CN105562030B - Alchlor catalyst for recovering sulfur of resistance to sulfation and preparation method thereof - Google Patents
Alchlor catalyst for recovering sulfur of resistance to sulfation and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 18
- 239000011593 sulfur Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000019635 sulfation Effects 0.000 title claims abstract description 10
- 238000005670 sulfation reaction Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 47
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 23
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 13
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 239000004411 aluminium Substances 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 26
- 229910001593 boehmite Inorganic materials 0.000 claims description 18
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 5
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 7
- 238000005245 sintering Methods 0.000 abstract description 5
- 231100000572 poisoning Toxicity 0.000 abstract description 2
- 230000000607 poisoning effect Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 15
- 229910002651 NO3 Inorganic materials 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000007654 immersion Methods 0.000 description 12
- 238000000643 oven drying Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 235000001508 sulfur Nutrition 0.000 description 12
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000003223 protective agent Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 241001370940 Dercas lycorias Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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 present invention relates to alchlor catalyst for recovering sulfur of resistance to sulfation and preparation method thereof, the catalyst is by active alchlor, graphene, Fe2O3Formed with R oxide, by weight percentage：Active oxidation aluminium content 75%~90%, graphene content are 1%~10%, Fe2O3The oxide content that content is 1%~8%, R is 0.5% 7%, and described R oxide is MnO2Or CuO.The present invention also provides the preparation method of the catalyst.Catalyst of the present invention overcomes it due to micro O compared with common aluminium oxide catalyst2And SO2Presence the shortcomings that being also easy to produce Sulphated Poisoning, and the shortcomings that active alundum (Al2O3) is easy to hydrothermal sintering and inactivated.
Description
Technical field
The present invention relates to a kind of alchlor catalyst for recovering sulfur of resistance to sulfation and preparation method thereof, particularly one
Kind is with high claus reaction activity and catalyst for recovering sulfur of long-life and preparation method thereof.
Background technology
Catalyst for recovering sulfur mainly makes caused H in fossil fuel process2S is changed into the member of non-toxic and safe
Plain sulphur.A large amount of H are produced in the process of oil, natural gas and coking of coal2S gases, for environmental protection and recovery sulphur member
Element, H is generally industrially contained using claus process processing2S sour gas environment protection, its main technique include：It is acid
H in gas2S partial oxidations in combustion furnace generate SO2, SO2With remaining H2S reaction generation elementary sulfurs；The H not reacted2S and
SO2Continue to react into follow-up claus reaction device, the key reaction equation in combustion furnace is as follows：
H2S+2/3O2=SO2+H2O (1)
H2S+SO2=3/xSx+2H2O (2)
Except reacting in addition to (1) (2), the SO in combustion furnace and follow-up claus reaction device2It is also possible to be oxidized to SO3,
And traditional claus catalyst is active alundum (Al2O3), during device long-play, in acid atmosphere and hydro-thermal bar
Under part, alundum (Al2O3) is gradually by SO3Poison or SO2Irreversible Adsorption (sulfation) and sintering and inactivate, have impact on device
Long, peace, steady operation.At present for solve this problem more using above claus catalyst load iron-based be left out oxygen protective agent or
Directly use the titanium-based catalyst of resistance to sulfation.The omitted oxygen protective agent of iron-based can prevent SO3Generation, but to SO2It is irreversible
Adsorption effect is little.Not only cost is high for Ti-base catalyst, and mechanical strength is low, and abrasion are high, increase operation difficulty.
In order to improve the activity of aluminum trioxide catalyst and life-span, it is necessary to poison and water resistant thermal sintering from sulfate resistance
Two aspects are started with.Traditional iron-based is left out oxygen protective agent by being catalyzed O2To H2S selective oxidation reaction generation sulphur, makes burning
Unreacted O in stove2(leakage oxygen) removes, and then effectively suppresses SO in claus reaction device2+O2Generate SO3Reaction, so as to reach
To the purpose of sulfuric-resisting salinization.But the concentration of " leakage oxygen " is usually less than 1% in claus reaction device so that de- " leakage oxygen " reaction
It is less efficient.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of alchlor catalyst for recovering sulfur of resistance to sulfation
Preparation method.
