WO2020260289A1 - A catalyst for the selective oxidation of hydrogen sulfide to sulfur - Google Patents
A catalyst for the selective oxidation of hydrogen sulfide to sulfur Download PDFInfo
- Publication number
- WO2020260289A1 WO2020260289A1 PCT/EP2020/067514 EP2020067514W WO2020260289A1 WO 2020260289 A1 WO2020260289 A1 WO 2020260289A1 EP 2020067514 W EP2020067514 W EP 2020067514W WO 2020260289 A1 WO2020260289 A1 WO 2020260289A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas
- catalyst
- sulfur
- elemental sulfur
- catalyst according
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 25
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims description 6
- 229910052717 sulfur Inorganic materials 0.000 title description 11
- 239000011593 sulfur Substances 0.000 title description 11
- 230000003647 oxidation Effects 0.000 title description 10
- 238000007254 oxidation reaction Methods 0.000 title description 10
- 239000007789 gas Substances 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 238000009833 condensation Methods 0.000 claims abstract description 6
- 230000005494 condensation Effects 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 150000002506 iron compounds Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000011152 fibreglass Substances 0.000 claims description 3
- 241000286904 Leptothecata Species 0.000 claims 1
- 239000011149 active material Substances 0.000 abstract 1
- 229920000297 Rayon Polymers 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 229960005349 sulfur Drugs 0.000 description 10
- 235000001508 sulfur Nutrition 0.000 description 10
- 230000008569 process Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229940065278 sulfur compound Drugs 0.000 description 4
- 150000003464 sulfur compounds Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 235000014666 liquid concentrate Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- IHYNKGRWCDKNEG-UHFFFAOYSA-N n-(4-bromophenyl)-2,6-dihydroxybenzamide Chemical compound OC1=CC=CC(O)=C1C(=O)NC1=CC=C(Br)C=C1 IHYNKGRWCDKNEG-UHFFFAOYSA-N 0.000 description 2
- 229960003903 oxygen Drugs 0.000 description 2
- 229940079101 sodium sulfide Drugs 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfate Natural products OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229940112112 capex Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- FEBLZLNTKCEFIT-VSXGLTOVSA-N fluocinolone acetonide Chemical compound C1([C@@H](F)C2)=CC(=O)C=C[C@]1(C)[C@]1(F)[C@@H]2[C@@H]2C[C@H]3OC(C)(C)O[C@@]3(C(=O)CO)[C@@]2(C)C[C@@H]1O FEBLZLNTKCEFIT-VSXGLTOVSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011746 zinc citrate Substances 0.000 description 1
- 229940068475 zinc citrate Drugs 0.000 description 1
- 235000006076 zinc citrate Nutrition 0.000 description 1
Classifications
-
- 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
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0426—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion
- C01B17/043—Catalytic converters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
-
- 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
- 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
- B01J23/80—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 zinc, cadmium or mercury
-
- B01J35/56—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/102—Oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20738—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20792—Zinc
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
Definitions
- the present invention relates to a catalyst for use in the selective oxidation of hydrogen sulfide (3 ⁇ 4S) to elemental sulfur.
- the Applicant has developed the POC (preferential oxidation catalyst) and a POC process to treat PhS-containing off-gases from the viscose industry, where the special POC catalyst is capable of catalyzing the 3 ⁇ 4S to S reaction but displays a very low activity for the Claus reaction, and thus the reaction of 3 ⁇ 4S to yield S is not reversed, even at the very high oxy gen levels present in a viscose off-gas. Furthermore, due to the fact that the viscose off-gases contain particulates and due to the advantages of a high surface area and a low diffusion resistance, the POC catalyst is in monolithic form.
- US 2005/0147554 A1 describes the use of a wet oxidation process to control the concentration of reduced sulfur com pounds from a viscose process.
- the wet oxidation process oxidizes the reduced sulfur compounds to convert them to an alkali sulfate and/or thiosulfate species.
- the alkali sul fate stream is recycled to the viscose process.
