CN105562030A - Aluminum trioxide sulfur recovery catalyst resistant to sulfation and preparation method thereof - Google Patents
Aluminum trioxide sulfur recovery catalyst resistant to sulfation and preparation method thereof Download PDFInfo
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- CN105562030A CN105562030A CN201610006588.0A CN201610006588A CN105562030A CN 105562030 A CN105562030 A CN 105562030A CN 201610006588 A CN201610006588 A CN 201610006588A CN 105562030 A CN105562030 A CN 105562030A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000019635 sulfation Effects 0.000 title claims abstract description 11
- 238000005670 sulfation reaction Methods 0.000 title claims abstract description 11
- 238000011084 recovery Methods 0.000 title abstract description 4
- QMVWWPIJZAORTR-UHFFFAOYSA-M [O-2].[OH-].O.[Al+3].S Chemical compound [O-2].[OH-].O.[Al+3].S QMVWWPIJZAORTR-UHFFFAOYSA-M 0.000 title abstract 2
- 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 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 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
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 4
- 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 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 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
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 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 description 24
- 238000000034 method Methods 0.000 description 20
- 230000008569 process Effects 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000007654 immersion Methods 0.000 description 12
- 238000004898 kneading Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 239000003223 protective agent Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 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
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 239000002131 composite material Substances 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
- 230000007812 deficiency Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 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
- 239000002808 molecular sieve Substances 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
- 230000003647 oxidation Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004044 response Effects 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
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to an aluminum trioxide sulfur recovery catalyst resistant to sulfation and a preparation method thereof. The catalyst is composed of the following components in percentage by weight: 75 to 90% of active aluminum trioxide, 1 to 10% of graphene, 1 to 8% of Fe2O3, and 0.5 to 7% of R oxide, wherein the R oxide represents MnO2 or CuO. The invention also provides a preparation method of the catalyst. Compared with the common alumina catalyst, the provided catalyst is resistant to poisoning caused by sulfation in the presence of trace O2 and SO2 and overcomes the shortage that active aluminum (III) trioxide is inactivated easily by hydrothermal sintering.
Description
Technical field
The present invention relates to alchlor catalyst for recovering sulfur of a kind of resistance to sulfation and preparation method thereof, particularly one and there is high claus reaction activity and long-life catalyst for recovering sulfur and preparation method thereof.
Background technology
Catalyst for recovering sulfur mainly makes the H of generation in fossil fuel process
2s changes the elementary sulfur of non-toxic and safe into.A large amount of H is produced in the process of oil, natural gas and coking of coal
2s gas, in order to protection of the environment and recovery element sulphur, the process of industrial generally employing claus process is containing H
2the sour gas environment protection of S, its main technique comprises: H in sour gas
2s partial oxidation in combustion furnace generates SO
2, SO
2with residue H
2s reacts generting element sulphur; The H do not reacted
2s and SO
2enter follow-up claus reaction device and continue reaction, the key reaction equation in combustion furnace is as follows:
H
2S+2/3O
2＝SO
2+H
2O(1)
H
2S+SO
2＝3/xSx+2H
2O(2)
Except reacting except (1) (2), SO in combustion furnace and follow-up claus reaction device
2also SO may be oxidized to
3, and traditional claus catalyst is active alundum (Al2O3), in device long-play process, under acid atmosphere and hydrothermal condition, alundum (Al2O3) is gradually by SO
3poison or SO
2irreversible Adsorption (sulfation) and sintering and inactivation, have impact on that device is long, peace, steady operation.At present above claus catalyst, load iron-based for the many employings of head it off to be left out oxygen protective agent or directly use the titanium base catalyst of resistance to sulfation.The iron-based oxygen protective agent that is left out can prevent SO
3generation, but to SO
2irreversible Adsorption have little effect.Ti-base catalyst not only cost is high, and mechanical strength is low, wears away high, and operation easier is increased.
In order to improve activity and the life-span of aluminum trioxide catalyst, just need to poison from sulfate resistance to start with water resistant thermal sintering two aspect.Tradition iron-based is left out oxygen protective agent by catalysis O
2to H
2the selective oxidation reaction of S generates sulphur, makes unreacted O in combustion furnace
2(leakage oxygen) removes, and then effectively suppresses SO in claus reaction device
2+ O
2generate SO
3reaction, thus reach the object of sulfuric-resisting salinization.But the concentration of " leakage oxygen " is usually less than 1% in claus reaction device, make to take off " leakage oxygen " reaction efficiency lower.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of alchlor catalyst for recovering sulfur of resistance to sulfation.
