CN115301246A - Method for removing oxygen in hydrogen sulfide-containing gas and application of catalyst - Google Patents
Method for removing oxygen in hydrogen sulfide-containing gas and application of catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 239000007789 gas Substances 0.000 title claims abstract description 68
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000001301 oxygen Substances 0.000 title claims abstract description 31
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 40
- 239000011787 zinc oxide Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 7
- 150000000703 Cerium Chemical class 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000002360 preparation method Methods 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011206 ternary composite Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GZSJSGZGZXGFOW-UHFFFAOYSA-N [Zn].[Ce].[Cu] Chemical compound [Zn].[Ce].[Cu] GZSJSGZGZXGFOW-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J23/002—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
- B01J23/76—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
- B01J23/83—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 rare earths or actinides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/16—Hydrogen sulfides
- C01B17/168—Purification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a method for removing oxygen in hydrogen sulfide-containing gas and application of a catalyst. The method comprises the following steps: contacting the hydrogen sulfide-containing gas with a catalyst to remove oxygen; wherein the catalyst comprises 1 to 7 weight portions of CuO and 5 to 15 weight portions of CeO 2 15 to 25 parts by weight of ZnO and 55 to 70 parts by weight of ZrO 2 (ii) a Wherein H in the hydrogen sulfide-containing gas 2 The concentration of S is 1-70 mg/Nm 3 ，O 2 The concentration of (B) is 100 to 5000ppm. The method can remove O in the gas containing hydrogen sulfide 2 And (4) effectively removing.
Description
Technical Field
The invention relates to a method for removing oxygen in hydrogen sulfide-containing gas and application of a catalyst.
Background
Blast furnace gas is a byproduct of the blast furnace ironmaking production process, and comprises the main components of nitrogen, carbon dioxide, carbon monoxide, oxygen, hydrogen and a small amount of sulfide. The sulfide is mainly organic sulfur and inorganic sulfur, the removal of the organic sulfur is mainly hydrolysis, and the oxygen contained in the blast furnace gas is easy to oxidize the sulfide converted by hydrolysis into elemental sulfur or sulfate, so that the poisoning and inactivation of the hydrolysis catalyst are caused, and therefore, the deoxidation of the blast furnace gas is an effective way for prolonging the service life of the hydrolysis catalyst. CO and O in blast furnace gas can be deoxidized by using a deoxidation catalyst 2 Reacting thereby to convert O 2 And (4) removing.
CN102319570A discloses a ternary composite oxide catalyst for carbon monoxide oxidation. The catalyst comprises CuO-CeO-M, wherein M is at least one of metal oxides of Co, ni, zn, mg and Zr, and the molar ratio of CuO to CeO: M =20 is (0.1-20). The catalyst is a ternary composite oxide catalyst, and the catalyst has high CeO content and poor catalytic oxidation effect on sulfide-containing gas.
CN104475114A discloses a copper-zinc-cerium based catalyst for removing carbon monoxide. The catalyst comprises a main component CuO, a second component ZnO and a third component CeO 2 An oxide of a fourth component M; m is selected from one or more of Zr, mn, mg, fe, la, pr, nd and Sm. The catalyst takes CuO as a main component, and has poor sulfur resistance.
At present, no relevant report about the removal of oxygen from hydrogen sulfide containing gas exists.
Disclosure of Invention
In view of the above, it is an object of the present invention to provide a method for removing oxygen from a hydrogen sulfide-containing gas, which method is capable of removing O from the hydrogen sulfide-containing gas 2 And (4) effectively removing. Another object of the present invention is to provide a use of the catalyst.
The technical purpose of the invention is realized by the following technical scheme.
In one aspect, the present invention provides a method for removing oxygen from a gas containing hydrogen sulfide, comprising the steps of:
contacting the hydrogen sulfide containing gas with a catalyst to remove oxygen;
wherein the catalyst comprises 1 to 7 weight portions of CuO and 5 to 15 weight portions of CeO 2 15 to 25 parts by weight of ZnO and 55 to 70 parts by weight of ZrO 2 ；
Wherein H in the hydrogen sulfide-containing gas 2 The concentration of S is 1-70 mg/Nm 3 ，O 2 The concentration of (A) is 100 to 5000ppm.
According to the method of the present invention, preferably, the catalyst consists essentially of 1 to 7 parts by weight of CuO,5 to 15 parts by weight of CeO 2 15 to 25 parts by weight of ZnO and 55 to 70 parts by weight of ZrO 2 And (4) forming.
