to solid and all dissolve, this solution is moved into high pressure water heating kettle, and immerse pretreated cordierite
The volume ratio of ceramic honey comb matrix, solution and ceramic matrix is 10:1, pH value is adjusted into ammoniacal liquor (weight concentration 25%)
Property, then seal water heating kettle.Water heating kettle is placed in oven heat to 160 DEG C of constant temperature 12h, material is taken out after terminating, spend from
Sub- water washing is to filtrate in neutrality.Obtained material is dried into 12h at 120 DEG C, cools down that (weight concentration is after the concentrated sulfuric acid
98%) immersion 5 minutes, are placed in high temperature furnace after taking-up and are calcined 1h at 800 DEG C in, you can obtain monoblock type tufted oxidation aluminium
The weight ratio of material, wherein tufted aluminum oxide coating layer and cordierite honeycomb ceramic matrix is 1:20, the specific surface area of coating is
150m2/ g, tortuosity 2.32.
Embodiment 2
The mullite ceramic honey comb for taking commercially available hole density to be 600cpsi, is cut into size 1.0cm × 1.0cm × 2.5cm
Matrix, weight 0.975g, be immersed in 20wt% oxalic acid solution and pretreatment 10h carried out at 50 DEG C, wash drying, and
6h is calcined at 1200 DEG C.Weigh aluminum nitrate (Al (NO3)3·9H2O) 0.3mol, urea 3.0mol are placed in beaker, in room temperature
Lower addition deionized water and absolute ethyl alcohol so that the volume ratio of ethanol and water is 10 in solution:1, aluminum ions molar concentration is
0.24mol/L, stir to solid and all dissolve, this solution is moved into high pressure water heating kettle, and immerse pretreated cordierite
The volume ratio of ceramic honey comb matrix, solution and ceramic matrix is 50:1, pH value is adjusted into ammoniacal liquor (weight concentration 25%)
Property, then seal water heating kettle.Water heating kettle is placed in oven heat to 180 DEG C of constant temperature 24h.Material is taken out after end, spend from
Sub- water washing is to filtrate in neutrality.Obtained material is dried into 12h at 120 DEG C, cools down that (weight concentration is after the concentrated sulfuric acid
98%) immersion 10 minutes, are placed in high temperature furnace after taking-up and are calcined 24h at 800 DEG C, you can obtain monoblock type tufted aluminum oxide in
The weight ratio of porous material, wherein tufted aluminum oxide coating layer and cordierite honeycomb ceramic matrix is 1:10, the specific surface area of coating
For 123m2/ g, tortuosity 2.43.
Embodiment 3
The cordierite honeycomb ceramic for taking commercially available hole density to be 400cpsi, is cut into size 1.0cm × 1.0cm × 2.5cm
Matrix, weight 1.175g, be immersed in 30wt% hydrochloric acid solution and pretreatment 1h carried out at 95 DEG C, wash drying, and
6h is calcined at 1200 DEG C.Weigh aluminum nitrate (Al (NO3)3·9H2O) 0.5mol, urea 5.0mol are placed in beaker, in room temperature
Lower addition deionized water and absolute ethyl alcohol so that the volume ratio of ethanol and water is 5 in solution:1, aluminum ions molar concentration is
10mol/L, stir to solid and all dissolve, this solution is moved into high pressure water heating kettle, and immerse pretreated cordierite honeybee
The volume ratio of nest ceramic matrix, solution and ceramic matrix is 20:1, pH value is adjusted to neutrality with ammoniacal liquor (weight concentration 25%),
Then sealing water heating kettle.Water heating kettle is placed in oven heat to 180 DEG C of constant temperature 6h.Material is taken out after hydro-thermal reaction terminates,
It is washed with deionized to filtrate in neutrality, 12h is then dried at 120 DEG C.
Above-mentioned material is reentered into water heating kettle, repeats above-mentioned water-heat process.Then material is put into the concentrated sulfuric acid (weight
Concentration be 98%) in immersion 1 minute, be placed in after taking-up in high temperature furnace and be calcined 6h at 800 DEG C, you can obtain monoblock type tufted oxygen
Change Lu porous material, the weight ratio of wherein tufted aluminum oxide coating layer and cordierite honeycomb ceramic matrix is 1:5, the ratio surface of coating
Product is 143m2/ g, tortuosity 2.67.
