CN115569649A - Catalyst for preparing sulfur by selective oxidation of hydrogen sulfide and preparation and use methods thereof - Google Patents
Catalyst for preparing sulfur by selective oxidation of hydrogen sulfide and preparation and use methods thereof Download PDFInfo
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- CN115569649A CN115569649A CN202211386236.4A CN202211386236A CN115569649A CN 115569649 A CN115569649 A CN 115569649A CN 202211386236 A CN202211386236 A CN 202211386236A CN 115569649 A CN115569649 A CN 115569649A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 31
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000011593 sulfur Substances 0.000 title claims abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000011148 porous material Substances 0.000 claims abstract description 34
- 239000007789 gas Substances 0.000 claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 16
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 4
- 229920000053 polysorbate 80 Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000011863 silicon-based powder Substances 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
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 239000004480 active ingredient Substances 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 238000011084 recovery Methods 0.000 abstract description 11
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract description 2
- 230000019635 sulfation Effects 0.000 abstract description 2
- 238000005670 sulfation reaction Methods 0.000 abstract description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 10
- 101150116295 CAT2 gene Proteins 0.000 description 7
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 7
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 7
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 7
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 7
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
Classifications
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- 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- C01B17/0434—Catalyst compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst for preparing sulfur by selective oxidation of hydrogen sulfide, and a preparation method and a use method thereof. The catalyst takes silicon dioxide as a carrier and ferric oxide as an active component. The temperature of the inlet section is low, the diffusion rate of gas molecules is low, and the conversion rate of hydrogen sulfide can be effectively ensured by selecting silicon dioxide with low specific surface area and small pore volume and pore diameter; the high-temperature section at the outlet is made of silicon dioxide with high specific surface area and large pore volume and pore diameter, so that the retention time of gas in the pore channel is shortened, and the recovery rate of sulfur can be obviously improved. When in preparation, silicon dioxide with high stability is selected as a carrier, so that the catalyst has strong sulfation resistance and can prolong the service life of the catalyst; the inlet low-temperature section and the outlet high-temperature section adopt raw materials produced by different methods, so that the high recovery rate of sulfur is ensured, and the use temperature zone of the catalyst is widened.
Description
Technical Field
The invention belongs to the field of preparation and use of catalysts, relates to a catalyst for preparing sulfur by selective oxidation of hydrogen sulfide and a preparation and use method thereof, and particularly relates to a catalyst for preparing sulfur by selective oxidation of hydrogen sulfide, which has higher hydrogen sulfide conversion rate and sulfur recovery rate, and a preparation and use method thereof.
Background
The petroleum industry, the refining of natural gas, the melting of metals in steel production, the liquefaction of coal and the like are often accompanied by the formation of considerable quantities of sulfides, mainly H 2 And S. It is a form of sulfide-type contaminant and also one of the sources of pollution caused by acid rain.
For high concentrations of H 2 S tail gas treatment, wherein a Claus tail gas recovery method is generally adopted in industry. For low concentrations of H 2 S (less than 15%) tail gas treatment is not economical due to the limitations of the Claus process on thermodynamics, and 3% -5% of H is still left after the Claus process treatment 2 S is not transformed.
The basic reaction principle of the sulfur recovery process by the direct oxidation method is as follows: h 2 S+O 2 →S+H 2 O + Q, which is not an equilibrium reaction, theoretically can reach 100 percent conversion rate to H in acid gas 2 The S concentration has no lower limit requirement and has simple deviceThe method has the advantages of large operation flexibility, less investment, high removal rate, low consumption, easy control and operation and the like, and is particularly suitable for treating the lean acid gas.
With the improvement of environmental protection laws and regulations and the improvement of national requirements on environmental emission standards, the direct oxidation sulfur recovery process draws high attention in the industry. The key to the process is reactor design, process optimization and catalyst development, which plays a key role.
The main problems existing when the oxidation sulfur recovery catalyst is selected for use at present are as follows: (1) The selectivity of the catalyst is low, mainly the selectivity of sulfur dioxide is high, so that the recovery rate of sulfur is low; (2) The catalyst has poor stability, mainly uses raw materials which are easy to be sulfated, and has short service life although the initial activity and the low-temperature activity are higher; (3) H 2 S+O 2 →S+H 2 The O + Q is a strong exothermic reaction, and the activity and the selectivity of the catalyst are reduced rapidly along with the increase of the temperature, so that the applicable temperature zone of the catalyst is narrow.
