CN100413566C - Direct oxidation desulfurization catalyst and preparation method thereof - Google Patents
Direct oxidation desulfurization catalyst and preparation method thereof Download PDFInfo
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- CN100413566C CN100413566C CNB2005100721222A CN200510072122A CN100413566C CN 100413566 C CN100413566 C CN 100413566C CN B2005100721222 A CNB2005100721222 A CN B2005100721222A CN 200510072122 A CN200510072122 A CN 200510072122A CN 100413566 C CN100413566 C CN 100413566C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 19
- 230000003647 oxidation Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 18
- 238000006477 desulfuration reaction Methods 0.000 title abstract description 3
- 230000023556 desulfurization Effects 0.000 title abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- 238000000975 co-precipitation Methods 0.000 claims abstract description 13
- 239000011787 zinc oxide Substances 0.000 claims abstract description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 238000000034 method Methods 0.000 abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 22
- 229910010413 TiO 2 Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- -1 stir Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KSECJOPEZIAKMU-UHFFFAOYSA-N [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] Chemical compound [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] KSECJOPEZIAKMU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
A direct oxidation desulfurization catalyst is an iron-based composite metal oxide catalyst, and is characterized in that the catalyst comprises, by weight, 20-60% of iron oxide, 15-45% of alumina, 15-45% of titanium oxide, 1-15% of zinc oxide and 1-15% of vanadium oxide; the specific surface area is 110-160 cm2A pore volume of 0.30-0.60 cm3(ii) in terms of/g. The catalyst can be prepared by a coprecipitation method, and has high activity and good selectivity. H-containing compounds treatable with the catalysts of the invention2Wide S gas range, for H2The acid gas with the S content ranging from 1 percent to 85 percent can be directly treated at normal pressure or low pressure (0.4MPa), 180 ℃ and space velocity of 1500h-1～3000h-1Under the condition of H2The conversion rate of S can reach more than 95.0 percent, and the selectivity to elemental sulfur can reach more than 90.0 percent.
Description
Technical field
The present invention relates to a kind of be applicable to handle contain H
2Direct oxidation desulphurization catalyst of S gas and preparation method thereof specifically, the present invention relates to a kind of catalyst and this Preparation of catalysts method that selectively hydrogen sulfide is oxidized to elementary sulfur.
Background technology
In synthesis gas production, gas production and the petroleum refining process, because the existence of sulphur in the oil, natural gas, coal, often (be H main the composition with the generation of the sulfur-containing compound of a great deal of
2S), and the existence of sulfide in the gas, the meeting corrosion pipeline; Cause catalyst poisoning so that inactivation; Influence product quality and cause environmental pollution.To the purification of synthesis gas, natural gas and refinery gas etc., that adopt mostly is wet-process beneficiation H at present
2S is again with the H of enrichment
2The S stripping gas changes into elemental sulfur with Claus method.Because be subjected to the restriction of chemical reaction equilibrium under the reaction temperature, the Claus sulfur recovery rate can reach about 97%, remaining sulphur of 3～4% is all with SO
2Form enter atmosphere, both caused the waste of sulphur resource, again severe contamination environment, this part Claus tail gases passes through H usually
2S direct oxidation technology (selective catalytic oxidation technology) further processes.
H
2S direct oxidation technology is containing H exactly
2Allocate oxygen or air in the process gas of S into, make the H in the process gas
2S directly in the reactor of solid catalyst is housed Catalytic Oxygen change into elemental sulfur and with its recovery, reach and remove H
2The purpose of S.H
2The S direct oxidation becomes the reaction of elementary sulfur, says and can be undertaken by following formula from thermodynamics:
2H
2S+SO
2→3/nS
n+2H
2O
Introduced a kind of TiO of the Modop of can be used for technology in the BP 2122597
2Catalyst based, US4311683 discloses BSR-Selectox technology, use be a kind of with non-alkaline porous refractory oxide as carrier, with barium oxide and vanadium sulfide catalyst as active constituent, and use the weak point of these two kinds of catalyst to be, high concentration water's content in the technical process gas there is certain requirement for restriction, because water has seriously disturbed H
2The absorption of S and oxidizing process, involved investment cost is higher, makes the cost of vent gas treatment in these known methods also very high; US 4818740 discloses a kind of catalyst that not influenced by technical process middle and high concentration water content, and this catalyst can be used for Super Claus technology, and used carrier is α-Al
2O
3, active constituent is Fe
2O
3-Cr
2O
3This catalyst is H in gas composition
2S 1% (V), O
2(V) 0.6%, H
2O (V) 30%, all the other are helium and 270 ℃ of reaction temperatures, 1000h
-1Under the air speed laboratory condition, H
2The conversion ratio of S can reach 100%, and selectivity can reach 93%.