- the oxida tion is performed under elevated temperature and pressure conditions, such that the off-gas has an oxygen concentra tion between about 2% and about 18%, and the alkali sulfate stream has a pH of about 2 to 10.
- sulfurous gas streams comprising 3 ⁇ 4S and CS2, such as produced as a by-product of the process of rayon-forming, are processed to recover the components in a usable form.
- First the gas stream is contacted with aqueous NaOH to dissolve out 3 ⁇ 4S and some of the CS2.
- the dissolved CS2 is driven off from the solution and condensed out as a liquid concentrate. Any CS2 remaining in the gas stream is recovered, such as by condensation.
- the aqueous sodium sul fide solution which remains from removal of CS2, is con centrated and the pH is adjusted, as necessary, to a value at which the sodium sulfide is predominantly in the form of sodium bisulfide.
- the concentrated sodium bisulfide solu tion is capable of being re-used in the rayon-forming pro cess along with the liquid concentrate of CS2.
- WO 97/32813 A1 describes a catalyst for the selective oxi- dation of sulfur compounds, in particular 3 ⁇ 4S to elemental S.
- cylindrical S1O2 (silica) extrusions of a diameter of 2.1 mm and a length of 10 mm (monoliths) were impregnated with iron cit rate and zinc citrate followed by drying and calcination.
- the loading of the S1O2 is described to be 5 wt% of iron oxide and 10 wt% of zinc oxide.
- a method for the selective oxidation of 3 ⁇ 4S to elemental S, where a H2S-containing gas together with an oxygen-containing gas is passed over the catalyst, is also described. Furthermore, it is disclosed that the temperature of the catalyst bed must be above the dew point temperature of the sulfur formed.
- the general standard solution for removing sul- fur from viscose off-gases is to use LoCat®-type technology for enrichment of 3 ⁇ 4S combined with a standard Claus reac tion situated downstream.
- This technology makes use of a proprietary liquid redox catalyst that converts 3 ⁇ 4S to solid elemental sulfur through a direct oxidation of 3 ⁇ 4S (3 ⁇ 4S + 1 ⁇ 2 O 2 H 2 O + S°) .
- This reaction consists of five se quential steps: Absorption of 3 ⁇ 4S, ionization of 3 ⁇ 4S, cata lytic oxidation of sulfide, absorption of oxygen and iron oxidation to get Fe 2+ back to the Fe 3+ state.
- Applicant's POC catalyst is ca pable of selectively converting 3 ⁇ 4S to elemental S in a gas containing up to more than 20 wt% oxygen, as is the case in off-gas in the viscose industry, by using the oxygen that is sometimes present in the gas and/or by adding oxygen.
- the sulfur can then be removed by condensation or by using a liquid contactor. This is very attractive in the applica tion of the POC catalyst to remove sulfur from coke oven gas and synthesis gas from coal gasification, biomass gasi fication and waste gasification.
- the present invention relates to a cata lyst for use in the selective conversion of hydrogen sul fide (3 ⁇ 4S) to elemental sulfur (S) and SO 2 in a gas that is passed through a catalytic reactor containing the catalyst, where the selective conversion of 3 ⁇ 4S in the gas is estab lished either via the oxygen present in the gas or via oxy gen added to the gas stream, and where removal of the ele mental sulfur from the effluent gas from the catalytic re actor is done by condensation or by contact with a liquid contactor .
- the monolithic catalyst of the invention comprises a silica carrier impregnated with a material that is catalytically active in oxidizing 3 ⁇ 4S to elemental sulfur and SO2, said material being embed ded in the walls of a corrugated monolith made from a fi- berglass matrix.
- a fibrous monolith provides a unique fea ture in that it provides a very open internal pore struc ture in the wall and simultaneously a high surface area which, uniquely, provides a benefit for the reaction versus side reactions. This cannot be accomplished with a standard extruded coated monolith or a coated corrugated metal mono lith.
- the material that is catalytically active in oxidizing 3 ⁇ 4S to elemental sulfur and SO2 comprises an iron compound .