Above-mentioned monoblock type tufted alumina material is calcined 1h at 1200 DEG C again, tufted aluminum oxide in the sample after cooling
Specific surface area be 96m2/ g, decline 32.9%, though illustrating that specific surface area has reduced, but still maintain bigger numerical, show this
The monoblock type tufted alumina support that invention provides has resistant to elevated temperatures superperformance.
Comparative example 1 (preparation of the common alumina material of monoblock type, contrasted with embodiment 3)
According to document (Chen Chunbo etc., the preparation of the high firmness cordierite honeycomb coating of Large ratio surface, Industrial Catalysis, 2010
Year the 3rd the 40-45 pages of phase) the disclosed Alumina gel obtained using boehmite powder (Shandong Aluminium Industrial Corp's production) peptization is coating
Slurries, active Al in Alumina gel2O3Content is 35%, and cordierite honeycomb ceramic (hole density 400psi) wall is impregnated
Coating, 12h is then dried in 120 DEG C of baking ovens.Above-mentioned sample is coated with Alumina gel again after taking-up, obtained honeycomb
Sample, which is placed in high temperature furnace, is warming up to 800 DEG C of stable 6h, obtains being coated with active Al after cooling2O3The monoblock type of coating is common
Aluminum oxide porous material sample, active Al2O3The weight of coating is 1 with the weight ratio of cordierite honeycomb matrix:5, coating compares surface
Product is 95m2/ g, tortuosity 4.08.The common alumina material of above-mentioned monoblock type is calcined 1h at 1200 DEG C again, after cooling
Sample in the specific surface area of common aluminum oxide coating layer be only 19m2/ g, decline 80.0%, illustrate that specific surface area drastically declines,
Become very little, illustrate obtained carrier non-refractory.
Comparative example 2 (using tufted alumina powder as raw material, monoblock type tufted oxidation aluminium is prepared using conventional cladding process
Material, is contrasted with embodiment 3)
According to the identical method of comparative example 1, boehmite powder is simply substituted with tufted alumina powder, peptization is applied
Layer slurries, the integral alumina material of tufted alumina powder coating is prepared, the ratio table of coating equally after 800 DEG C of stable 6h
Area is 86m2/ g, tortuosity 3.96.Fig. 3 be coating electromicroscopic photograph, show peptization after tufted aluminum oxide structure
Destroyed, blade sticks together, and loses tufted structure function substantially.
Embodiment 4
The Alpha-alumina foamed ceramics for taking commercially available hole density to be 20ppi, is cut into size 1.0cm × 1.0cm × 2.5cm
Matrix, weight 1.375g, be immersed in 20wt% hydrochloric acid solution and pretreatment 6h carried out at 75 DEG C, wash drying, and
6h is calcined at 1200 DEG C.Weigh aluminum nitrate (Al (NO3)3·9H2O) 0.02mol, urea 0.2mol are placed in beaker, in room temperature
Lower addition deionized water and absolute ethyl alcohol so that the volume ratio of ethanol and water is 4 in solution:1, aluminum ions molar concentration is
1.6mol/L, stir to solid and all dissolve, this solution is moved into high pressure water heating kettle, and immerse pretreated cordierite honeybee
The volume ratio of nest ceramic matrix, solution and ceramic matrix is 5:1, pH value is adjusted to neutrality with ammoniacal liquor (weight concentration 25%),
Then sealing water heating kettle.Water heating kettle is placed in oven heat to 180 DEG C of constant temperature 1h.Material is taken out after hydro-thermal reaction terminates,
It is washed with deionized to filtrate in neutrality, 12h is then dried at 120 DEG C, cools down that (weight concentration is after the concentrated sulfuric acid
98%) immersion 3 minutes, are placed in high temperature furnace after taking-up and are calcined 12h at 800 DEG C, you can obtain monoblock type tufted aluminum oxide in
The weight ratio of material, wherein tufted aluminum oxide coating layer and Alpha-alumina foamed ceramics matrix is 1:100, the specific surface area of coating is
93m2/ g, coating total surface area are 1.28m2, tortuosity 1.89.