Summary of the invention
The present invention, by the compound of metal oxide, effectively improves redox reaction process, and then improves catalytic efficiency.That is: by the coupling of the oxide of Mn or Cu and Fe is formed composite metal oxide, reach and improve de-" leakage oxygen " catalytic efficiency.The present invention is directed to Al
2o
3base catalyst for recovering sulfur is to SO
2irreversible Adsorption and hydrothermal sintering process in the defect of easily assembling, carry out Modification on Al by adding Graphene
2o
3, thus reduce SO
2adsorption strength and reduce Al
2o
3the gathering of particle; Effectively can increase specific surface area of catalyst simultaneously, improve the service life of catalyst.
Detailed Description Of The Invention
Technical scheme of the present invention is as follows:
An alchlor catalyst for recovering sulfur for resistance to sulfation, this catalyst is by active alchlor, Graphene, Fe
2o
3form with the oxide of R, by weight percentage: activated alumina content 75% ~ 90%, Graphene content is 1% ~ 10%, Fe
2o
3content is the oxide content of 1% ~ 8%, R is 0.5%-7%, and the oxide of described R is MnO
2or CuO.
According to the present invention, preferably, the composition of described catalyst by weight percentage: activated alumina content 80% ~ 85%, Graphene content is 3% ~ 8%, Fe
2o
3content is the oxide content of 2% ~ 6%, R is 1%-6%.
According to the present invention, preferably, the specific area of described catalyst is 230-350m
2/ g, average crush strength is 270-310N/cm.
According to the present invention, the preparation method of above-mentioned catalyst, comprises step as follows:
(1) by Graphene ultrasonic disperse in water, add boehmite and mix;
(2) by the material that step (1) obtains, MnO is added
2or CuO, mediate evenly, dry;
(3) material after being dried by step (2) gained impregnated in 1-15h in iron salt solutions, again dries after having flooded;
(4) material after step (3) being dried is in 450-550 DEG C, and constant temperature 3-6 hour, obtains finished catalyst.
According to the present invention, preferably, the mass ratio of the Graphene described in step (1) and boehmite is (1-10): 125, further preferably (3-8): 125.
According to the present invention, preferably, MnO in step (2)
2or the mass ratio of boehmite in CuO and step (1) is (1-8): 125, further preferably (2-6): 125.
According to the present invention, preferably, the iron salt solutions described in step (3) is iron nitrate solution; Preferred further, the concentration of iron nitrate solution is 5%-30%g/mL.
According to the present invention, preferably, in step (4), holding temperature is 500 DEG C.
According to the present invention, preferably, step (2) and the oven dry described in (3) are dry 12h at 110 DEG C.
Catalyst Applicable temperature of the present invention is 200 ~ 360 DEG C, be 500 ~ 3000h in gas volume air speed
-1condition under use.Catalyst of the present invention is applicable to the claus reaction in Sulfur Recovery Procedure Gas.
Beneficial effect of the present invention:
1, catalyst of the present invention is compared with common aluminium oxide catalyst, overcomes it due to micro-O
2and SO
2existence easily produce the shortcoming of Sulphated Poisoning, and active alundum (Al2O3) is easy to the shortcoming of hydrothermal sintering and inactivation.
2, catalyst of the present invention is compared with traditional catalyst, has the advantages such as higher, the resistance to sulfation ability of Crouse's activity is strong.
Detailed description of the invention
Below by specific embodiment, the invention will be further described, but be not limited thereto.
Embodiment 1:
Take Graphene 5g, join in 100mL water, ultrasonic disperse is even, then takes 125g boehmite (water content 24.5%), joins in above-mentioned graphene aqueous solution, after stirring, joins in banded extruder, then adds 3g and enter MnO
2continue kneading 1 hour, be then extruded into the bar shaped of φ 3mm, put into baking oven 110 DEG C × 12h and dry; Take 10g nine water ferric nitrate (Fe (NO
3)
39H
2o), add the above-mentioned bar samples 12h of room temperature immersion after the water-soluble solution of 100mL, 110 DEG C × 12h is dried, and with the heating rate to 500 of 15 DEG C/min DEG C roasting 4h, obtains catalyst sample A.This sample specific area 276m
2/ g, average crush strength 292N/cm.