- the iron compound is combined with zinc oxide. It is preferred that the iron compound in the catalyst according to the in vention contains from 1 to 15 wt% iron.
- Applicant's POC monolith which is a monolithic catalyst where a silica carrier is embedded in the walls of a corrugated monolith made from a fiberglass sheet matrix, selectively oxidizes the 3 ⁇ 4S present in a gas into elemental sulfur.
- the silica carrier is impregnated with an iron catalyst, optionally in combination with zinc oxide.
- the catalyst has very specific measurements in terms of height, width and depth as well as the distance between the corrugated glass fiber sheets.
- the catalyst of the invention is a monolithic cata lyst embedded in the walls of a corrugated monolith made from a fiberglass matrix. It comprises a silica carrier that is preferably impregnated with a catalytic iron com pound.
- the iron compound can be combined with zinc oxide.
- Fig. 1 and Fig. 2 are schematic drawings of a catalytic monolith of the present invention seen from the end and in cross-section, respectively, and
- Fig. 3 is an enlarged view of the cross-sectional view of the catalytic monolith of the invention.
- Fig. 1 shows a catalytic monolith 1 in the shape of a box
- Fig. 2 shows a spirally wound monolith 1' in cylin drical shape
- the monoliths 1, 1' comprise full body porous material in the form of porous substrates coated and im pregnated with a catalytic substance.
- the substrates of the monolith of figures 1 and 2 are corrugated sheets of full body porous material 2, 2', also denoted “corrugated sheets”, which are supported and separated from each other by substrates 3, 3' of substantially flat sheets of full body porous material, also denoted “liners” or “plates”.
- the corrugated and flat sheets 2,2’ ,3,3’ are full body po- rous material, i.e. they each comprise a porous substrate and a catalyst coating homogeneously distributed throughout the substrate, and each of the sheets 2,2' ,3,3' are suita bly impregnated.
- the catalyst of the invention enables a simpler and more effective way to remove sulfur from viscose off-gas.
- the method is suitable for low and medium high sulfur contents.
- the technology is low in CAPEX and has a low OPEX due to the fact that no additional chemicals are needed to remove the sulfur compounds.
- the technology can be combined with 3 ⁇ 4S sorbent technology and further combined with hydrogenation of any slip of sul- fur components.
Abstract
A monolithic catalyst for use in the selective conversion of H2S to S and SO2 in a gas that is passed through a catalytic reactor containing the catalyst, where the selective conversion of H2S in the gas is effected either via the oxygen present in the gas or via oxygen added to the gas stream, and where removal of the elemental sulfur from the effluent gas from the catalytic reactor is done by condensation or by contact with a liquid contactor. The catalyst comprises a silica carrier impregnated with a catalytically active material embedded in the walls of a corrugated monolith.
Description
Title: A catalyst for the selective oxidation of hydrogen sulfide to sulfur
The present invention relates to a catalyst for use in the selective oxidation of hydrogen sulfide (¾S) to elemental sulfur.
It is known from the refinery industry that the selective reaction of ¾S to elementary sulfur can be catalyzed, and this reaction is used as a final catalytic reaction step connected to the well-known Claus technology under the trade names SuperClaus and EuroClaus, where EuroClaus (a trade mark of Jacobs Nederland B.V.) is a process including an upstream hydrogenation of all sulfur components followed by the selective ¾S to S conversion step. The Applicant has developed the POC (preferential oxidation catalyst) and a POC process to treat PhS-containing off-gases from the viscose industry, where the special POC catalyst is capable of catalyzing the ¾S to S reaction but displays a very low activity for the Claus reaction, and thus the reaction of ¾S to yield S is not reversed, even at the very high oxy gen levels present in a viscose off-gas. Furthermore, due to the fact that the viscose off-gases contain particulates and due to the advantages of a high surface area and a low diffusion resistance, the POC catalyst is in monolithic form.