According to the process of the present invention, preferably, the hydrogen sulfide-containing gas is contacted with the catalyst at a temperature of 50 to 160 ℃.
According to the process of the present invention, the hydrogen sulfide-containing gas is preferably fed at a space velocity of 500 to 3000 hours -1 Under conditions such that the catalyst is contacted.
According to the process of the present invention, preferably, the hydrogen sulfide-containing gas is contacted with the catalyst in a fixed bed reactor.
According to the process of the present invention, preferably, the catalyst is cylindrical and has a diameter of 2 to 8mm.
The method according to the present invention preferably further comprises a catalyst preparation step:
(1) Dipping a mixture comprising zinc oxide, zirconium oxide and sesbania powder into an aqueous solution containing a soluble copper salt and a soluble cerium salt; then kneading to obtain a kneaded material;
(2) Molding the kneaded material to obtain a blank body;
(3) And drying the green body, and then roasting to obtain the catalyst.
According to the method of the invention, preferably, the soaking time is 4-10 h by using an isovolumetric soaking method.
According to the method of the invention, preferably, the drying temperature is 100-150 ℃, and the drying time is 1-6 h; the roasting temperature is 400-600 ℃, and the roasting time is 2-7 h.
In another aspect, the present invention provides a use of a catalyst for removing oxygen from a hydrogen sulfide-containing gas, the catalyst comprising 1 to 7 parts by weight of CuO and 5 to 15 parts by weight of CeO 2 15 to 25 parts by weight of ZnO and 55 to 70 parts by weight of ZrO 2 (ii) a H in the gas containing hydrogen sulfide 2 The concentration of S is 1-70 mg/Nm 3 ，O 2 The concentration of (A) is 100 to 5000ppm.
The invention discovers that the alloy contains CuO and CeO with specific contents 2 ZnO and ZrO 2 The catalyst of (2) can remove oxygen from a gas containing hydrogen sulfide. The catalyst has stronger sulfur resistance under proper conditions, so the catalytic effect is better.
Detailed Description
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto.
< method for removing oxygen from gas containing hydrogen sulfide >
The method for removing oxygen in the hydrogen sulfide-containing gas comprises the following steps: the hydrogen sulfide-containing gas is contacted with a catalyst to remove oxygen. Specifically, a hydrogen sulfide-containing gas is contacted with a catalyst in a fixed bed reactor. The hydrogen sulfide-containing gas may be introduced into the fixed bed reactor from the inlet thereof. The contacted gas can be discharged from the outlet of the fixed bed reactor.
An example of the hydrogen sulfide-containing gas may be blast furnace gas. In the gas containing hydrogen sulfide, H 2 The concentration of S may be 1 to 70mg/Nm 3 (ii) a Preferably 10 to 60mg/Nm 3 (ii) a More preferably 30 to 50mg/Nm 3 . The invention discovers that H 2 The S concentration is controlled within the above range, and the catalyst poisoning can be avoided.
In the gas containing hydrogen sulfide, O 2 The concentration of (A) is 100-5000 ppm; preferably 500 to 4000ppm; more preferably 1000 to 3000ppm. It has been found in the present invention that the oxygen concentration in the hydrogen sulphide containing gas should not be too high, which would otherwise result in a reduced deoxygenation efficiency. The invention has better removal effect on the hydrogen sulfide-containing gas with low oxygen concentration.
The concentration of CO in the gas containing hydrogen sulfide is 5-50 vol%; preferably 10 to 35vol%; more preferably 15 to 25vol%. This is advantageous in improving the deoxidation efficiency.
The catalyst comprises CuO and CeO 2 ZnO and ZrO 2 . In certain embodiments, the catalysts of the present invention consist essentially of CuO, ceO 2 ZnO and ZrO 2 And (4) forming. In certain embodiments, the catalyst of the present invention is comprised of CuO, ceO 2 ZnO and ZrO 2 And (4) forming.
The content of CuO is 1 to 7 parts by weight; preferably 2 to 5 parts by weight; more preferably 3 to 4 parts by weight.
CeO 2 The content of (A) is 5-15 parts by weight; preferably 8 to 13Weighing parts; more preferably 10 to 11 parts by weight.
The content of ZnO is 15-25 weight portions; preferably 17 to 23 parts by weight; more preferably 20 to 21 parts by weight.