Summary of the invention
The present invention is effectively improved redox reaction process, and then improve catalytic efficiency by the compound of metal oxide.
I.e.：By coupling to form metal composite oxide Mn or Cu and Fe oxide, reach de- " leakage oxygen " catalytic efficiency of raising.This
Invention is directed to Al2O3Base catalyst for recovering sulfur is to SO2Irreversible Adsorption and hydrothermal sintering during easily aggregation the defects of,
By adding graphene come Modification on Al2O3, so as to reduce SO2Adsorption strength and reduce Al2O3The aggregation of particle；Simultaneously can be effective
Increase specific surface area of catalyst, improve the service life of catalyst.
Detailed description of the invention
Technical scheme is as follows：
A kind of alchlor catalyst for recovering sulfur of resistance to sulfation, the catalyst by active alchlor, graphene,
Fe2O3Formed with R oxide, by weight percentage：Active oxidation aluminium content 75%~90%, graphene content be 1%~
10%, Fe2O3The oxide content that content is 1%~8%, R is 0.5%-7%, and described R oxide is MnO2Or CuO.
, according to the invention it is preferred to, the composition of described catalyst is by weight percentage：Active oxidation aluminium content 80%
~85%, graphene content is 3%~8%, Fe2O3The oxide content that content is 2%~6%, R is 1%-6%.
, according to the invention it is preferred to, the specific surface area of described catalyst is 230-350m2/ g, average crush strength are
270-310N/cm。
According to the present invention, the preparation method of above-mentioned catalyst, including step are as follows：
(1) by graphene ultrasonic disperse in water, add boehmite and be well mixed；
(2) material for obtaining step (1), MnO is added2Or CuO, mediate uniform, drying；
(3) material after being dried obtained by step (2) is impregnated in 1-15h in iron salt solutions, dried again after the completion of dipping；
(4) material after step (3) is dried constant temperature 3-6 hours, produces finished catalyst in 450-550 DEG C.
, according to the invention it is preferred to, the mass ratio of graphene and boehmite described in step (1) is (1-10)：
125, further preferred (3-8)：125.
, according to the invention it is preferred to, MnO in step (2)2Or CuO and the boehmite in step (1) mass ratio are
(1-8)：125, further preferred (2-6)：125.
, according to the invention it is preferred to, the iron salt solutions described in step (3) are iron nitrate solution；It is further preferred that nitre
The concentration of sour ferrous solution is 5%-30%g/mL.
, according to the invention it is preferred to, holding temperature is 500 DEG C in step (4).
, according to the invention it is preferred to, the drying described in step (2) and (3) is to dry 12h at 110 DEG C.
The catalyst Applicable temperature of the present invention is 200~360 DEG C, is 500~3000h in gas volume air speed-1Condition
Lower use.Claus reaction of the catalyst of the present invention suitable for Sulfur Recovery Procedure Gas.
Beneficial effects of the present invention：
1st, catalyst of the present invention overcomes it due to micro O compared with common aluminium oxide catalyst2And SO2Presence easily produce
The shortcomings that raw Sulphated Poisoning, and the shortcomings that active alundum (Al2O3) is easy to hydrothermal sintering and inactivated.
2nd, catalyst of the present invention has Crouse's activity is higher, resistance to sulfation ability is strong etc. compared with traditional catalyst
Advantage.
Embodiment
Below by specific embodiment, the invention will be further described, but not limited to this.