The advantageous result is that plugging is avoided, and a high reaction rate is achieved along with a low degree of by-product formation. A patent application directed to the POC process was filed by the Applicant in 2016. Said patent application, now pub lished as WO 2016/065173 A1 , concerns a method for cleaning an off-gas from viscose production, essentially containing ¾S and CS2, which comprises passing the gas through a cat- alytic reactor to convert ¾S in the gas to elemental sul fur, SO2 or mixtures thereof, either via the oxygen present in the gas or via oxygen added to the gas stream. Elemental sulfur and SO2 are removed from the effluent gas from the catalytic reactor, and the unconverted CS2 is recycled to the viscose production process.
US 2005/0147554 A1 describes the use of a wet oxidation process to control the concentration of reduced sulfur com pounds from a viscose process. The wet oxidation process oxidizes the reduced sulfur compounds to convert them to an alkali sulfate and/or thiosulfate species. The alkali sul fate stream is recycled to the viscose process. The oxida tion is performed under elevated temperature and pressure conditions, such that the off-gas has an oxygen concentra tion between about 2% and about 18%, and the alkali sulfate stream has a pH of about 2 to 10.
In US 6.416.725 Bl, sulfurous gas streams comprising ¾S and CS2, such as produced as a by-product of the process of rayon-forming, are processed to recover the components in a usable form. First the gas stream is contacted with aqueous NaOH to dissolve out ¾S and some of the CS2. The dissolved CS2 is driven off from the solution and condensed out as a
liquid concentrate. Any CS2 remaining in the gas stream is recovered, such as by condensation. The aqueous sodium sul fide solution, which remains from removal of CS2, is con centrated and the pH is adjusted, as necessary, to a value at which the sodium sulfide is predominantly in the form of sodium bisulfide. The concentrated sodium bisulfide solu tion is capable of being re-used in the rayon-forming pro cess along with the liquid concentrate of CS2.
WO 97/32813 A1 describes a catalyst for the selective oxi- dation of sulfur compounds, in particular ¾S to elemental S. In an example of preparing the catalyst, cylindrical S1O2 (silica) extrusions of a diameter of 2.1 mm and a length of 10 mm (monoliths) were impregnated with iron cit rate and zinc citrate followed by drying and calcination. The loading of the S1O2 is described to be 5 wt% of iron oxide and 10 wt% of zinc oxide. A method for the selective oxidation of ¾S to elemental S, where a H2S-containing gas together with an oxygen-containing gas is passed over the catalyst, is also described. Furthermore, it is disclosed that the temperature of the catalyst bed must be above the dew point temperature of the sulfur formed.
Various embodiments of waste gas recovery and adsorption systems for waste gases from viscose fiber production are described in Chinese utility model and patent applications CN 204107303 U, CN 204134460 U, CN 201115810 Y and CN
101219319 A, generally employing alkali cleaning/adsorption and condensation methods. While relevant, however, these CN applications do not anticipate the present invention.
At present, the general standard solution for removing sul- fur from viscose off-gases is to use LoCat®-type technology
for enrichment of ¾S combined with a standard Claus reac tion situated downstream. This technology makes use of a proprietary liquid redox catalyst that converts ¾S to solid elemental sulfur through a direct oxidation of ¾S (¾S + ½ O2 H2O + S°) . This reaction consists of five se quential steps: Absorption of ¾S, ionization of ¾S, cata lytic oxidation of sulfide, absorption of oxygen and iron oxidation to get Fe2+ back to the Fe3+ state.
It has now been found that Applicant's POC catalyst is ca pable of selectively converting ¾S to elemental S in a gas containing up to more than 20 wt% oxygen, as is the case in off-gas in the viscose industry, by using the oxygen that is sometimes present in the gas and/or by adding oxygen.
The sulfur can then be removed by condensation or by using a liquid contactor. This is very attractive in the applica tion of the POC catalyst to remove sulfur from coke oven gas and synthesis gas from coal gasification, biomass gasi fication and waste gasification.