ZrO 2 The content of (A) is 55 to 70 parts by weight; preferably 60 to 65 parts by weight; more preferably 62 to 63 parts by weight.
The catalyst with the composition can avoid catalyst poisoning and ensure good deoxidation effect.
The catalyst may be cylindrical. The diameter can be 2-8 mm; preferably 3-6 mm; more preferably 4 to 5mm.
The method for removing oxygen in the hydrogen sulfide-containing gas of the invention can also comprise the preparation steps of the catalyst: (1) dipping and kneading; (2) molding; and (3) drying and calcining.
A mixture including zinc oxide, zirconium oxide and sesbania powder is dipped into an aqueous solution containing a soluble copper salt and a soluble cerium salt, and then kneaded to obtain a kneaded matter.
The soluble copper salt may be selected from one or more of copper nitrate, copper chloride, copper sulphate. According to one embodiment of the invention, the soluble copper salt is copper nitrate.
The soluble cerium salt may be selected from one or more of cerium nitrate, cerium chloride, cerium sulphate. According to one embodiment of the invention, the soluble cerium salt is cerium nitrate.
The dosage of zinc oxide, zirconium oxide, soluble copper salt and soluble cerium salt is determined according to the composition of the catalyst. The mass ratio of the zinc oxide to the sesbania powder is (2-6) to 1; preferably (3-5) 1; more preferably 4.
Preferably, an equal volume impregnation method is used. The dipping time can be 4-10 h; preferably 5 to 8 hours; more preferably 6 to 7 hours.
And molding the kneaded material to obtain a blank. The shaping can be carried out in an extrusion apparatus. The blank may be a cylinder. The diameter of the blank body can be 2-8 mm; preferably 3-6 mm; more preferably 4 to 5mm.
And drying the green body, and then roasting to obtain the catalyst. The drying temperature can be 100-150 ℃; preferably 110 to 140 ℃; more preferably 120 to 130 ℃. The drying time can be 1-6 h; preferably 2 to 5 hours; more preferably 3 to 4 hours.
The roasting temperature can be 400-600 ℃; preferably 450 to 550 ℃; more preferably 500 to 550 ℃. The roasting time can be 2-7 h; preferably 3 to 6 hours; more preferably from 4 to 5 hours.
The catalyst contacts with gas containing hydrogen sulfide at 50-160 deg.c; preferably, the catalyst is contacted with a hydrogen sulfide-containing gas at a temperature of 70 to 140 ℃; more preferably, the catalyst is contacted with a hydrogen sulphide containing gas at a temperature of from 80 to 120 ℃.
Hydrogen sulfide-containing gas is put at a space velocity of 500-3000 h -1 With a catalyst under conditions such that the catalyst is contacted; preferably, the catalyst and the hydrogen sulfide-containing gas are reacted at a space velocity of 1000 to 2500h -1 Under conditions such that; more preferably, the catalyst is mixed with the hydrogen sulfide-containing gas at a space velocity of 1500 to 2000h -1 Under the condition of (1).
O in the contacted gas 2 The concentration of (b) is less than or equal to 55ppm; preferably, O in the contacted gas 2 The concentration of the (B) is less than or equal to 50ppm.
< uses of the catalyst >
The catalyst has good deoxidation catalysis effect on hydrogen sulfide gas. Therefore, the invention provides the application of the catalyst in removing oxygen in the hydrogen sulfide-containing gas.
In the gas containing hydrogen sulfide, H 2 The concentration of S is 1-70 mg/Nm 3 (ii) a Preferably 10 to 60mg/Nm 3 (ii) a More preferably 30 to 50mg/Nm 3 。O 2 The concentration of (A) is 100-5000 ppm; preferably 500 to 4000ppm; more preferably 1000 to 3000ppm. The concentration of CO is 5-50 vol%; preferably 10 to 35vol%; more preferably 15 to 25vol%.
The catalyst comprises CuO and CeO 2 ZnO and ZrO 2 . The catalyst of the present invention is as described above and will not be described in detail here. Generally, such catalysts are used for CO removal, and no report has been made on their use for oxygen removal, nor for the removal of oxygen from hydrogen sulfide-containing gases. In fact, different application scenarios require the selection of different compositions of the catalystAnd (4) an agent. The present inventors have found that the above-mentioned catalysts are suitable for removing oxygen from a gas containing hydrogen sulphide and are therefore not a conventional choice. The oxygen removal process is as described above and will not be described further herein.