Embodiment 1：
Graphene 5g is weighed, is added in 100mL water, ultrasonic disperse is uniform, then weighs 125g boehmite (water content
24.5%), it is added in above-mentioned graphene aqueous solution, after stirring, is added in banded extruder, then adds 3g to enter MnO2Continue to pinch
Close 1 hour, be then extruded into φ 3mm bar shaped, be put into 110 DEG C × 12h of baking oven drying；Weigh the water ferric nitrate (Fe of 10g nine
(NO3)3·9H2O), add room temperature immersion above-mentioned bar samples 12h, 110 DEG C × 12h drying after the dissolving of 100mL water, with 15 DEG C/
Min heating rate produces catalyst sample A to 500 DEG C of roasting 4h.Sample specific surface area 276m2/ g, average crush strength
292N/cm。
Embodiment 2：
Graphene 5g is weighed, is added in 100mL water, ultrasonic disperse is uniform, then weighs 125g boehmite (water content
24.5%), it is added in above-mentioned graphene aqueous solution, after stirring, is added in banded extruder, then adds 3g to enter MnO2Continue to pinch
Close 1 hour, be then extruded into φ 3mm bar shaped, be put into 110 DEG C × 12h of baking oven drying；Weigh the water ferric nitrate (Fe of 15g nine
(NO3)3·9H2O), room temperature immersion after the dissolving of the 100mL water above-mentioned bar samples 12h handled with graphene is added, 110 DEG C ×
12h is dried, and catalyst sample B is produced with 15 DEG C/min heating rate to 500 DEG C of roasting 4h.Sample specific surface area 267m2/
G, average crush strength 290N/cm.
Embodiment 3：
Graphene 5g is weighed, is added in 100mL water, ultrasonic disperse is uniform, then weighs 125g boehmite (water content
24.5%), it is added in above-mentioned graphene aqueous solution, after stirring, is added in banded extruder, then adds 3g to enter MnO2Continue to pinch
Close 1 hour, be then extruded into φ 3mm bar shaped, be put into 110 DEG C × 12h of baking oven drying；Weigh the water ferric nitrate (Fe of 20g nine
(NO3)3·9H2O), room temperature immersion after the dissolving of the 100mL water above-mentioned bar samples 12h handled with graphene is added, 110 DEG C ×
12h is dried, and catalyst sample C is produced with 15 DEG C/min heating rate to 500 DEG C of roasting 4h.Sample specific surface area 261m2/
G, average crush strength 281N/cm.
Embodiment 4：
Graphene 5g is weighed, is added in 100mL water, ultrasonic disperse is uniform, then weighs 125g boehmite (water content
24.5%), it is added in above-mentioned graphene aqueous solution, after stirring, is added in banded extruder, then adds 3g to enter MnO2Continue to pinch
Close 1 hour, be then extruded into φ 3mm bar shaped, be put into 110 DEG C × 12h of baking oven drying；Weigh the water ferric nitrate (Fe of 25g nine
(NO3)3·9H2O), room temperature immersion after the dissolving of the 100mL water above-mentioned bar samples 12h handled with graphene is added, 110 DEG C ×
12h is dried, and catalyst sample D is produced with 15 DEG C/min heating rate to 500 DEG C of roasting 4h.Sample specific surface area 281m2/
G, average crush strength 282N/cm.
Embodiment 5：
Graphene 5g is weighed, is added in 100mL water, ultrasonic disperse is uniform, then weighs 125g boehmite (water content
24.5%), it is added in above-mentioned graphene aqueous solution, after stirring, is added in banded extruder, then adds 1g to enter MnO2Continue to pinch
Close 1 hour, be then extruded into φ 3mm bar shaped, be put into 110 DEG C × 12h of baking oven drying；Weigh the water ferric nitrate (Fe of 20g nine
(NO3)3·9H2O), room temperature immersion after the dissolving of the 100mL water above-mentioned bar samples 12h handled with graphene is added, 110 DEG C ×
12h is dried, and catalyst sample E is produced with 15 DEG C/min heating rate to 500 DEG C of roasting 4h.Sample specific surface area 284m2/
G, average crush strength 296N/cm.