CN201110255125.5 discloses a method for preparing a catalyst for preparing sulfur by hydrogen sulfide selective oxidation by using silicon dioxide as a raw material, adding an alkali metal oxide and an alkaline earth metal oxide for modification, extruding a strip-shaped carrier, taking iron oxide as an active component, and preparing the catalyst for preparing sulfur by hydrogen sulfide selective oxidation by an impregnation method, wherein the pore volume of the carrier is more than 0.5ml/g, and the average pore diameter is more than 30 nm. The catalyst has high activity and selectivity at low temperature, and the selectivity and yield are obviously reduced when the use temperature is higher than 220 ℃.
CN201310256676.2 discloses a preparation method of a catalyst for preparing sulfur by selective oxidation of hydrogen sulfide, which uses silicon dioxide, beta-silicon carbide, modifier and the like as carriers and iron oxide as active components. The specific surface area of the carrier is not more than 100m by adding beta-silicon carbide 2 (ii)/g, the average pore diameter is greater than 20nm. When the use temperature is increased, the sulfur yield of the catalyst is also obviously reduced.
CN201710652988.3 discloses a method for preparing a sulfur preparation catalyst by selective oxidation of hydrogen sulfide with metatitanic acid, silica powder and calcium silicate as raw materials and iron oxide and calcium oxide as active components. Although the occurrence of the Claus reaction reverse reaction can be reduced, the conversion of hydrogen sulfide is about 97% because the added metatitanic acid is active for the Claus reaction reverse reaction.
The reaction of selective oxidation of hydrogen sulfide to sulfur is a strongly exothermic reaction, described by Wangzhong et al (petrochemical applications, 2016, 35 (3), 10-14) at 1% H per reaction 2 S, which can cause the temperature rise of 60 ℃, when the catalyst is used in an adiabatic reactor, the reaction environment on the whole bed layer is greatly different.
CN201780058737.0 discloses a method for using a catalyst, i.e. a first bed layer is filled with a catalyst with a higher content of active components, and a second bed layer is filled with a catalyst with a lower content of active components, which can improve the yield of sulfur, but the method is applicable to a narrower temperature zone.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a catalyst for preparing sulfur by selective oxidation of hydrogen sulfide and a preparation method and a use method thereof. When in preparation, silicon dioxide with high stability is selected as a carrier, so that the catalyst has strong sulfation resistance and can prolong the service life of the catalyst; the carrier raw materials produced by different methods are selected in the inlet low-temperature section and the outlet high-temperature section, so that the high recovery rate of sulfur is ensured, and the use temperature zone of the catalyst is widened. The invention can actively promote the development and popularization of a new sulfur recovery process, and has good economic benefit and environmental benefit.
The key points of the invention are as follows: the catalyst is prepared by taking silicon dioxide as a carrier and ferric oxide as an active component and adding a certain amount of active auxiliary agent, pore-forming agent, binder, dispersant and the like. The temperature of the inlet section is low, the diffusion rate of gas molecules is low, and the conversion rate of hydrogen sulfide can be effectively ensured by selecting silicon dioxide which is produced by a gas phase method and has low specific surface area and small pore volume and pore diameter; the high-temperature section of the outlet selects silicon dioxide which is produced by a silicon powder precipitation method and has high specific surface area and large pore volume and pore diameter, and the retention time of gas in the pore channel is shortened.
The specific technical scheme for solving the technical key point of the invention is as follows:
(1) A selective oxidation sulfur recovery catalyst comprises a carrier, an auxiliary agent and an active component. Preparing a carrier by extruding and molding silicon dioxide powder, an active auxiliary agent, a pore-forming agent and a binder, and then impregnating soluble salts of iron and the auxiliary agent in equal volume. The silicon dioxide in the catalyst accounts for more than 90 wt%; the iron oxide accounts for 2-8wt% of the catalyst, and the active assistant accounts for 0.5-5wt% of the catalyst in terms of oxide.
(2) The catalyst is used according to a layered loading method. The specific surface area of the catalyst filled in the inlet low-temperature section is 20-60m 2 Per g, pore volume of 0.15-0.40ml/g, average pore diameter of 10-25nm, preferably specific surface area of 30-50m 2 The pore volume is 0.20-0.35ml/g, and the average pore diameter is 15-20nm; the specific surface area of the catalyst filled in the high-temperature section at the outlet is 61-120m 2 Per g, pore volume of 0.41-1.20ml/g, average pore diameter of 26-60nm, preferably specific surface area of 80-100m 2 Per g, pore volume of 0.50-0.80ml/g, and average pore diameter of 30-50nm. The filling amount of the lower-temperature section at the inlet of the upper layer accounts for 20-70% of the total volume of the catalyst, and the filling amount of the high-temperature section at the outlet of the lower layer accounts for 30-80% of the total volume of the catalyst.
