CN114558622B - Desulfurization catalyst for cooperatively removing hydrogen sulfide and carbonyl sulfide and preparation method thereof - Google Patents
Desulfurization catalyst for cooperatively removing hydrogen sulfide and carbonyl sulfide and preparation method thereof Download PDFInfo
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- CN114558622B CN114558622B CN202210284695.5A CN202210284695A CN114558622B CN 114558622 B CN114558622 B CN 114558622B CN 202210284695 A CN202210284695 A CN 202210284695A CN 114558622 B CN114558622 B CN 114558622B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 34
- 230000023556 desulfurization Effects 0.000 title claims abstract description 34
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000002131 composite material Substances 0.000 claims abstract description 61
- 239000000243 solution Substances 0.000 claims abstract description 52
- 229910052742 iron Inorganic materials 0.000 claims abstract description 48
- 239000012670 alkaline solution Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000008139 complexing agent Substances 0.000 claims abstract description 27
- 230000000536 complexating effect Effects 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 230000001105 regulatory effect Effects 0.000 claims abstract description 6
- 238000010668 complexation reaction Methods 0.000 claims abstract description 5
- 239000004480 active ingredient Substances 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 238000007865 diluting Methods 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical group [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 239000001433 sodium tartrate Substances 0.000 claims description 4
- 229960002167 sodium tartrate Drugs 0.000 claims description 4
- 235000011004 sodium tartrates Nutrition 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 235000015110 jellies Nutrition 0.000 claims description 3
- 239000008274 jelly Substances 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229960001790 sodium citrate Drugs 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 claims 5
- 239000007789 gas Substances 0.000 abstract description 18
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 8
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 7
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- DLNUHLNXAUGFKN-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;iron Chemical group [Fe].OCCN(CCO)CCO DLNUHLNXAUGFKN-UHFFFAOYSA-N 0.000 description 2
- HUTBITLDXCEAPZ-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;iron Chemical group [Fe].OC(=O)CC(O)(C(O)=O)CC(O)=O HUTBITLDXCEAPZ-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229940032296 ferric chloride Drugs 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- KBPZVLXARDTGGD-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;iron Chemical group [Fe].OC(=O)C(O)C(O)C(O)=O KBPZVLXARDTGGD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000779 smoke Substances 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- 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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a desulfurization catalyst for cooperatively removing hydrogen sulfide and carbonyl sulfide and a preparation method thereof, wherein the desulfurization catalyst adopts a base composite complex iron catalyst and comprises the following raw materials in percentage by weight: active components: 0.01-0.5mol/L; organic complexing agent: 0.01-0.2mol/L; auxiliary agent: 10-30 g/L; the balance: water; the pH of the alkaline solution is adjusted to 8.0-10.0. The preparation method comprises the following steps: step 1, preparing a solution: preparing an active component solution; preparing an organic complexing agent solution; preparing an alkaline solution; step 2, complexation: mixing the prepared active ingredient solution and the organic complexing agent solution in proportion, diluting with water, uniformly stirring, and standing for 2 hours to carry out a complexing reaction to obtain a complex reactant solution; and 3, regulating the pH value of the complexing reaction liquid by using an alkaline solution, fixing the volume, and standing to obtain the base compound complexing iron catalyst. The invention can stably and efficiently remove the hydrogen sulfide and carbonyl sulfide in the blast furnace gas.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a desulfurization catalyst for cooperatively removing hydrogen sulfide and carbonyl sulfide and a preparation method thereof.
Background
The energy conservation and emission reduction of the steel industry is an optimized economic structure and is an important ring for promoting the development of high quality. The blast furnace gas is used as a byproduct of the blast furnace ironmaking process of iron and steel enterprises, and the total sulfur content of the gas is about 100-200 mg/Nm 3 Mainly by H 2 S, COS and CS 2 Mainly. In order to achieve better policy emission requirements, it is necessary to remove inorganic sulfur from blast furnace gas together with the removal of organic sulfur. Due to organic matterThe method has the advantages that sulfur is relatively stable, direct removal is difficult by using a conventional method, COS is usually subjected to hydrolysis and conversion into hydrogen sulfide, and then the hydrogen sulfide is removed, but in the process of hydrolyzing COS, a lot of side reactions exist, hydrolysis activity temperature is high, sulfate poisoning easily occurs under the atmosphere of micro oxygen of the blast furnace gas, catalyst deactivation phenomenon is caused, and the problems of high energy consumption, high investment, unsuitable temperature conditions and the like also exist, so that the desulfurization catalyst for cooperatively removing the hydrogen sulfide and the carbonyl sulfide is developed, and H in the blast furnace gas can be efficiently and stably removed 2 S and COS appear to be critical.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a desulfurization catalyst for cooperatively removing hydrogen sulfide and carbonyl sulfide and a preparation method thereof, which can stably and efficiently remove the hydrogen sulfide and the carbonyl sulfide in blast furnace gas.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the technical scheme is as follows:
a desulfurization catalyst for cooperatively removing hydrogen sulfide and carbonyl sulfide adopts a base composite complex iron catalyst, and the base composite complex iron catalyst comprises the following raw materials in percentage by weight:
active components: 0.01-0.5mol/L;
organic complexing agent: 0.01-0.2mol/L;
auxiliary agent: 10-30 g/L;
the balance: water;
the pH of the alkaline solution is adjusted to 8.0-10.0.