Embodiment 6：
Graphene 5g is weighed, is added in 100mL water, ultrasonic disperse is uniform, then weighs 125g boehmite (water content
24.5%), it is added in above-mentioned graphene aqueous solution, after stirring, is added in banded extruder, then adds 6g to enter MnO2Continue to pinch
Close 1 hour, be then extruded into φ 3mm bar shaped, be put into 110 DEG C × 12h of baking oven drying；Weigh the water ferric nitrate (Fe of 20g nine
(NO3)3·9H2O), room temperature immersion after the dissolving of the 100mL water above-mentioned bar samples 12h handled with graphene is added, 110 DEG C ×
12h is dried, and catalyst sample F is produced with 15 DEG C/min heating rate to 500 DEG C of roasting 4h.Sample specific surface area 258m2/
G, average crush strength 301N/cm.
Embodiment 7：
Graphene 3g is weighed, is added in 100mL water, ultrasonic disperse is uniform, then weighs 125g boehmite (water content
24.5%), it is added in above-mentioned graphene aqueous solution, after stirring, is added in banded extruder, then adds 3g to enter MnO2Continue to pinch
Close 1 hour, be then extruded into φ 3mm bar shaped, be put into 110 DEG C × 12h of baking oven drying；Weigh the water ferric nitrate (Fe of 20g nine
(NO3)3·9H2O), room temperature immersion after the dissolving of the 100mL water above-mentioned bar samples 12h handled with graphene is added, 110 DEG C ×
12h is dried, and catalyst sample G is produced with 15 DEG C/min heating rate to 500 DEG C of roasting 4h.Sample specific surface area 248m2/
G, average crush strength 308N/cm.
Embodiment 8：
Graphene 8g is weighed, is added in 100mL water, ultrasonic disperse is uniform, then weighs 125g boehmite (water content
24.5%), it is added in above-mentioned graphene aqueous solution, after stirring, is added in banded extruder, then adds 3g to enter MnO2Continue to pinch
Close 1 hour, be then extruded into φ 3mm bar shaped, be put into 110 DEG C × 12h of baking oven drying；Weigh the water ferric nitrate (Fe of 20g nine
(NO3)3·9H2O), room temperature immersion after the dissolving of the 100mL water above-mentioned bar samples 12h handled with graphene is added, 110 DEG C ×
12h is dried, and catalyst sample H is produced with 15 DEG C/min heating rate to 500 DEG C of roasting 4h.Sample specific surface area 312m2/
G, average crush strength 271N/cm.
Embodiment 9：
Graphene 5g is weighed, is added in 100mL water, ultrasonic disperse is uniform, then weighs 125g boehmite (water content
24.5%), it is added in above-mentioned graphene aqueous solution, after stirring, is added in banded extruder, then adds 3g to enter CuO and continue to pinch
Close 1 hour, be then extruded into φ 3mm bar shaped, be put into 110 DEG C × 12h of baking oven drying；Weigh the water ferric nitrate (Fe of 10g nine
(NO3)3·9H2O), room temperature immersion after the dissolving of the 100mL water above-mentioned bar samples 12h handled with graphene is added, 110 DEG C ×
12h is dried, and catalyst sample I is produced with 15 DEG C/min heating rate to 500 DEG C of roasting 4h.Sample specific surface area 279m2/
G, average crush strength 290N/cm.
Embodiment 10：
Graphene 8g is weighed, is added in 100mL water, ultrasonic disperse is uniform, then weighs 125g boehmite (water content
24.5%), it is added in above-mentioned graphene aqueous solution, after stirring, is added in banded extruder, then adds 3g to enter CuO and continue to pinch
Close 1 hour, be then extruded into φ 3mm bar shaped, be put into 110 DEG C × 12h of baking oven drying；Weigh the water ferric nitrate (Fe of 20g nine
(NO3)3·9H2O), room temperature immersion after the dissolving of the 100mL water above-mentioned bar samples 12h handled with graphene is added, 110 DEG C ×
12h is dried, and catalyst sample J is produced with 15 DEG C/min heating rate to 500 DEG C of roasting 4h.Sample specific surface area 311m2/
G, average crush strength 278N/cm.