Embodiment 2:
Take Graphene 5g, join in 100mL water, ultrasonic disperse is even, then takes 125g boehmite (water content 24.5%), joins in above-mentioned graphene aqueous solution, after stirring, joins in banded extruder, then adds 3g and enter MnO
2continue kneading 1 hour, be then extruded into the bar shaped of φ 3mm, put into baking oven 110 DEG C × 12h and dry; Take 15g nine water ferric nitrate (Fe (NO
3)
39H
2o), after adding the water-soluble solution of 100mL, room temperature immersion is above-mentioned dries with the bar samples 12h of Graphene process, 110 DEG C × 12h, namely obtains catalyst sample B with the heating rate to 500 of a 15 DEG C/min DEG C roasting 4h.This sample specific area 267m
2/ g, average crush strength 290N/cm.
Embodiment 3:
Take Graphene 5g, join in 100mL water, ultrasonic disperse is even, then takes 125g boehmite (water content 24.5%), joins in above-mentioned graphene aqueous solution, after stirring, joins in banded extruder, then adds 3g and enter MnO
2continue kneading 1 hour, be then extruded into the bar shaped of φ 3mm, put into baking oven 110 DEG C × 12h and dry; Take 20g nine water ferric nitrate (Fe (NO
3)
39H
2o), after adding the water-soluble solution of 100mL, room temperature immersion is above-mentioned dries with the bar samples 12h of Graphene process, 110 DEG C × 12h, namely obtains catalyst sample C with the heating rate to 500 of a 15 DEG C/min DEG C roasting 4h.This sample specific area 261m
2/ g, average crush strength 281N/cm.
Embodiment 4:
Take Graphene 5g, join in 100mL water, ultrasonic disperse is even, then takes 125g boehmite (water content 24.5%), joins in above-mentioned graphene aqueous solution, after stirring, joins in banded extruder, then adds 3g and enter MnO
2continue kneading 1 hour, be then extruded into the bar shaped of φ 3mm, put into baking oven 110 DEG C × 12h and dry; Take 25g nine water ferric nitrate (Fe (NO
3)
39H
2o), after adding the water-soluble solution of 100mL, room temperature immersion is above-mentioned dries with the bar samples 12h of Graphene process, 110 DEG C × 12h, namely obtains catalyst sample D with the heating rate to 500 of a 15 DEG C/min DEG C roasting 4h.This sample specific area 281m
2/ g, average crush strength 282N/cm.
Embodiment 5:
Take Graphene 5g, join in 100mL water, ultrasonic disperse is even, then takes 125g boehmite (water content 24.5%), joins in above-mentioned graphene aqueous solution, after stirring, joins in banded extruder, then adds 1g and enter MnO
2continue kneading 1 hour, be then extruded into the bar shaped of φ 3mm, put into baking oven 110 DEG C × 12h and dry; Take 20g nine water ferric nitrate (Fe (NO
3)
39H
2o), after adding the water-soluble solution of 100mL, room temperature immersion is above-mentioned dries with the bar samples 12h of Graphene process, 110 DEG C × 12h, namely obtains catalyst sample E with the heating rate to 500 of a 15 DEG C/min DEG C roasting 4h.This sample specific area 284m
2/ g, average crush strength 296N/cm.
Embodiment 6:
Take Graphene 5g, join in 100mL water, ultrasonic disperse is even, then takes 125g boehmite (water content 24.5%), joins in above-mentioned graphene aqueous solution, after stirring, joins in banded extruder, then adds 6g and enter MnO
2continue kneading 1 hour, be then extruded into the bar shaped of φ 3mm, put into baking oven 110 DEG C × 12h and dry; Take 20g nine water ferric nitrate (Fe (NO
3)
39H
2o), after adding the water-soluble solution of 100mL, room temperature immersion is above-mentioned dries with the bar samples 12h of Graphene process, 110 DEG C × 12h, namely obtains catalyst sample F with the heating rate to 500 of a 15 DEG C/min DEG C roasting 4h.This sample specific area 258m
2/ g, average crush strength 301N/cm.
Embodiment 7:
Take Graphene 3g, join in 100mL water, ultrasonic disperse is even, then takes 125g boehmite (water content 24.5%), joins in above-mentioned graphene aqueous solution, after stirring, joins in banded extruder, then adds 3g and enter MnO
2continue kneading 1 hour, be then extruded into the bar shaped of φ 3mm, put into baking oven 110 DEG C × 12h and dry; Take 20g nine water ferric nitrate (Fe (NO
3)
39H
2o), after adding the water-soluble solution of 100mL, room temperature immersion is above-mentioned dries with the bar samples 12h of Graphene process, 110 DEG C × 12h, namely obtains catalyst sample G with the heating rate to 500 of a 15 DEG C/min DEG C roasting 4h.This sample specific area 248m
2/ g, average crush strength 308N/cm.