(3) The silicon dioxide used for preparing the carrier is silicon dioxide powder produced by a gas phase method at a low temperature section, the product has low specific surface area and small pore volume and pore diameter, can prolong the retention time of gas molecules in a pore channel, and is favorable for improving the conversion rate of hydrogen sulfide. The silicon dioxide powder produced by the silicon powder precipitation method is selected in the high-temperature section, the product has large pore volume and pore diameter, gas molecules can pass through the product quickly, and the selectivity of sulfur dioxide can be reduced, so that the yield of sulfur is improved.
(4) The raw materials of the active component are nitrate, sulfate, sulfite, chloride and the like containing iron, preferably nitrate; the addition amount is 2-8wt%, preferably 3-7wt% of the total mass of the catalyst calculated by oxide.
(5) The raw materials of the active auxiliary agent are oxides, hydroxides, nitrates, sulfates, chlorides, carbonates or phosphates of calcium, copper, sodium, zinc, magnesium, aluminum, potassium, lanthanum, cerium and the like, and the nitrates of alkali metals or/and alkaline earth metals are preferred; the addition amount is 0.5-5wt%, preferably 1-3 wt%, calculated by oxide, of the total mass of the catalyst.
(6) The pore-forming agent is selected from sesbania powder, flour, carboxymethyl cellulose and the like, and is added during the preparation of the carrier. In the dry powder mixing step in the carrier preparation process, the content is 2-8wt%, preferably 3-6wt% of the total weight of all dry powders.
(7) The dispersant is Tween-80, glycerol, polyethylene glycol-400, etc., and is used for carrier impregnation, and accounts for 0.2-5%, preferably 0.5-3% of the total volume of the impregnation solution.
(8) The binder is selected from any one of nitric acid, polyvinyl alcohol and silica sol, and the addition amount is 2-10wt% of the total mass of the catalyst, preferably 4-7 wt%.
(9) The preparation method of the catalyst comprises the following steps:
preparation of the carrier: mixing silicon dioxide powder and pore-forming agent dry powder for 5-20min, adding solution prepared from binder and active auxiliary agent, wet mixing for 15-40min, preferably 20-30min, extruding with 2.5-4.5mm template for molding, aging for 8-24h, preferably 12-18h, drying at 40-100 deg.C for 5-24h, and calcining at 400-600 deg.C for 2-6h.
Preparation of the catalyst: preparing active components, auxiliary agent and dispersant into impregnation solution according to equal volume of impregnation, impregnating at normal temperature for 3-12h, or impregnating at 40-80 deg.C for 1-5h, drying at 80-120 deg.C for 2-8h, and roasting at 350-500 deg.C for 2-6h.
Detailed Description
The technical solutions of the present invention will be further described in this section with reference to detailed examples. The embodiments disclosed herein are examples of the present invention, which may be embodied in various forms. Therefore, specific details disclosed, including specific structural and functional details, are not intended to limit the invention, but merely serve as a basis for the claims.
Example 1:
224.6g of silicon dioxide produced by a gas phase method, 9.2g of sesbania powder and 5.6g of calcium oxide are mixed for 10min and marked as a material A.50.0g of polyvinyl alcohol are added to 1000mL of water to prepare a solution, denoted as B. Adding a proper amount of the solution B into the powder A, kneading for 30min, and extruding a 3.5mm template. Aging for 12h, baking for 12h at 50 ℃, and roasting for 4h at 550 ℃ to obtain a carrier C.
32.4g of ferric nitrate and 3.2g of sodium nitrate were dissolved in 46mL of water, and 5mL of Tween-80 was added thereto and mixed well to prepare a maceration extract D. 100g of the support C was added to the impregnation solution D, and the impregnation was carried out in an equal volume. After dipping for 8h, drying for 5h at 100 ℃ and decomposing for 4h at 500 ℃ to obtain the catalyst with the serial number of Cat-1.
The indexes of Cat-1 are tested as follows: specific surface area of 45.6m 2 G, pore volume 0.28cm 3 G, average pore diameter 17.8nm.
The catalyst was evaluated on a normal pressure microreaction evaluation apparatus. The reactor was made of a stainless steel tube with an inner diameter of 20mm and the catalyst loading was 10mL. The gas composition at the inlet and outlet of the reaction is analyzed on line by a 3420A gas chromatograph of North Branch Rayleigh.