CN 1203828A discloses a kind of direct oxidation desulphurization catalyst, and this catalyst does not show the α-Al of alkalescence with the surface
2O
3Be carrier, make complex solution with the nitrate of iron, chromium and phosphorylated ligand and flood and make.This catalyst is with consisting of H
2S 1% (V), O
20.6% (V), H
2O30% (V), all the other are that the gas of nitrogen is at 270 ℃ of reaction temperatures, air speed 2500h
-1Estimate selectivity 92.3～96%, conversion ratio 83.6%～100% under the condition.
Its preparation process of disclosed catalyst and method and CN 1203828A are roughly the same among the CN 1153136A, but used carrier is the SiO of Large ratio surface
2Carrier, but not α-Al
2O
3Carrier, the high temperature active of this catalyst is not as the α-Al of small specific surface
2O
3Catalyst based, but its low temperature active obviously is better than α-Al
2O
3Catalyst based.
Above-mentioned catalyst is the loaded catalyst that adopts infusion process to make, and range of application all concentrates on the processing that hydrogen sulfide content is lower than 20% gas, is higher than 20% gas for hydrogen sulfide content and still can not directly uses above-mentioned catalyst.
Summary of the invention
The object of the present invention is to provide direct oxidation desulphurization catalyst that a kind of preparation method is simple, activity is higher and preparation method thereof, catalyst is applicable to handles the bigger gas of hydrogen sulfide content scope.
Of the present invention be used for handling contain H
2The direct oxidation desulphurization catalyst of S gas is that iron is O composite metallic oxide catalyst, and by weight percentage, wherein containing iron oxide is 20～60%, salic 15～45%, contain titanium oxide 15～45%, contain zinc oxide 1%～15%, contain vanadium oxide 1%～15%; Specific surface is 110～160cm
2/ g, pore volume 0.30～0.60cm
3/ g.
Direct oxidation desulphurization catalyst of the present invention preferably consists of by weight percentage, and wherein containing iron oxide is 40～60%, and is salic 25～40%, contains titanium oxide 25～40%; Specific surface is 120～150cm
2/ g, pore volume 0.40～0.60cm
3/ g.
Direct oxidation desulphurization catalyst of the present invention, has added the oxide of V, Zn simultaneously and has made auxiliary agent as its active constituent with the metal oxide of Fe, Al, Ti.Component Fe wherein
2O
3Effect be to promote H
2The oxidation reaction of S, component Al
2O
3Main promotion claus reaction, the component TiO of plaing a part
2Main effect be the structure of adjusting catalyst, also have the oxidation catalysis effect simultaneously, test shows, Fe
2O
3Content high catalyst conversion ratio more is high more and selectivity is poor more; Al
2O
3The catalyst selectivity that content is high more is good more and conversion ratio is poor more; TiO
2Content change with the variation of iron aluminium content, Ti content is crossed the low catalyst overall performance and is reduced, if but too high, then active constituent content influences the performance of catalyst equally with deficiency.The oxide of co-catalyst V, Zn mainly plays the effect of smart desulfurization, find in the test: make used additives zinc oxide separately, catalyst activity is obviously relatively poor, make the oxide of used additives vanadium separately, catalyst activity is also undesirable, when the oxide of iron, aluminium, titanium, zinc, vanadium existed simultaneously, prepared catalyst combination property more only contained wherein that the catalyst of certain several composition is significantly improved.
A kind of preparation method of above-mentioned direct oxidation desulphurization catalyst also is provided among the present invention:
1, under 30 ℃～90 ℃ the temperature, in the coprecipitation reaction device, adds oxide or its precursor of Al, Fe, Zn, Ti, V,, make regulator solution pH value to 7.0～10.0 behind the solution, make it co-precipitation as soluble-salt;
2, in sediment, add the adhesive of 1～20% (in catalyst quality) and (in catalyst quality) pore creating material of 1～20%; the roasting under 400～850 ℃ of conditions of dry back is no less than 4 hours, promptly makes catalyst of the present invention by extrusion granulation or compression molding afterwards.