Comparative example 3 (cancels concentrated sulfuric acid immersion process, contrast with embodiment 4)
Except cancelling concentrated sulfuric acid immersion process, remaining step and process conditions are same as Example 4, obtained monoblock type cluster
In shape alumina material, the weight ratio of tufted aluminum oxide coating layer and Alpha-alumina foamed ceramics matrix is still 1:100, but coating ratio
Surface area drops to 61m2/g。
To find out its cause, it is due in the presence of sulfuric acid, oxidation aluminium surface can form aluminum sulfate, and aluminum sulfate is at nearly 800 DEG C points
Solution, produces new aluminum oxide, so that aluminum oxide surface roughening, improves specific surface area.In addition, aluminum oxide and nitric acid,
Other aluminium salts such as the aluminum nitrates of the formation such as hydrochloric acid, aluminium chloride all lower temperature (<500 DEG C) under will decompose, can not to oxidation
Aluminium high temperature (>800 DEG C) under specific surface area have an impact, so, after the immersion such as nitric acid or hydrochloric acid is used in trial instead, do not find also not
The specific surface area of tufted aluminum oxide coating layer can be improved.
Embodiment 5
The Alpha-alumina foamed ceramics for taking commercially available hole density to be 60ppi, is cut into size 1.0cm × 1.0cm × 2.5cm
Matrix, weight 1.55g, the oxalic acid solution for being immersed in 40wt% carries out pretreatment 6h at 65 DEG C, washs drying, and
6h is calcined at 1200 DEG C.Weigh aluminum nitrate (Al (NO3)3·9H2O) 0.02mol, urea 2.0mol are placed in beaker, at room temperature
Add deionized water and absolute ethyl alcohol so that the volume ratio of ethanol and water is 10 in solution:1, aluminum ions molar concentration is
0.2mol/L, stir to solid and all dissolve, this solution is moved into high pressure water heating kettle, and immerse pretreated cordierite honeybee
The volume ratio of nest ceramic matrix, solution and ceramic matrix is 40:1, pH value is adjusted to neutrality with ammoniacal liquor (weight concentration 25%),
Then sealing water heating kettle.Water heating kettle is placed in oven heat to 160 DEG C of constant temperature 12h.Material is taken out after hydro-thermal reaction terminates,
It is washed with deionized to filtrate in neutrality, 12h is then dried at 120 DEG C, is reentered into water heating kettle and repeats after cooling
Water-heat process is stated, water-heat process is repeated after terminating again, is combined with tufted alumina precursor (boehmite) by what is obtained afterwards
The Alpha-alumina foamed ceramics of coating immersion 2 minutes in the concentrated sulfuric acid (weight concentration 98%), are placed in high temperature furnace after taking-up
24h is calcined at 1000 DEG C, you can obtains monoblock type tufted alumina material, wherein tufted aluminum oxide coating layer steeps with Alpha-alumina
The weight ratio of foam ceramic matrix is 1:3, the specific surface area of coating is 65m2/ g, tortuosity 3.15.
Embodiment 6
Water-heat process in embodiment 5 is repeated once, process afterwards also with the subsequent process phase in embodiment 5
Together, the weight of tufted aluminum oxide coating layer and Alpha-alumina foamed ceramics matrix in the monoblock type tufted alumina material finally obtained
Than for 1:2, but most ducts are blocked in monolithic construction material, substantially without practical value.
The preparation and application of monolithic construction catalyst
Embodiment 7
Weigh solid ammonium metatungstate ((NH4)6H2W12O40·xH2O) 0.1g, it is placed in beaker, adds quality point at room temperature
Number is 5% oxalic acid solution 5g, is stirred to solid and all dissolves, and it is molten to be made into the ammonium metatungstate that W weight contents are 6.8%
Liquid.The gained cordierite honeycomb of Example 2 be matrix monoblock type tufted aluminum oxide 0.5g, wherein tufted aluminum oxide coating layer with it is whole
The weight ratio of body formula ceramic matrix is 1:10, the specific surface area of coating is 123m2/ g, above-mentioned solution is instilled into sample, at room temperature
24h is placed, is then placed in 120 DEG C of baking ovens, 12h is kept, makes sample drying.Transfer in 1100 DEG C of high temperature furnaces under air atmosphere
Keep 6h.The integral catalyst that W weight contents are 12.0% is obtained after cooling.