Embodiment 8:
Take Graphene 8g, join in 100mL water, ultrasonic disperse is even, then takes 125g boehmite (water content 24.5%), joins in above-mentioned graphene aqueous solution, after stirring, joins in banded extruder, then adds 3g and enter MnO
2continue kneading 1 hour, be then extruded into the bar shaped of φ 3mm, put into baking oven 110 DEG C × 12h and dry; Take 20g nine water ferric nitrate (Fe (NO
3)
39H
2o), after adding the water-soluble solution of 100mL, room temperature immersion is above-mentioned dries with the bar samples 12h of Graphene process, 110 DEG C × 12h, namely obtains catalyst sample H with the heating rate to 500 of a 15 DEG C/min DEG C roasting 4h.This sample specific area 312m
2/ g, average crush strength 271N/cm.
Embodiment 9:
Take Graphene 5g, join in 100mL water, ultrasonic disperse is even, take 125g boehmite (water content 24.5%) again, join in above-mentioned graphene aqueous solution, after stirring, join in banded extruder, add 3g again and enter CuO continuation kneading 1 hour, be then extruded into the bar shaped of φ 3mm, put into baking oven 110 DEG C × 12h and dry; Take 10g nine water ferric nitrate (Fe (NO
3)
39H
2o), after adding the water-soluble solution of 100mL, room temperature immersion is above-mentioned dries with the bar samples 12h of Graphene process, 110 DEG C × 12h, namely obtains catalyst sample I with the heating rate to 500 of a 15 DEG C/min DEG C roasting 4h.This sample specific area 279m
2/ g, average crush strength 290N/cm.
Embodiment 10:
Take Graphene 8g, join in 100mL water, ultrasonic disperse is even, take 125g boehmite (water content 24.5%) again, join in above-mentioned graphene aqueous solution, after stirring, join in banded extruder, add 3g again and enter CuO continuation kneading 1 hour, be then extruded into the bar shaped of φ 3mm, put into baking oven 110 DEG C × 12h and dry; Take 20g nine water ferric nitrate (Fe (NO
3)
39H
2o), after adding the water-soluble solution of 100mL, room temperature immersion is above-mentioned dries with the bar samples 12h of Graphene process, 110 DEG C × 12h, namely obtains catalyst sample J with the heating rate to 500 of a 15 DEG C/min DEG C roasting 4h.This sample specific area 311m
2/ g, average crush strength 278N/cm.
Embodiment 11:
Take Graphene 5g, join in 100mL water, ultrasonic disperse is even, take 125g boehmite (water content 24.5%) again, join in above-mentioned graphene aqueous solution, after stirring, join in banded extruder, add 6g again and enter CuO continuation kneading 1 hour, be then extruded into the bar shaped of φ 3mm, put into baking oven 110 DEG C × 12h and dry; Take 20g nine water ferric nitrate (Fe (NO
3)
39H
2o), after adding the water-soluble solution of 100mL, room temperature immersion is above-mentioned dries with the bar samples 12h of Graphene process, 110 DEG C × 12h, namely obtains catalyst sample K with the heating rate to 500 of a 15 DEG C/min DEG C roasting 4h.This sample specific area 262m
2/ g, average crush strength 294N/cm.
Embodiment 12:
Take Graphene 8g, join in 100mL water, ultrasonic disperse is even, take 125g boehmite (water content 24.5%) again, join in above-mentioned graphene aqueous solution, after stirring, join in banded extruder, add 1g again and enter CuO continuation kneading 1 hour, be then extruded into the bar shaped of φ 3mm, put into baking oven 110 DEG C × 12h and dry; Take 20g nine water ferric nitrate (Fe (NO
3)
39H
2o), after adding the water-soluble solution of 100mL, room temperature immersion is above-mentioned dries with the bar samples 12h of Graphene process, 110 DEG C × 12h, namely obtains catalyst sample L with the heating rate to 500 of a 15 DEG C/min DEG C roasting 4h.This sample specific area 306m
2/ g, average crush strength 282N/cm.
Test example 1:
The catalyst sample that embodiment 1-12 is obtained is ground into 20 ~ 40 orders, and then getting 5mL loading internal diameter is in the stainless steel qualitative response device of 14mm, and the quartz sand of top filling same particle sizes carries out mixing preheating.Reacting furnace adopts Electric heating, and beds position is similar to isothermal body of heater.Adopt H in Japanese Shimadzu GC-14B gas chromatograph on-line analysis reactor inlet and exit gas
2s, SO
2content, adopt GDX-301 carrier to analyze sulfide, adopt 5A molecular sieve to analyze O
2content, column temperature 120 DEG C, thermal conductivity detector (TCD), hydrogen is carrier gas, flow velocity 28mL/min after post.