Sintering temperature is low excessively, and metal hydroxides decomposition and inversion fully becomes to have the oxide of catalytic activity, and the oxide crystal formation can not fully be reset, and influences the catalytic performance of catalyst; Sintering temperature is too high, causes the oxide crystal formation to change, and occurs the excessive sintering of catalyst simultaneously, also can reduce the catalyst performance of catalyst.
The soluble-salt of being mentioned among the present invention can be the chloride of metal, or nitrate, or soluble sulphate.
Adhesive can be with the typical catalyst adhesive among the present invention, and as being: polyvinyl alcohol, aluminium colloidal sol, Ludox, five polyaluminium chlorides etc., aluminium colloidal sol class adhesive more is applicable to the present invention.
Pore creating material can be with the typical catalyst pore creating material, as being among the present invention: polyethylene glycol, urea, methyl cellulose etc., test show that to select polyethylene glycol, urea effect for use best.
Catalyst among the present invention adopts the preparation of coprecipitation method, has higher activity and selectivity preferably.The accessible H that contains of this catalyst
2S gas wide ranges is to H
2Sour gas between the S content range 1%～85% can directly be handled, at normal pressure or low pressure (0.4MPa), 180 ℃, air speed 1500h
-1～3000h
-1Under the condition, H
2The conversion ratio of S can reach more than 95.0%, can reach more than 90.0% the selectivity of elemental sulfur.
The specific embodiment
Embodiment 1
With 70ml 10%AlCl
3, 80ml 10%FeCl
3, 20ml 5%ZnCl
2, 200ml 5%Ti (SO4)
2Solution, 120ml 1%V
2O
5Aqueous slkali be added dropwise to simultaneously in the coprecipitation reaction device, regulate PH to 8.0 ± 0.5, precipitate.Add five polyaluminium chlorides and the 5g urea of 15ml in sediment, stir, air dry is extrusion, granulation after 24 hours, following dry 8 hours at 120 ℃ again, 600 ℃ of following roasting 8h in Muffle furnace promptly obtain catalyst sample A then, and each component content is in the sample: Al
2O
325%, Fe
2O
335%, ZnO 5%, TiO
230%, V
2O
55%.
Embodiment 2
With 80ml 10%Al (NO
3)
3, 179ml 10%Fe (NO
3)
3, 35ml 5%ZnCl
2, 115ml 5%Ti (SO4)
2Solution, 70ml 1%V
2O
5Aqueous slkali be added dropwise to simultaneously in the coprecipitation reaction device, regulate PH to 8.5 ± 0.5, make precipitated metal.Add aluminium colloidal sol and the 5g urea of 15ml in sediment, stir, air dry is extrusion, granulation after 24 hours, dries by the fire 8 hours down at 120 ℃ again, and 550 ℃ of following roasting 8h in Muffle furnace promptly obtain catalyst sample B then, and each component content is in the sample: Al
2O
317%, Fe
2O
352.3%, ZnO 10.7%, TiO
217%, V
2O
53%.
Embodiment 3
With 115ml 10%AlCl
3, 60ml 10%FeCl
3, 15ml 5%ZnCl
2, 140ml 5%Ti (SO4)
2Solution, 228ml 1%V
2O
5Aqueous slkali be added dropwise to simultaneously in the coprecipitation reaction device, regulate PH to 9.0 ± 0.5, make precipitated metal.Add polyvinyl alcohol and the 5g polyethylene glycol of 10g in sediment, stir, air dry is extrusion, granulation after 24 hours, dried by the fire 8 hours down at 120 ℃ again, 450 ℃ of following roasting 8h in Muffle furnace promptly obtain catalyst sample C then, and each component content is in the sample: Al
2O
339.1%, Fe
2O
326.2%, ZnO 4%, TiO
220.7%, V
2O
510%.
Embodiment 4
With 70ml 10%AlCl
3, 60ml 10%FeCl
3, 15ml 5%ZnCl
2, 280ml 5%Ti (SO4)
2Solution, 108ml 1%V
2O
5Aqueous slkali be added dropwise to simultaneously in the coprecipitation reaction device, regulate PH to 8.0 ± 0.5, make precipitated metal.Add Ludox and the 5g urea of 15ml in sediment, stir, air dry is extrusion, granulation after 24 hours, dries by the fire 8 hours down at 120 ℃ again, and 800 ℃ of following roasting 8h in Muffle furnace promptly obtain catalyst sample D then, and each component content is in the sample: Al
2O
323.8%, Fe
2O
326.2%, ZnO 4%, TiO
241.2%, V
2O
54.8%.