Above-mentioned catalyst sample is fitted into fixed bed reactors, is passed through containing CH4、H2S and N2Gaseous mixture, wherein H2S
Volume fraction is 5%, CH4With H2S volume ratios are 5:1, remaining is N2, gas space velocity 50000h-1, it is warming up to 1000 DEG C and is urged
Change reforming reaction.Reactor outlet gas composition is determined after 0.5h, it is 10.2% that methane conversion, which is calculated, hydrogen sulfide conversion
Rate is 53.9%.Both conversion ratios of measure are held essentially constant after 10h.
Embodiment 8
Weigh solid ammonium molybdate ((NH4)6Mo7O24·4H2O) 0.3g, it is placed in beaker, adds deionized water at room temperature
5g, it is stirred to solid and all dissolves, is made into the ammonium molybdate solution that Mo weight contents are 9.1%.The gained violet of Example 1 is blue or green
Stone honeycomb is the monoblock type tufted aluminum oxide 1g of matrix, and the weight ratio of wherein tufted aluminum oxide coating layer and monoblock type ceramic matrix is
1:20, the specific surface area of coating is 150m2/ g, above-mentioned solution is instilled into sample, 24h is placed at room temperature, is then placed in 120 DEG C of bakings
In case, 12h is kept, makes sample drying.Transfer in 800 DEG C of high temperature furnaces, 24h is kept under air atmosphere.Mo is obtained after cooling
Weight content is 13.3% integral catalyzer.
The integral catalyzer sample being prepared is fitted into fixed bed reactors, is passed through containing CH4、H2S and N2It is mixed
Close gas, wherein H2S volume fractions are 1%, CH4With H2S volume ratios are 2:1, remaining is N2, gas space velocity 40000h-1, it is warming up to
800 DEG C of progress catalytic reforming reactions.Reactor outlet gas composition is determined after 0.5h, methane conversion, which is calculated, is
27.8%, hydrogen sulfide conversion ratio is 62.5%.Both conversion ratios of measure are held essentially constant after 10h.
Embodiment 9
Solid magnesium sulfate 1g is weighed, is placed in beaker, addition deionized water is stirred all molten to solid at room temperature
Solution, it is made into the solution that Mg weight contents are 12%.The Alpha-alumina foamed ceramics of Example 4 is the monoblock type tufted oxygen of matrix
Change aluminium 0.5g, the weight ratio of wherein tufted aluminum oxide coating layer and monoblock type ceramic matrix is 1:After 100,800 DEG C are calcined 12 hours
Coating specific surface area be 93m2/g.Above-mentioned solution is instilled into sample, 24h is placed at room temperature, is then placed in 120 DEG C of baking ovens,
12h is kept, makes sample drying.Transfer in 600 DEG C of high temperature furnaces, 24h is kept under air atmosphere.Mg weight is obtained after cooling to contain
Measure the integral catalyzer for 19.4%.
The integral catalyzer sample being prepared is fitted into fixed bed reactors, is passed through containing CH4、H2S and N2It is mixed
Close gas, wherein H2S volume fractions are 25%, CH4With H2S volume ratios are 1:2, remaining is N2, gas space velocity 10000h-1, it is warming up to
600 DEG C of progress catalytic reforming reactions.Reactor outlet gas composition is determined after 0.5h, methane conversion, which is calculated, is
15.3%, hydrogen sulfide conversion ratio is 12.1%.Both conversion ratios of measure keep constant after 10h.