More specifically, the present invention relates to a cata lyst for use in the selective conversion of hydrogen sul fide (¾S) to elemental sulfur (S) and SO2 in a gas that is passed through a catalytic reactor containing the catalyst, where the selective conversion of ¾S in the gas is estab lished either via the oxygen present in the gas or via oxy gen added to the gas stream, and where removal of the ele mental sulfur from the effluent gas from the catalytic re actor is done by condensation or by contact with a liquid contactor .
In the most preferred embodiment, the monolithic catalyst
of the invention comprises a silica carrier impregnated with a material that is catalytically active in oxidizing ¾S to elemental sulfur and SO2, said material being embed ded in the walls of a corrugated monolith made from a fi- berglass matrix. A fibrous monolith provides a unique fea ture in that it provides a very open internal pore struc ture in the wall and simultaneously a high surface area which, uniquely, provides a benefit for the reaction versus side reactions. This cannot be accomplished with a standard extruded coated monolith or a coated corrugated metal mono lith.
Preferably, the material that is catalytically active in oxidizing ¾S to elemental sulfur and SO2 comprises an iron compound . In a preferred catalyst according to the invention, the iron compound is combined with zinc oxide. It is preferred that the iron compound in the catalyst according to the in vention contains from 1 to 15 wt% iron.
Laboratory experiments have demonstrated that Applicant's POC monolith, which is a monolithic catalyst where a silica carrier is embedded in the walls of a corrugated monolith made from a fiberglass sheet matrix, selectively oxidizes the ¾S present in a gas into elemental sulfur. The silica carrier is impregnated with an iron catalyst, optionally in combination with zinc oxide. The catalyst has very specific measurements in terms of height, width and depth as well as the distance between the corrugated glass fiber sheets.
Thus, the catalyst of the invention is a monolithic cata lyst embedded in the walls of a corrugated monolith made
from a fiberglass matrix. It comprises a silica carrier that is preferably impregnated with a catalytic iron com pound. Advantageously, the iron compound can be combined with zinc oxide. The invention is further illustrated with reference to the attached figures, where
Fig. 1 and Fig. 2 are schematic drawings of a catalytic monolith of the present invention seen from the end and in cross-section, respectively, and
Fig. 3 is an enlarged view of the cross-sectional view of the catalytic monolith of the invention.
Fig. 1 shows a catalytic monolith 1 in the shape of a box, whilst Fig. 2 shows a spirally wound monolith 1' in cylin drical shape. The monoliths 1, 1' comprise full body porous material in the form of porous substrates coated and im pregnated with a catalytic substance. The substrates of the monolith of figures 1 and 2 are corrugated sheets of full body porous material 2, 2', also denoted "corrugated sheets", which are supported and separated from each other by substrates 3, 3' of substantially flat sheets of full body porous material, also denoted "liners" or "plates".
The corrugated and flat sheets 2,2’ ,3,3’ are full body po- rous material, i.e. they each comprise a porous substrate and a catalyst coating homogeneously distributed throughout the substrate, and each of the sheets 2,2' ,3,3' are suita bly impregnated.
The effects and advantages of the invention are as follows:
The catalyst of the invention enables a simpler and more effective way to remove sulfur from viscose off-gas. The method is suitable for low and medium high sulfur contents. The technology is low in CAPEX and has a low OPEX due to the fact that no additional chemicals are needed to remove the sulfur compounds.
The technology can be combined with ¾S sorbent technology and further combined with hydrogenation of any slip of sul- fur components.
Claims
1. A catalyst for use in the selective conversion of hydrogen sulfide (¾S) to elemental sulfur (S) and SO2 in a gas that is passed through a catalytic reactor containing the catalyst, where the selective conversion of ¾S in the gas is effected either via the oxygen present in the gas or via oxygen added to the gas stream, and where removal of the elemental sulfur from the effluent gas from the cata lytic reactor is done by condensation or by contact with a liquid contactor.
2. Catalyst according to claim 1, which is a mono- lithic catalyst comprising a silica carrier impregnated with a material catalytically active in oxidizing ¾S to elemental sulfur and SO2 and embedded in the walls of a corrugated monolith made from a fiberglass matrix.