Embodiment 5
With 1.0gV
2O
5, the 1.0gZnO pressed powder is put into the coprecipitation reaction device, adds 70ml 10%AlCl
3, 60ml 10%FeCl
3, 180ml 5%Ti (SO4)
2Solution is regulated PH to 8.0 ± 0.5, makes the metal co-precipitation.All the other preparation processes are identical with embodiment 1, make catalyst sample E, and each component content is in the sample: Al
2O
320.4%, Fe
2O
335%, ZnO 9%, TiO
226.6%, V
2O
59%.
Comparative Examples 1
According to the method for embodiment 1, with 120ml 10%AlCl
3, 35ml 10%FeCl
3, 20ml 5%ZnCl
2, 228ml 5%Ti (SO4)
2Solution, 113ml 1%V
2O
5Aqueous slkali be added dropwise to simultaneously in the coprecipitation reaction device, all the other preparation processes are identical with embodiment 1, make catalyst sample F, each component content is in the sample: Al
2O
341%, Fe
2O
3L5%, ZnO 5%, TiO
234%, V
2O
55%.
Comparative Examples 2
According to the method for embodiment 2, with 30ml 10%Al (NO
3)
3, 160ml 10%Fe (NO
3)
3, 40ml5%ZnCl
2, 220ml 5%Ti (SO4)
2Solution, 85ml 1%V
2O
5Aqueous slkali be added dropwise to simultaneously in the coprecipitation reaction device, regulate PH to 8.0 ± 0.5, all the other preparation processes are identical with embodiment 2, make catalyst sample G, each component content is in the sample: Al
2O
36.4%, Fe
2O
346.8%, ZnO 10.6%, TiO
232.5%, V
2O
53.8%
Comparative Examples 3
Composition and method by embodiment 5 prepare catalyst, do not add V
2O
5, making catalyst sample H, each component content is in the sample: Al
2O
322.4%, Fe
2O
338.3%, ZnO 10.2%, TiO
229.1%.
Comparative Examples 4
Composition and method by embodiment 5 prepare catalyst, do not add ZnO, make catalyst sample I, and each component content is in the sample: Al
2O
322.5%, Fe
2O
338.5%, TiO
229.2%, V
2O
59.8%.
Comparative Examples 5
Composition and method by embodiment 2 prepare catalyst, 900 ℃ of following roastings, make catalyst J.
Comparative Examples 6
Composition and method by embodiment 2 prepare catalyst, 400 ℃ of following roastings, make catalyst K.
The physical property of each catalyst sample is as shown in table 1:
Table 1 catalyst sample physical data
Evaluation result
1, above-mentioned A～K catalyst breakage and sieve are got 10～40 order particle 5ml, be seated in the miniature continuous fixed bed reactor, feeding composition (V%) is CO
2: ≈ 76.6%, CO: ≈ 8.9%, N
2: ≈ 7.5%, H
2: ≈ 4.2%, H
2The reaction gas of S: ≈ 3%, at normal pressure, 180 ℃ of temperature and air speed 3000
-1Carry out evaluation test, H under the condition of h
2S conversion ratio, as follows to the selectivity computational methods of elemental sulfur:
By evaluation test, the conversion ratio of each catalyst, selective data see Table 2 respectively, table 3:
Table 2 embodiment evaluating catalyst result
| Catalyst | Conversion ratio (%) | Selectivity (%) |
| A | 96.7 | 94.3 |
| B | 99.6 | 91.7 |
| C | 95.3 | 98.2 |
| D | 95.7 | 92.1 |
| E | 97.3 | 93.4 |
Table 3 Comparative Examples evaluating catalyst result
| Catalyst | Conversion ratio (%) | Selectivity (%) |
| F | 58.4 | 98.6 |
| G | 98.1 | 64.3 |
| H | 81.2 | 83.9 |
| I | 83.5 | 84.7 |
| J | 70.3 | 62.9 |
| K | 79.6 | 70.2 |
2, the broken also sieve of catalyst E is got 10～40 order particle 5ml, be seated in the miniature continuous fixed bed reactor, feed H
2S content is the gas of 85% (reducing to about 27.5% after allocating air into), at normal pressure, and 180 ℃ of temperature and air speed 3000
-1Carry out evaluation test under the condition of h, its conversion ratio, selective data see Table 3:
Table 4 uses catalyst of the present invention in high-concentration hydrogen sulfide content evaluation test result
| Catalyst | Conversion ratio (%) | Selectivity (%) |
| E | 97.9 | 92.5 |
From table 2～4 as can be seen: use the catalyst of preparation method of the present invention and condition preparation, H
2The conversion ratio of S can reach more than 95.0%, can reach more than 90.0% the selectivity of elemental sulfur, has good catalytic performance; When the processing hydrogen sulfide content was higher than 20% gas, conversion ratio and selectivity still remained on respectively more than 95.0% and 92.5%, are applicable to the processing of high concentration H 2 S-containing gas fully.