Embodiment 10
It is respectively 0.25g and 1g to weigh solid magnesium sulfate and ammonium molybdate weight, is placed in beaker, at room temperature add go from
Sub- water, which is stirred to solid, all to be dissolved, and is made into the solution of the ion containing Mg and Mo.The cordierite honeycomb ceramic of Example 3 is
The weight ratio of the monoblock type tufted aluminum oxide 2g of matrix, wherein tufted aluminum oxide coating layer and monoblock type ceramic matrix is 1:5,900
DEG C calcining 24 hours after coating specific surface area be 119m2/g.Above-mentioned solution is instilled into sample, places 24h, Ran Houfang at room temperature
Enter in 120 DEG C of baking ovens, keep 12h, make sample drying.Transfer in 700 DEG C of high temperature furnaces, 12h is kept under air atmosphere.After cooling
Obtain the integral catalyzer that Mg and Mo weight contents are respectively 2.0% and 18%.
The integral catalyzer sample being prepared is fitted into fixed bed reactors, is passed through containing CH4、H2S and N2It is mixed
Close gas, wherein H2S volume fractions are 15%, CH4With H2S volume ratios are 1:5, remaining is N2, gas space velocity 20000h-1, it is warming up to
700 DEG C of progress catalytic reforming reactions.Reactor outlet gas composition is determined after 1h, it is 60.1% that methane conversion, which is calculated,
Hydrogen sulfide conversion ratio is 25.9%.Both conversion ratios of measure are held essentially constant after 20h.
Embodiment 11
It is respectively 0.15g and 1.0g to weigh solid magnesium sulfate and ammonium metatungstate weight, is placed in beaker, adds at room temperature
Deionized water, which is stirred to solid, all to be dissolved, and is made into the solution containing Mg and W ion.α-the Al of Example 52O3Foam is made pottery
Porcelain is the monoblock type tufted aluminum oxide 2g of matrix, and the weight ratio of wherein tufted aluminum oxide coating layer and monoblock type ceramic matrix is 1:3,
1200 DEG C calcining 24 hours after coating specific surface area be 50m2Above-mentioned solution is instilled sample by/g, places 24h at room temperature, then
It is put into 120 DEG C of baking ovens, keeps 12h, make sample drying.Transfer in 900 DEG C of high temperature furnaces, 12h is kept under air atmosphere.Cooling
Obtain the integral catalyzer that Mg and W weight contents are respectively 1.0% and 24.0% afterwards.
The integral catalyzer sample being prepared is fitted into fixed bed reactors, is passed through containing CH4、H2S and N2It is mixed
Close gas, wherein H2S volume fractions are 10%, CH4With H2S volume ratios are 1:10, remaining is N2, gas space velocity 30000h-1, heating
To 900 DEG C of progress catalytic reforming reactions.Reactor outlet gas composition is determined after 1h, methane conversion, which is calculated, is
65.8%, hydrogen sulfide conversion ratio is 18.6%.Both conversion ratios of measure are held essentially constant after 20h.
Embodiment 12
It is respectively 0.5g to weigh solid ammonium metatungstate and ammonium molybdate weight, is placed in beaker, adds deionized water at room temperature
It is stirred to solid and all dissolves, is made into the solution of the ion containing W and Mo.The cordierite honeycomb ceramic of Example 2 is matrix
Monoblock type tufted aluminum oxide 2g, the wherein weight ratio of tufted aluminum oxide coating layer and monoblock type ceramic matrix is 1:10,1100 DEG C
Coating specific surface area after calcining 24 hours is 61m2Above-mentioned solution is instilled sample by/g, is placed 24h at room temperature, is then placed in
In 120 DEG C of baking ovens, 12h is kept, makes sample drying.Transfer in 900 DEG C of high temperature furnaces, 12h is kept under air atmosphere.After cooling i.e.
Obtain the integral catalyzer that W and Mo weight contents are respectively 13.0% and 9%.
The integral catalyzer sample being prepared is fitted into fixed bed reactors, is passed through containing CH4、H2S and N2It is mixed
Close gas, wherein H2S volume fractions are 3%, CH4With H2S volume ratios are 10:1, remaining is N2, gas space velocity 45000h-1, it is warming up to
800 DEG C of progress catalytic reforming reactions.Reactor outlet gas composition is determined after 1h, it is 11.7% that methane conversion, which is calculated,
Both conversion ratios of measure are held essentially constant after hydrogen sulfide conversion ratio is 63.3%, 20h.