Embodiment 11：
Graphene 5g is weighed, is added in 100mL water, ultrasonic disperse is uniform, then weighs 125g boehmite (water content
24.5%), it is added in above-mentioned graphene aqueous solution, after stirring, is added in banded extruder, then adds 6g to enter CuO and continue to pinch
Close 1 hour, be then extruded into φ 3mm bar shaped, be put into 110 DEG C × 12h of baking oven drying；Weigh the water ferric nitrate (Fe of 20g nine
(NO3)3·9H2O), room temperature immersion after the dissolving of the 100mL water above-mentioned bar samples 12h handled with graphene is added, 110 DEG C ×
12h is dried, and catalyst sample K is produced with 15 DEG C/min heating rate to 500 DEG C of roasting 4h.Sample specific surface area 262m2/
G, average crush strength 294N/cm.
Embodiment 12：
Graphene 8g is weighed, is added in 100mL water, ultrasonic disperse is uniform, then weighs 125g boehmite (water content
24.5%), it is added in above-mentioned graphene aqueous solution, after stirring, is added in banded extruder, then adds 1g to enter CuO and continue to pinch
Close 1 hour, be then extruded into φ 3mm bar shaped, be put into 110 DEG C × 12h of baking oven drying；Weigh the water ferric nitrate (Fe of 20g nine
(NO3)3·9H2O), room temperature immersion after the dissolving of the 100mL water above-mentioned bar samples 12h handled with graphene is added, 110 DEG C ×
12h is dried, and catalyst sample L is produced with 15 DEG C/min heating rate to 500 DEG C of roasting 4h.Sample specific surface area 306m2/
G, average crush strength 282N/cm.
Test example 1：
Catalyst sample made from embodiment 1-12 is ground into 20~40 mesh, it is 14mm's then to take 5mL to load internal diameter
In stainless steel qualitative response device, the quartz sand of top filling same particle sizes carries out mixing preheating.Reacting furnace uses Electric heating, urges
Agent bed position approximation isothermal body of heater.Using Japanese Shimadzu GC-14B gas chromatograph on-line analysis reactor inlets and outlet
H in gas2S, SO2Content, using GDX-301 carriers analyze sulfide, using 5A molecule mesh analysis O2Content, column temperature 120
DEG C, thermal conductivity detector (TCD), hydrogen is carrier gas, flow velocity 28mL/min after post.
With H2S+SO2→3S+H2O reacts for index, investigates Crouse's activity of catalyst sample, and inlet gas composition is
H2S 2%, SO21%, O23000ppm, H2O 30%, remaining is N2, gas volume air speed is 2500h-1, reaction temperature 230
DEG C, according to the Glaus conversion of following formula calculating catalyst：
Wherein M0, M1Entrance and exit H are represented respectively2S and SO2Volumetric concentration and.
Catalyst sample A~L Activity evaluation is shown in table 1, and activity data therein is what is continuously run within 48 hours
Average value.
The activity contrast of the different catalysts sample of table 1.
M*, N* are a kind of industrial iron-based catalyst for recovering sulfur generally used and the catalysis of activated alumina sulphur recovery
Agent, its main component are activated alumina and iron oxide or pure alumina, similarly hereinafter.
Test example 2：
According to the claus reaction evaluation method of test example 1,500 hours claus reaction test runs are investigated, are as a result shown
In table 2.