Preparation example 1
7.05g of copper nitrate and 25.2g of cerium nitrate hexahydrate were dissolved in water to form an aqueous solution.
20g of zinc oxide, 5g of sesbania powder and 62g of zirconium oxide were immersed in an aqueous solution for 6 hours by an equal-volume immersion method, and then kneaded to obtain a kneaded matter.
The kneaded material was extruded to obtain a cylindrical green body having a diameter of 4 mm.
And drying the green body at 120 ℃ for 3h, and then roasting at 500 ℃ for 4h to obtain the catalyst.
The CuO content of the catalyst is 3 parts by weight and CeO 2 Is 10 parts by weight, znO is 20 parts by weight, zrO 2 The content of (B) is 62 parts by weight.
Preparation example 2
The same procedure as in preparation example 1 was repeated except that 62g of zirconia was replaced with 62g of silica.
Preparation example 3
Except that 62g of zirconia was replaced with 62g of gamma-Al 2 O 3 Otherwise, the same procedure as in preparation example 1 was repeated.
Preparation example 4
Preparation example 1 was repeated except that 7.05g of copper nitrate was replaced with 7.32g of cobalt nitrate.
Preparation example 5
The product was prepared using the procedure of CN104475114A, example 3. And (3) granulating, tabletting and crushing the product, and screening out the catalyst with the particle size of 20-50 meshes. The catalyst comprises the following components: 70wt% CuO-15wt% ZnO-10wt% 2 -5wt％ZrO 2 。
Example 1 and comparative examples 1 to 4
Continuously introducing a hydrogen sulfide-containing gas into a fixed bed reactor containing a catalyst to make the catalyst andthe hydrogen sulfide-containing gas has the temperature of 80 ℃ and the space velocity of 2000h -1 The gas after contact is obtained. H in gas containing hydrogen sulfide 2 The concentration of S is 50mg/Nm 3 ，O 2 The concentration of (A) was 2000ppm, and the concentration of CO was 25vol%. The catalyst is specifically shown in table 1. The oxygen content of the contacted gas at the outlet of the fixed bed reactor was measured while continuously feeding the hydrogen sulfide-containing gas for 50 hours, and the results are shown in Table 1.
TABLE 1
Comparing example 1 with comparative examples 1 to 3, it is clear that the composition of the catalyst has an important influence on the oxygen removal performance of the catalyst. Is reacted with ZrO 2 Substitution with Al 2 O 3 Or SiO 2 Or the CuO is replaced by Co oxide, the oxygen removal performance is obviously reduced, and O in the contacted gas 2 The content increases.
As is clear from comparison of example 1 with comparative example 4, the content of each oxide in the catalyst was determined with respect to O in the hydrogen sulfide-containing gas 2 The removal effect of (2) has an important influence, the catalyst of preparation example 5 has an excessive CuO content and ZrO 2 And the ZnO content is too low, the sulfur resistance is weak, and the performance of removing oxygen from the gas containing hydrogen sulfide is poor.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and alterations that may occur to those skilled in the art may fall within the scope of the present invention without departing from the spirit of the present invention.
Claims (10)
1. A method for removing oxygen in a gas containing hydrogen sulfide is characterized by comprising the following steps:
contacting the hydrogen sulfide-containing gas with a catalyst to remove oxygen;
wherein the catalyst comprises 1 to 7 weight portions of CuO and 5 to 15 weight portions of CeO 2 15 to 25 parts by weight of ZnO and 55 to 70 parts by weight of ZrO 2 ；
Wherein H in the hydrogen sulfide-containing gas 2 The concentration of S is 1-70 mg/Nm 3 ，O 2 The concentration of (A) is 100 to 5000ppm.
2. The method of claim 1, wherein the catalyst consists essentially of 1 to 7 parts by weight of CuO,5 to 15 parts by weight of CeO 2 15 to 25 parts by weight of ZnO and 55 to 70 parts by weight of ZrO 2 And (4) forming.
3. The process of claim 1, wherein the hydrogen sulfide-containing gas is contacted with the catalyst at a temperature of 50 to 160 ℃.
4. The process of claim 1, wherein the hydrogen sulfide-containing gas is fed at a space velocity of 500 to 3000h -1 Under conditions such that the catalyst is contacted.