Comparative example 4 (makees carrier, compared with embodiment 7) using common commercial alumina globule
Weigh solid ammonium metatungstate ((NH4)6H2W12O40·xH2O) 0.5g, it is placed in beaker, adds quality point at room temperature
Number is 5% oxalic acid solution 5g, is stirred to solid and all dissolves, and it is molten to be made into the ammonium metatungstate that W weight contents are 6.8%
Liquid.Common commercial alumina globule (φ 4mm, Shanghai molecular sieve factory) 0.5g is taken, the specific surface area after 24h is calcined at 800 DEG C is
74m2/ g, above-mentioned solution is instilled into sample, 24h is placed at room temperature, is then placed in 120 DEG C of baking ovens, 12h is kept, does sample
It is dry.Transfer in 1100 DEG C of high temperature furnaces and keep 6h under air atmosphere.It is 12.0% spherical to urge that W weight contents are obtained after cooling
Agent.
Above-mentioned catalyst sample is fitted into fixed bed reactors, is passed through containing CH4、H2S and N2Gaseous mixture, wherein H2S
Volume fraction is 5%, CH4With H2S volume ratios are 5:1, remaining is N2, gas space velocity 50000h-1, it is warming up to 1000 DEG C and is urged
Change reforming reaction.Reactor outlet gas composition is determined after 0.5h, it is 5.8% that methane conversion, which is calculated, hydrogen sulfide conversion
Rate is 41.5%.Both conversion ratios of measure drop to 4.7% and 36.4% respectively after 10h.
Comparative example 5 (makees carrier, compared with embodiment 12) using the monoblock type ceramics with common aluminum oxide coating layer
It is respectively 0.5g to weigh solid ammonium metatungstate and ammonium molybdate weight, is placed in beaker, adds deionized water at room temperature
It is stirred to solid and all dissolves, is made into the solution of the ion containing W and Mo.Take α-Al2O3Foamed ceramics is general for the monoblock type of matrix
Logical aluminum oxide is (according to document：Chen Chunbo etc., the preparation of the high firmness cordierite honeycomb coating of Large ratio surface, Industrial Catalysis, 2010
It is prepared by the method described in the 3rd the 40-45 pages of the phase of year) 2g, wherein the weight of common aluminum oxide coating layer and monoblock type ceramic matrix
Than for 1:The specific surface area of common aluminum oxide coating layer is 28.2m after calcining 24h at 10,1100 DEG C2/ g, above-mentioned solution is instilled into sample
Product, 24h is placed at room temperature, be then placed in 120 DEG C of baking ovens, keep 12h, make sample drying.Transfer to 900 DEG C of high temperature furnaces
In, keep 12h under air atmosphere.The integral catalyzer that W and Mo weight contents are respectively 13.0% and 9% is obtained after cooling.
The integral catalyzer sample being prepared is fitted into fixed bed reactors, is passed through containing CH4、H2S and N2It is mixed
Close gas, wherein H2S volume fractions are 3%, CH4With H2S volume ratios are 10:1, remaining is N2, gas space velocity 45000h-1, it is warming up to
800 DEG C of progress catalytic reforming reactions.Reactor outlet gas composition is determined after 1h, it is 6.4% that methane conversion, which is calculated, sulphur
Change both conversion ratios of measure, methane 3.8%, hydrogen sulfide 25.5% after hydrogen conversion ratio is 39.3%, 20h.
Comparative example 6 (prepares monoblock type tufted alumina material using conventional cladding process and makees carrier, compared with embodiment 12
Compared with)
The solution of the ion containing W and Mo is prepared first.Using the monoblock type being prepared in comparative example 2 by conventional cladding process
The weight ratio of tufted alumina support 2g, wherein tufted aluminum oxide coating layer and monoblock type ceramic matrix is 1:Forged at 10,1100 DEG C
The specific surface area of common aluminum oxide coating layer is 37.8m after burning 24h2/g.Then above-mentioned solution is instilled into carrier, placed at room temperature
24h, it is then placed in 120 DEG C of baking ovens, keeps 12h, make sample drying.Transfer in 900 DEG C of high temperature furnaces, kept under air atmosphere
12h.The integral catalyzer that W and Mo weight contents are respectively 13.0% and 9% is obtained after cooling.