3. Catalyst according to claim 2, wherein the material catalytically active in oxidizing ¾S to elemental sulfur and SO2 comprises an iron compound.
4. Catalyst according to claim 3, wherein the iron compound is combined with zinc oxide.
5. Catalyst according to any of the claims 2-4,
wherein the iron compound contains 1 to 15 wt% iron.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2019105562440 | 2019-06-25 | ||
CN2019209644055 | 2019-06-25 | ||
CN201910556244.0A CN112121796A (en) | 2019-06-25 | 2019-06-25 | Catalyst for selective oxidation of hydrogen sulfide to sulfur |
CN201920964405 | 2019-06-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020260289A1 true WO2020260289A1 (en) | 2020-12-30 |
Family
ID=71266628
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2020/067514 WO2020260289A1 (en) | 2019-06-25 | 2020-06-23 | A catalyst for the selective oxidation of hydrogen sulfide to sulfur |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2020260289A1 (en) |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0422999A1 (en) * | 1989-10-09 | 1991-04-17 | Rhone-Poulenc Chimie | Catalysts for treating exhaust gases and process for treating these exhaust gases |
WO1996036422A1 (en) * | 1995-05-17 | 1996-11-21 | Parsons Process Group Inc. | Process for selective oxidation |
WO1997032813A1 (en) | 1996-03-04 | 1997-09-12 | Gastec N.V. | Catalyst for the selective oxidation of sulfur compounds to elemental sulfur, method for the preparation of such a catalyst, and method for the selective oxidation of sulfur compounds to elemental sulfur |
US5948382A (en) * | 1995-09-05 | 1999-09-07 | National Science Council | Selective oxidation of hydrogen sulfide in the presence of mixed-oxide catalyst containing iron, molybdenum and antimony |
US6416725B1 (en) | 1997-05-21 | 2002-07-09 | Turbotak Technologies Inc. | Removal of contaminants from gas streams in rayon production |
US20050147554A1 (en) | 2003-10-29 | 2005-07-07 | Usfilter Corporation | System and method of wet oxidation of a viscose process stream |
CN101219319A (en) | 2007-09-30 | 2008-07-16 | 泉州市天龙环境工程有限公司 | Device for recovering viscose fiber production exhaust-gas with soda washing-adsorption condensing method |
CN201115810Y (en) | 2007-09-30 | 2008-09-17 | 泉州市天龙环境工程有限公司 | Device for recovering viscose fiber production exhaust-gas by alkali cleaning-adsorption condensation method |
CN204107303U (en) | 2014-06-10 | 2015-01-21 | 江苏申江环境科技有限公司 | Viscose rayon waste gas recovery adsorption system |
CN204134460U (en) | 2014-06-10 | 2015-02-04 | 江苏申江环境科技有限公司 | Viscose rayon process gas recovery system |
WO2016065173A1 (en) | 2014-10-22 | 2016-04-28 | Alibaba Group Holding Limited | Method and apparatus for displaying statistical graphs on a terminal display |
WO2018138200A1 (en) * | 2017-01-25 | 2018-08-02 | Haldor Topsøe A/S | A process for treating the off gas from a carbon black plant to recover sulphur |
-
2020
- 2020-06-23 WO PCT/EP2020/067514 patent/WO2020260289A1/en active Application Filing
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0422999A1 (en) * | 1989-10-09 | 1991-04-17 | Rhone-Poulenc Chimie | Catalysts for treating exhaust gases and process for treating these exhaust gases |
WO1996036422A1 (en) * | 1995-05-17 | 1996-11-21 | Parsons Process Group Inc. | Process for selective oxidation |
US5948382A (en) * | 1995-09-05 | 1999-09-07 | National Science Council | Selective oxidation of hydrogen sulfide in the presence of mixed-oxide catalyst containing iron, molybdenum and antimony |
WO1997032813A1 (en) | 1996-03-04 | 1997-09-12 | Gastec N.V. | Catalyst for the selective oxidation of sulfur compounds to elemental sulfur, method for the preparation of such a catalyst, and method for the selective oxidation of sulfur compounds to elemental sulfur |