5. The process of claim 1, wherein the hydrogen sulfide-containing gas is contacted with the catalyst in a fixed bed reactor.
6. The process of claim 1 wherein the catalyst is cylindrical and has a diameter of 2 to 8mm.
7. The method according to any one of claims 1 to 6, further comprising a step of preparing a catalyst:
(1) Dipping a mixture comprising zinc oxide, zirconium oxide and sesbania powder into an aqueous solution containing a soluble copper salt and a soluble cerium salt; then kneading to obtain a kneaded material;
(2) Molding the kneaded material to obtain a blank;
(3) And drying the green body, and then roasting to obtain the catalyst.
8. The method as claimed in claim 7, wherein the method of isovolumetric impregnation is used for a period of 4 to 10 hours.
9. The method according to claim 7, wherein the drying temperature is 100 to 150 ℃ and the drying time is 1 to 6 hours; the roasting temperature is 400-600 ℃, and the roasting time is 2-7 h.
10. The application of a catalyst in removing oxygen in gas containing hydrogen sulfide is characterized in that the catalyst comprises 1-7 parts by weight of CuO and 5-15 parts by weight of CeO 2 15 to 25 parts by weight of ZnO and 55 to 70 parts by weight of ZrO 2 (ii) a H in the gas containing hydrogen sulfide 2 The concentration of S is 1-70 mg/Nm 3 ，O 2 The concentration of (A) is 100 to 5000ppm.
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| CN202211082273.6A CN115301246A (en) | 2022-09-06 | 2022-09-06 | Method for removing oxygen in hydrogen sulfide-containing gas and application of catalyst |
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| CN202211082273.6A CN115301246A (en) | 2022-09-06 | 2022-09-06 | Method for removing oxygen in hydrogen sulfide-containing gas and application of catalyst |
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Citations (6)
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| JPS60161317A (en) * | 1984-01-31 | 1985-08-23 | Kansai Coke & Chem Co Ltd | Method for removing oxygen from oxygen-containing gas consisting essentially of carbon monoxide |
| US20060289024A1 (en) * | 2005-03-11 | 2006-12-28 | Philip Morris Usa Inc. | Catalysts for low temperature oxidation of carbon monoxide |
| CN101301611A (en) * | 2008-07-07 | 2008-11-12 | 西南化工研究设计院 | Sulfur-tolerance deoxidation catalyst and preparation and use thereof |
| CN104475114A (en) * | 2014-11-19 | 2015-04-01 | 上海化工研究院 | Copper-zinc-cerium-based catalyst for low-temperature deep removal of carbon monoxide and preparation method and application of catalyst |
| CN104888798A (en) * | 2015-06-10 | 2015-09-09 | 西南化工研究设计院有限公司 | High-activity catalyst for sulfur-tolerant deoxidization of CO-rich gas and preparation method of high-activity catalyst |
| CN109647380A (en) * | 2018-12-29 | 2019-04-19 | 武汉科林精细化工有限公司 | A kind of composite oxide catalysts and its preparation method and application for rich CO qi exhaustion oxygen |
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2022
- 2022-09-06 CN CN202211082273.6A patent/CN115301246A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60161317A (en) * | 1984-01-31 | 1985-08-23 | Kansai Coke & Chem Co Ltd | Method for removing oxygen from oxygen-containing gas consisting essentially of carbon monoxide |
| US20060289024A1 (en) * | 2005-03-11 | 2006-12-28 | Philip Morris Usa Inc. | Catalysts for low temperature oxidation of carbon monoxide |
| CN101301611A (en) * | 2008-07-07 | 2008-11-12 | 西南化工研究设计院 | Sulfur-tolerance deoxidation catalyst and preparation and use thereof |
| CN104475114A (en) * | 2014-11-19 | 2015-04-01 | 上海化工研究院 | Copper-zinc-cerium-based catalyst for low-temperature deep removal of carbon monoxide and preparation method and application of catalyst |
| CN104888798A (en) * | 2015-06-10 | 2015-09-09 | 西南化工研究设计院有限公司 | High-activity catalyst for sulfur-tolerant deoxidization of CO-rich gas and preparation method of high-activity catalyst |
| CN109647380A (en) * | 2018-12-29 | 2019-04-19 | 武汉科林精细化工有限公司 | A kind of composite oxide catalysts and its preparation method and application for rich CO qi exhaustion oxygen |
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