Catalyst evaluation conditions: inlet gas H 2 S 1％，O 2 0.7％，H 2 O30%, the balance being N 2 Gas space velocity of 1000h -1 。
The calculation method comprises the following steps:
conversion rate: alpha H 2 S＝(Y H2S 0 -Y H2S )/Y H2S 0
And (3) selectivity: eta S n ＝(Y H2S 0 -Y H2S -Y SO2 )/(Y H2S 0 -Y H2S )
Yield: x Sn ＝(Y H2S 0 -Y H2S -Y SO2 )/Y H2S 0
αH 2 S——H 2 Conversion of S
ηS n -selectivity
X Sn Yield of
Y H2S 0 -reaction inlet H 2 Content of S
Y H2S -H in the post-reaction off-gas 2 Content of S
Y SO2 -SO in the post-reaction off-gas 2 In a content of
TABLE 1 Performance when Cat-1 catalyst is fully loaded
As can be seen from Table 1, when Cat-1 is filled in the whole catalyst bed, the conversion rate, selectivity and yield of the catalyst are high at the low temperature section of the inlet, namely 180-220 ℃, but the performances of the catalyst are obviously reduced along with the increase of the temperature.
Example 2:
232.7g of silicon dioxide produced by a silicon powder precipitation method, 9.6g of sesbania powder and 6.2g of calcium oxide are uniformly mixed and marked as a material A.50.0g of polyvinyl alcohol are added to 1000mL of water to prepare a solution, denoted as B. Adding a proper amount of the solution B into the powder A, kneading for 30min, and extruding a 3.5mm template. Aging for 12h, baking for 8h at 50 ℃, and roasting for 4h at 550 ℃ to obtain a carrier C.
32.8g of ferric nitrate and 3.6g of sodium nitrate were dissolved in 49mL of water, and 5mL of Tween-80 was added thereto and mixed well to prepare a maceration extract D. 100g of the support C was added to the impregnation solution D, and the impregnation was carried out in an equal volume. After dipping for 8h, drying at 100 ℃ for 5h, and decomposing at 500 ℃ for 4h to obtain the catalyst with the serial number of Cat-2.
The indexes of Cat-2 are tested as follows: specific surface area 89.5m 2 Per g, pore volume 0.61cm 3 G, average pore diameter of 35.2nm.
Catalyst evaluation conditions: inlet gas H 2 S 1％，O 2 0.7％，H 2 O30% and the balance of N 2 Gas space velocity of 1000h -1 。
TABLE 2 Performance when Cat-2 catalyst was fully loaded
As can be seen from Table 2, when Cat-2 is filled in the whole catalyst bed, the performance of the catalyst is inferior to that of Cat-1 at the low temperature of 180-220 ℃, but the advantage of using Cat-2 is obvious when the temperature is increased to 240 ℃ or higher.
Example 3
Cat-1 in example 1 accounted for 40% of the total charged volume and was installed in the upper inlet low temperature section of the reactor, and Cat-2 in example 2 accounted for 60% of the total charged volume and was installed in the lower outlet high temperature section of the reactor.
Catalyst evaluation conditions: inlet gas H 2 S 1％，O 2 0.7％，H 2 O30%, the balance being N 2 Gas space velocity of 1000h -1 。
TABLE 3 Performance of catalyst when layered packing
As can be seen from Table 3, when Cat-1 and Cat-2 were loaded in layers, the catalyst exhibited better conversion, selectivity and yield at each temperature point than when loaded alone.
Stability tests were carried out according to the loading method of Table 3 and compared with industrial samples, the results of which are shown in Table 4. The conversion and yield of the catalyst did not change substantially after 1000h compared to the commercial samples, since more stable silica was used as starting material.
Table 4 experimental comparison of catalyst stability
Evaluation conditions were as follows: inlet gas H 2 S 1％，O 2 0.7％，H 2 O30%, the balance being N 2 Gas space velocity of 1000h -1 And the temperature is 220 ℃.
It should be understood that the preferred embodiment processes of this example are not intended to limit the invention to the particular forms disclosed, but that the invention is to cover all modifications, equivalents, and alternatives falling within the scope of the description and the appended claims.