The integral catalyzer sample being prepared is fitted into fixed bed reactors, is passed through containing CH4、H2S and N2It is mixed
Close gas, wherein H2S volume fractions are 3%, CH4With H2S volume ratios are 10:1, remaining is N2, gas space velocity 45000h-1, it is warming up to
800 DEG C of progress catalytic reforming reactions.Reactor outlet gas composition is determined after 1h, it is 7.9% that methane conversion, which is calculated, sulphur
Change both conversion ratios of measure, methane 6.8%, hydrogen sulfide 41.5% after hydrogen conversion ratio is 50.4%, 20h.
Comparative example 7 (cancel concentrated sulfuric acid immersion, use concentrated hydrochloric acid immersion instead, prepare monoblock type tufted alumina material and make carrier,
Compared with embodiment 7)
First, the monoblock type tufted aluminum oxide that cordierite honeycomb ceramic is matrix is prepared：Step in embodiment 2 and
Process conditions are operated, but concentrated sulfuric acid immersion is changed into concentrated hydrochloric acid and soaked, in obtained monoblock type tufted alumina material, cluster
The weight ratio of shape aluminum oxide coating layer and cordierite honeycomb ceramic matrix is still 1:10, but coating compares surface after roasting 24h at 800 DEG C
Product drops to 93.1m2Coating specific surface area continues to drop to 45.2m after/g, 1200 DEG C of roasting 24h2/g.Secondly, according to embodiment
7 prepare integral catalyzer, obtain the integral catalyst that W weight contents are 12.0%.Finally, should by the integral catalyzer
For hydrogen sulfide-methane reforming reaction：It is passed through containing CH4、H2S and N2Gaseous mixture, wherein H2S volume fractions are 5%, CH4With
H2S volume ratios are 5:1, remaining is N2, gas space velocity 50000h-1, it is warming up to 1000 DEG C of progress catalytic reforming reactions.Surveyed after 0.5h
Determine reactor outlet gas composition, it is 6.4% that methane conversion, which is calculated, and hydrogen sulfide conversion ratio is 31.6%.Determined after 10h
Both are held essentially constant conversion ratio.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not limited to the substantial technological content model of the present invention
Enclose, substantial technological content of the invention is broadly to be defined in the right of application, any technology that other people complete
Entity or method, if with the right of application defined in it is identical, also or a kind of equivalent change, will
It is considered as being covered by among the right.
Claims (10)
1. a kind of monoblock type tufted alumina support, it is characterised in that the carrier includes hierarchical aluminium oxide coating and whole
Body formula porous ceramic matrices suitable；The hierarchical aluminium oxide coating is the micron order tufted that the blade for having thickness to be nanometer is piled into
Thing, in flower-like structure.
2. carrier as claimed in claim 1, it is characterised in that the hierarchical aluminium oxide coating is growth in situ in entirety
Coating on formula porous ceramic matrices suitable.
3. carrier as claimed in claim 1, it is characterised in that the specific surface area of the coating is 50-150m2/g；The coating
Tortuosity be 1.0-3.5 (preferably 1.0-3.0).
4. carrier as claimed in claim 1, it is characterised in that the monolithic porous ceramic matrix is made pottery selected from cordierite honeycomb
Porcelain, α-Al2O3Foamed ceramics, mullite ceramic honey comb.
5. the carrier as described in claim any one of 1-4, it is characterised in that the hierarchical aluminium oxide coating and monoblock type
The weight ratio of porous ceramic matrices suitable is 1: 100-1: 3；Preferably 1: 50-1: 5.