US6416725B1 (en) | 1997-05-21 | 2002-07-09 | Turbotak Technologies Inc. | Removal of contaminants from gas streams in rayon production |
US20050147554A1 (en) | 2003-10-29 | 2005-07-07 | Usfilter Corporation | System and method of wet oxidation of a viscose process stream |
CN101219319A (en) | 2007-09-30 | 2008-07-16 | 泉州市天龙环境工程有限公司 | Device for recovering viscose fiber production exhaust-gas with soda washing-adsorption condensing method |
CN201115810Y (en) | 2007-09-30 | 2008-09-17 | 泉州市天龙环境工程有限公司 | Device for recovering viscose fiber production exhaust-gas by alkali cleaning-adsorption condensation method |
CN204107303U (en) | 2014-06-10 | 2015-01-21 | 江苏申江环境科技有限公司 | Viscose rayon waste gas recovery adsorption system |
CN204134460U (en) | 2014-06-10 | 2015-02-04 | 江苏申江环境科技有限公司 | Viscose rayon process gas recovery system |
WO2016065173A1 (en) | 2014-10-22 | 2016-04-28 | Alibaba Group Holding Limited | Method and apparatus for displaying statistical graphs on a terminal display |
WO2018138200A1 (en) * | 2017-01-25 | 2018-08-02 | Haldor Topsøe A/S | A process for treating the off gas from a carbon black plant to recover sulphur |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
FI85661C (en) | A catalyst and process for the oxidation of sulfur-containing compounds | |
KR102376149B1 (en) | Production of sulfuric acid from coke oven gas desulfurisation product | |
CA2361676C (en) | Method for desulphurization of gases | |
EP0078690B1 (en) | Process for the reduction of the sulfur content in a gaseous stream | |
KR910002508A (en) | Catalyst for oxidation of sulfur compound and its manufacturing method | |
CN103331095B (en) | Simultaneous desulphurization and denitration device for seawater smoke with membrane absorption method, as well as process of device | |
JP2017528315A (en) | Method for oxidizing hydrogen sulfide to sulfur trioxide, including later removal of sulfur trioxide, and plant for performing the method | |
JP4831295B2 (en) | Exhaust gas desulfurization method | |
CN100475689C (en) | Recovery of sulfur from a hydrogen sulfide containing gas | |
US7279148B1 (en) | Oxidizer and oxidation process for a desulphurization process | |
WO2016198369A1 (en) | Hydrogen sulfide abatement via removal of sulfur trioxide | |
CA2237744A1 (en) | Catalyst and process for oxidation of sulphur dioxide | |
JP2000248286A (en) | Purification process for coke oven gas | |
WO2020260289A1 (en) | A catalyst for the selective oxidation of hydrogen sulfide to sulfur | |
WO2019158474A1 (en) | Production of fertilizers from landfill gas or digester gas | |
CN112121796A (en) | Catalyst for selective oxidation of hydrogen sulfide to sulfur | |
SK182099A3 (en) | Method for desulfurizing off-gases | |
JP2009149460A (en) | Surface modification method of carbonaceous material, and carbonaceous material or activated carbon fiber | |
Mashapa et al. | Catalytic performance and deactivation of precipitated iron catalyst for selective oxidation of hydrogen sulfide to elemental sulfur in the waste gas streams from coal gasification | |
CA2361210C (en) | Method for continuously producing thiosulfate ions | |
WO2020254578A1 (en) | Method and catalyst for selective oxidation of hydrogen sulfide to elemental sulfur in a reducing gas | |
US4003987A (en) | Waste stream treatment | |
CN112608773A (en) | Method for blast furnace gas photocatalytic hydrolysis fine desulfurization | |
CN216711600U (en) | Containing H2S synthetic gas low-temperature chemical-looping desulfurization and sulfuric acid co-production system | |
CN216726614U (en) | Desulfurization regeneration tail gas processing system |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20735109 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 20735109 Country of ref document: EP Kind code of ref document: A1 |