Claims (8)
1. A catalyst for preparing sulfur by selective oxidation of hydrogen sulfide comprises a silicon dioxide carrier, an active assistant and an active component iron oxide, and is prepared by an impregnation method; the silicon dioxide accounts for more than 90wt% of the catalyst; the iron oxide accounts for 2-8wt% of the catalyst; the active assistant accounts for the catalyst in terms of oxide0.5-5wt% of the agent; the method is characterized in that: the catalyst is filled in layers, and the specific surface area of the catalyst filled at the lower-temperature section of the upper layer inlet is 20-60m 2 G, the pore volume is 0.15-0.40ml/g, and the average pore diameter is 10-25nm; the specific surface area of the catalyst filled in the high-temperature section at the outlet of the lower layer is 61-120m 2 The pore volume is 0.41-1.20ml/g, and the average pore diameter is 26-60nm; the filling amount of the lower-temperature section at the inlet of the upper layer accounts for 20-70% of the total volume of the catalyst, and the filling amount of the high-temperature section at the outlet of the lower layer accounts for 30-80% of the total volume of the catalyst.
2. The catalyst of claim 1, wherein: the low-temperature section selects the silicon dioxide powder with low specific surface area produced by a gas phase method, and the high-temperature section selects the macroporous silicon dioxide powder produced by a silicon powder precipitation method.
3. The catalyst of claim 1, wherein: the raw material used by the active component is any one of nitrate, sulfate, sulfite and chloride containing iron, and the adding amount is 2-8wt% of the total mass of the catalyst according to oxide.
4. The catalyst of claim 1, wherein: the raw materials of the active auxiliary agent are oxides, hydroxides, nitrates, sulfates, chlorides, carbonates or phosphates of any one of calcium, copper, sodium, zinc, magnesium, aluminum, potassium, lanthanum and cerium, and the addition amount of the active auxiliary agent is 0.5 to 5 weight percent of the total mass of the catalyst according to the oxide.
5. The catalyst of claim 1, wherein: adding a pore-forming agent into the carrier, wherein the pore-forming agent is any one of sesbania powder, flour and carboxymethyl cellulose; in the dry powder mixing step in the carrier preparation process, the content of the active ingredients accounts for 2-8wt% of the total mass of all dry powders.
6. The catalyst of claim 1, wherein: when the carrier is soaked, a dispersing agent is used, and the dispersing agent is any one of tween-80, glycerol and polyethylene glycol-400 and accounts for 0.2-5% of the total volume of the soaking solution.
7. The catalyst of claim 1, wherein: the binder is any one of nitric acid, polyvinyl alcohol and silica sol, and the addition amount accounts for 2-10wt% of the total mass of the catalyst.
8. The method for preparing a catalyst according to any one of claims 1 to 7, comprising the steps of:
(1) Preparation of the carrier: uniformly mixing silicon dioxide powder and dry powder of a pore-forming agent, adding a solution of a binder and an active assistant for wet mixing, extruding and forming, aging for 8-24h, drying for 5-24h at 40-100 ℃, and roasting for 2-6h at 400-600 ℃;
(2) Preparation of the catalyst: preparing an active component, an auxiliary agent and a dispersing agent into a steeping liquor according to the equal volume steeping amount, steeping for 3-12h at normal temperature, or steeping for 1-5h at 40-80 ℃, drying for 2-8h at 80-120 ℃, and roasting for 2-6h at 350-500 ℃.
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|---|---|---|---|---|
| US5286697A (en) * | 1989-07-21 | 1994-02-15 | Veg-Gasinstituut N.V. | Catalyst for the selective oxidation of sulphur compounds to elemental sulphur, process for preparing such a catalyst and method for the selective oxidation of sulphur compounds to elemental sulphur |
| CN102950000A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | Catalyst for preparing sulfur by selective oxidation of hydrogen sulfide and preparation method thereof |
| CN110841641A (en) * | 2019-11-23 | 2020-02-28 | 青岛联信催化材料有限公司 | Catalyst for preparing sulfur by selective oxidation of hydrogen sulfide and preparation method thereof |
| CN111100700A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Hydrocracking pretreatment method for high-nitrogen high-dry-point raw material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5286697A (en) * | 1989-07-21 | 1994-02-15 | Veg-Gasinstituut N.V. | Catalyst for the selective oxidation of sulphur compounds to elemental sulphur, process for preparing such a catalyst and method for the selective oxidation of sulphur compounds to elemental sulphur |
| CN102950000A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | Catalyst for preparing sulfur by selective oxidation of hydrogen sulfide and preparation method thereof |
| CN111100700A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Hydrocracking pretreatment method for high-nitrogen high-dry-point raw material |
| CN110841641A (en) * | 2019-11-23 | 2020-02-28 | 青岛联信催化材料有限公司 | Catalyst for preparing sulfur by selective oxidation of hydrogen sulfide and preparation method thereof |
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