2. 500 hours catalyst sample C and J of table and control sample M*, N* claus reaction test run result
| Time, h | 40 | 80 | 120 | 160 | 200 | 240 | 300 | 340 | 400 | 450 | 500 |
| Catalyst sample C | 77 | 76 | 76 | 77 | 76 | 76 | 75 | 76 | 76 | 75 | 76 |
| Catalyst sample J | 77 | 77 | 77 | 77 | 76 | 76 | 75 | 76 | 75 | 76 | 75 |
| M* | 74 | 73 | 73 | 73 | 71 | 71 | 70 | 71 | 70 | 71 | 70 |
| N* | 71 | 71 | 71 | 70 | 68 | 68 | 67 | 66 | 64 | 64 | 63 |
The operating of 500 hours has little to no effect to catalyst sample C and J it can be seen from the result of table 2, and control sample
M*, N* have started to active downward trend, illustrate that catalyst sample C and J sulfate resistance ability are strong, catalyst life is excellent
In the iron-based catalyst for recovering sulfur and activated alumina catalyst for recovering sulfur that industrially generally use.
Claims (11)
1. a kind of aluminum oxide catalyst for recovering sulfur of resistance to sulfation, it is characterised in that the catalyst is by activated alumina, stone
Black alkene, Fe2O3Formed with R oxide, by weight percentage：Active oxidation aluminium content 75% ~ 90%, graphene content be 1% ~
10%, Fe2O3The oxide content that content is 1% ~ 8%, R is 0.5%-7%, and described R oxide is MnO2Or CuO.
2. aluminum oxide catalyst for recovering sulfur according to claim 1, it is characterised in that the composition of described catalyst is pressed
Percentage by weight meter：Active oxidation aluminium content 80% ~ 85%, graphene content are 3% ~ 8%, Fe2O3Content is 2% ~ 6%, R oxidation
Thing content is 1%-6%.
3. aluminum oxide catalyst for recovering sulfur according to claim 1, it is characterised in that the ratio surface of described catalyst
Product is 230-350 m2/g。
4. aluminum oxide catalyst for recovering sulfur according to claim 1, it is characterised in that the mean pressure of described catalyst
Broken intensity is 270-310N/cm.
5. a kind of preparation method of the aluminum oxide catalyst for recovering sulfur described in claim 1, including step are as follows：
（1）By graphene ultrasonic disperse in water, add boehmite and be well mixed；
（2）By step（1）Obtained material, add MnO2Or CuO, mediate uniform, drying；
（3）By step（2）Material after gained drying is impregnated in 1-15h in iron salt solutions, is dried again after the completion of dipping；
（4）By step（3）Material after drying constant temperature 3-6 hours, produces finished catalyst in 450-550 DEG C.
6. the preparation method of catalyst according to claim 5, it is characterised in that step（1）Described in graphene with
The mass ratio of boehmite is（1-10）：125.
7. the preparation method of catalyst according to claim 5, it is characterised in that step（2）Middle MnO2Or CuO and step
（1）In the mass ratio of boehmite be（1-8）：125.
8. the preparation method of catalyst according to claim 5, it is characterised in that step（3）Described in iron salt solutions
For iron nitrate solution.
9. the preparation method of catalyst according to claim 8, it is characterised in that step（3）Described in ferric nitrate it is molten
The concentration of liquid is 0.05-0.3g/mL.
10. the preparation method of catalyst according to claim 5, it is characterised in that step（4）Middle holding temperature is 500
℃。
11. the preparation method of catalyst according to claim 5, it is characterised in that step（2）With（3）Described in baking
Do to dry 12h at 110 DEG C.
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| CN108499573B (en) * | 2018-04-26 | 2021-07-09 | 江苏天东新材料科技有限公司 | Titanium dioxide-based sulfur recovery catalyst and preparation method thereof |
| CN108671936A (en) * | 2018-04-26 | 2018-10-19 | 江苏天东新材料科技有限公司 | A kind of de-oxygen type catalyst for recovering sulfur and preparation method thereof |
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