A kind of 6. preparation method of monoblock type tufted alumina support as described in claim any one of 1-5, it is characterised in that
Methods described includes step：
(1) handled after monolithic porous ceramic matrix is pre-processed in an acidic solution in high temperature furnace, cool down, be stand-by；
The acid solution is nitric acid, hydrochloric acid or oxalic acid；
(2) by the stand-by monolithic porous ceramic matrix that step (1) obtains be put into aluminum nitrate mix with the alcohol-water of urea it is molten
In liquid, kept at 160-180 DEG C 1-24 hours, cooling, washing, obtain being combined with tufted alumina precursor (i.e. suddenly after drying
Nurse stone) coating monolithic porous ceramic material；
(3) after the material that step (2) obtains being soaked into 1-10 minutes in the concentrated sulfuric acid (weight concentration 98%), in 800-1200
DEG C roasting 1-24 hours, the monoblock type tufted alumina support as described in claim any one of 1-5 is obtained after cooling.
7. the purposes of a kind of monoblock type tufted alumina support as described in claim any one of 1-5, it is characterised in that be used as
The carrier of monolithic construction catalyst or for obtaining monolithic construction catalyst.
8. a kind of monolithic construction catalyst, it is characterised in that the catalyst is as described in claim any one of 1-5
Monoblock type tufted alumina support supporting catalytic active component.
A kind of 9. purposes of monolithic construction catalyst as claimed in claim 8.
10. a kind of methane hydrogen sulfide catalystic reforming method, it is characterised in that described method includes step：Make containing CH4、H2S
And N2Gaseous mixture be catalyzed by the fixed bed reactors for being filled with monolithic construction catalyst as claimed in claim 8
Reforming reaction.
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| CN104826668A (en) * | 2014-02-11 | 2015-08-12 | 现代自动车株式会社 | Catalyst carrier for purification of exhausted gas, method for preparing the same, and catalyst for purification of exhausted gas |
| CN113101948A (en) * | 2021-04-15 | 2021-07-13 | 华东理工大学 | Catalyst for methane-hydrogen sulfide reforming hydrogen production process and regeneration method thereof |
| CN114073945A (en) * | 2020-08-21 | 2022-02-22 | 中国石油天然气股份有限公司 | Composite alumina catalyst and preparation method and application thereof |
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| CN101913912A (en) * | 2010-07-02 | 2010-12-15 | 华东理工大学 | Method for coating cordierite honeycomb |
| JP2011092852A (en) * | 2009-10-29 | 2011-05-12 | Asahi Kasei Corp | Composite monolithic catalyst for cleaning exhaust gas |
| CN102259901A (en) * | 2011-05-23 | 2011-11-30 | 华东理工大学 | Hierarchical aluminium oxide and catalysis application thereof |
| CN102718236A (en) * | 2012-05-10 | 2012-10-10 | 华东理工大学 | Activated alumina with vane possessing oriented staging structure and preparation method |
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| CN1652869A (en) * | 2002-04-12 | 2005-08-10 | 康宁股份有限公司 | In situ theta alumina coated monolithic catalyst supports |
| JP2011092852A (en) * | 2009-10-29 | 2011-05-12 | Asahi Kasei Corp | Composite monolithic catalyst for cleaning exhaust gas |
| CN101913912A (en) * | 2010-07-02 | 2010-12-15 | 华东理工大学 | Method for coating cordierite honeycomb |
| CN102259901A (en) * | 2011-05-23 | 2011-11-30 | 华东理工大学 | Hierarchical aluminium oxide and catalysis application thereof |
| CN102718236A (en) * | 2012-05-10 | 2012-10-10 | 华东理工大学 | Activated alumina with vane possessing oriented staging structure and preparation method |
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| CN104826668A (en) * | 2014-02-11 | 2015-08-12 | 现代自动车株式会社 | Catalyst carrier for purification of exhausted gas, method for preparing the same, and catalyst for purification of exhausted gas |
| CN114073945A (en) * | 2020-08-21 | 2022-02-22 | 中国石油天然气股份有限公司 | Composite alumina catalyst and preparation method and application thereof |
| CN114073945B (en) * | 2020-08-21 | 2023-05-26 | 中国石油天然气股份有限公司 | Composite alumina catalyst and preparation method and application thereof |
| CN113101948A (en) * | 2021-04-15 | 2021-07-13 | 华东理工大学 | Catalyst for methane-hydrogen sulfide reforming hydrogen production process and regeneration method thereof |
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| CN107497499B (en) | 2020-05-05 |
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