Claims (6)
1. a direct oxidation desulphurization catalyst for iron is O composite metallic oxide catalyst, is characterized by catalyst by weight percentage, wherein containing iron oxide is 20～60%, salic 15～45%, contains titanium oxide 15～45%, contain zinc oxide 1%～15%, contain vanadium oxide 1%～15%; Specific surface is 110～160cm
2/ g, pore volume 0.30～0.60cm
3/ g.
2. direct oxidation desulphurization catalyst according to claim 1 is characterized by: the consisting of by weight percentage of catalyst, and wherein containing iron oxide is 40～60%, salic 25～40%, contains titanium oxide 25～40%; Specific surface is 120～150cm
2/ g, pore volume 0.40～0.60cm
3/ g.
3. the preparation method of the described direct oxidation desulphurization catalyst of claim 1, the steps include: (1). under 30 ℃～90 ℃ temperature, the oxide or its precursor that in reactor, add Al, Fe, Zn, Ti, V, make regulator solution pH value to 7.0～10.0 behind the solution, make it co-precipitation;
(2). in catalyst quality, add 1～20% adhesive and 1～20% pore creating material in sediment, the roasting under 400～850 ℃ of conditions of dry back is no less than 4 hours, promptly makes catalyst of the present invention by extrusion granulation or compression molding afterwards.
4. preparation method according to claim 3, the precursor that it is characterized in that the oxide of Al, Fe, Zn, Ti, V is meant the chloride of metal, or nitrate, or soluble sulphate.
5. preparation method according to claim 3 is characterized in that adhesive is one or more in polyvinyl alcohol, aluminium colloidal sol, Ludox, five polyaluminium chlorides.
6. preparation method according to claim 3 is characterized in that pore creating material is one or more in polyethylene glycol, urea, the methyl cellulose.
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| CN101380578B (en) * | 2007-09-06 | 2011-07-20 | 中国科学院生态环境研究中心 | Ferrotitanium composite oxides catalyst for ammonia selective reduction nitric oxides |
| CN102039137B (en) * | 2009-10-21 | 2012-09-12 | 中国石油化工股份有限公司 | Honeycomb catalyst for catalytically incinerating sulfur recovery tail gases and preparation method |
| CN103127821A (en) * | 2011-11-30 | 2013-06-05 | 中国石油化工股份有限公司 | Gas purification method |
| CN103436287B (en) * | 2013-09-23 | 2015-08-19 | 南通宝聚颜料有限公司 | A kind of metal oxide modified nano iron oxide catalyst carries out the method for diesel oxidation desulfurizing |
| CN104475104B (en) * | 2014-11-05 | 2018-03-23 | 杨楠 | Selective catalytic oxidation vulcanizes the technique that hydrogen catalyst, tail gas catalyst to burned and treating technology hydrogen sulfide are sulphur |
| CN104474894B (en) * | 2014-11-20 | 2019-01-25 | 王在仕 | A kind of cyclone cylinder dry fume catalytic desulfurization device and technique |
| CN105435623B (en) * | 2015-12-17 | 2018-08-14 | 盘锦北方沥青股份有限公司 | A kind of desulfurizing agent filling structure and its loading method for desulfurization reactor |
| CN105617996A (en) * | 2016-03-28 | 2016-06-01 | 无锡锡能锅炉有限公司 | Adsorptive desulfurizer for biomass boiler |
| CN106336889A (en) * | 2016-10-13 | 2017-01-18 | 宁夏宝塔石化科技实业发展有限公司 | Crude oil desulfurizer and preparation method and desulfurization process |
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| US5278123A (en) * | 1990-02-19 | 1994-01-11 | Rhone-Poulenc Chimie | Monolithic catalysts for converting sulfur compounds into SO2 |
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| US5278123A (en) * | 1990-02-19 | 1994-01-11 | Rhone-Poulenc Chimie | Monolithic catalysts for converting sulfur compounds into SO2 |
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