With H
2s+SO
2→ 3S+H
2o is index reaction, and the Crouse investigating catalyst sample is active, and inlet gas consists of H
2s2%, SO
21%, O
23000ppm, H
2o30%, all the other are N
2, gas volume air speed is 2500h
-1, reaction temperature is 230 DEG C, calculates the Glaus conversion of catalyst according to following formula:
Wherein M
0, M
1represent entrance and exit H respectively
2s and SO
2volumetric concentration and.
The Activity evaluation of catalyst sample A ~ L is shown in table 1, and activity data is wherein the 48 hours mean value run continuously.
The activity contrast of table 1. different catalysts sample
M*, N* are industrial a kind of iron-based catalyst for recovering sulfur of generally using and activated alumina catalyst for recovering sulfur, and its main component is activated alumina and iron oxide or pure alumina, lower with.
Test example 2:
According to the claus reaction evaluation method of test example 1, investigate 500 hours claus reaction test run, result is shown in table 2.
Table 2.500 hour catalyst sample C and J and contrast 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 |
As can be seen from table 2 result, the running of 500 hours does not almost affect catalyst sample C and J, and contrast sample M*, N* has started the trend having activity decrease, the sulfate resistance ability describing catalyst sample C and J is strong, and catalyst life is better than the industrial iron-based catalyst for recovering sulfur that generally uses and activated alumina catalyst for recovering sulfur.
Claims (10)
1. an alchlor catalyst for recovering sulfur for resistance to sulfation, is characterized in that, this catalyst is by active alchlor, Graphene, Fe
2o
3form with the oxide of R, by weight percentage: activated alumina content 75% ~ 90%, Graphene content is 1% ~ 10%, Fe
2o
3content is the oxide content of 1% ~ 8%, R is 0.5%-7%, and the oxide of described R is MnO
2or CuO.
2. alchlor catalyst for recovering sulfur according to claim 1, is characterized in that, the composition of described catalyst by weight percentage: activated alumina content 80% ~ 85%, Graphene content is 3% ~ 8%, Fe
2o
3content is the oxide content of 2% ~ 6%, R is 1%-6%.
3. alchlor catalyst for recovering sulfur according to claim 1, is characterized in that, the specific area of described catalyst is 230-350m
2/ g.
4. alchlor catalyst for recovering sulfur according to claim 1, is characterized in that, the average crush strength of described catalyst is 270-310N/cm.
5. a preparation method for alchlor catalyst for recovering sulfur according to claim 1, comprises step as follows:
(1) by Graphene ultrasonic disperse in water, add boehmite and mix;
(2) by the material that step (1) obtains, MnO is added
2or CuO, mediate evenly, dry;
(3) material after being dried by step (2) gained impregnated in 1-15h in iron salt solutions, again dries after having flooded;
(4) material after step (3) being dried is in 450-550 DEG C, and constant temperature 3-6 hour, obtains finished catalyst.
6. the preparation method of catalyst according to claim 5, is characterized in that, the mass ratio of the Graphene described in step (1) and boehmite is (1-10): 125.
7. the preparation method of catalyst according to claim 5, is characterized in that, MnO in step (2)
2or the mass ratio of boehmite in CuO and step (1) is (1-8): 125.
8. the preparation method of catalyst according to claim 5, is characterized in that, the iron salt solutions described in step (3) is iron nitrate solution; Preferably, the concentration of iron nitrate solution is 5%-30%g/mL.
9. the preparation method of catalyst according to claim 5, is characterized in that, in step (4), holding temperature is 500 DEG C.
10. the preparation method of catalyst according to claim 5, is characterized in that, step (2) and the oven dry described in (3) are dry 12h at 110 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108499573A (en) * | 2018-04-26 | 2018-09-07 | 江苏天东新材料科技有限公司 | A kind of titania-based catalyst for recovering sulfur and preparation method thereof |
| CN108525672A (en) * | 2018-04-26 | 2018-09-14 | 江苏天东新材料科技有限公司 | A kind of multifunctional and composite type catalyst for recovering sulfur and preparation method thereof |
| CN108671932A (en) * | 2018-04-26 | 2018-10-19 | 江苏天东新材料科技有限公司 | A kind of alumina base catalyst for recovering sulfur 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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| EP4012809A1 (en) * | 2020-12-09 | 2022-06-15 | Gnanomat SL | Catalyst and metal-air battery |
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