Further, the active component adopts ferric chloride; the ferric chloride adopts ferric chloride hexahydrate.
Further, the alkaline solution is prepared by dissolving an alkaline reagent with water; the alkaline reagent comprises one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide.
Further, the active component comprises one or more of sodium hexametaphosphate, triethanolamine, sodium ethylenediamine tetraacetate, sodium tartrate and sodium citrate.
Further, the auxiliary agent is titanium-aluminum composite oxide.
Further, the preparation method of the titanium-aluminum composite oxide comprises the following steps: the molar ratio of aluminum nitrate to titanium tetrachloride is 2-4:1, weighing all raw materials, dissolving aluminum nitrate with deionized water, adding titanium tetrachloride into the solution, stirring the solution until the solution is completely dissolved, adjusting the pH value to 9 with ammonia water, standing the solution to precipitate after jelly appears, filtering supernatant, drying the precipitate, grinding the precipitate, and calcining the precipitate in a muffle furnace to obtain the titanium-aluminum composite oxide.
Further, the gum was allowed to settle for 6 hours.
Further, the temperature of the drying is 105 ℃ and the time is 12 hours.
Further, the calcination treatment was carried out at 550℃for 5 hours.
The second technical scheme is as follows:
the preparation method of the desulfurization catalyst for cooperatively removing hydrogen sulfide and carbonyl sulfide comprises the following steps:
step 1, preparing a solution: dissolving active components with water to prepare an active component solution;
dissolving an organic complexing agent with water to prepare an organic complexing agent solution;
dissolving an alkaline reagent with water to prepare an alkaline solution;
step 2, complexation: mixing the prepared active ingredient solution and the organic complexing agent solution in proportion, diluting with water, uniformly stirring, and standing for 2 hours to carry out a complexing reaction to obtain a complex reactant solution;
step 3, regulating the pH value of the complexing reaction solution by using an alkaline solution, fixing the volume, and standing to obtain a base compound complexing iron solution;
and step 4, adding the titanium aluminum composite oxide into the base composite complexing iron solution to obtain the base composite complexing iron catalyst.
Further, the standing in the step 2 is performed under normal temperature and normal pressure conditions.
Further, the standing in the step 3 is performed under a solution-tight condition, and the standing time in the step 3 is 24 hours.
In the step 1, the organic complexing agent solution is prepared by stirring and dissolving at 50-70 ℃ and 40-60 r/s rotation speed, and cooling to room temperature after dissolving.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention has the advantages of wide raw material sources, low price, simple preparation method and short time consumption; the method can be widely applied in the steel industry, not only can completely convert hydrogen sulfide in blast furnace gas, but also has higher removal rate for carbonyl sulfide;
2. the method prepares the solution in stages, the prepared catalyst has good stability and high activity, the used instruments are laboratory conventional instruments, the operation is simple, and the cost is low;
3. the addition of the additive titanium-aluminum-based metal oxide is beneficial to improving the sulfur poisoning resistance of the catalyst, and the total desulfurization rate of the catalyst under the conditions of normal temperature and normal pressure can be improved to more than 80 percent.
4. The raw materials used in the invention are nontoxic and harmless, the combination of the organic complexing agent and the iron ions has a strong complexing effect, and the oxidation capability is strong.
5. The base composite complex iron catalyst is a liquid phase catalyst, and when the blast furnace gas is desulfurized, the blast furnace gas is directly fed into the catalyst, secondary treatment is not needed, the removal rate is high, the desulfurization reaction is rapid, and various gases such as hydrogen sulfide, carbonyl sulfide, carbon disulfide and the like can be removed simultaneously; the preparation and the use of the catalyst are carried out at normal temperature and normal pressure, the temperature threshold value is large, and the direct operation can be carried out.
Detailed Description
The technical solutions of the present invention will be clearly and fully described below with reference to specific embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
a desulfurization catalyst for cooperatively removing hydrogen sulfide and carbonyl sulfide adopts a base composite complex iron catalyst, wherein the base composite complex iron catalyst is an EDTA-Fe catalyst; the base composite complex iron catalyst comprises the following raw materials in concentration:
active components: ferric chloride hexahydrate 0.02mol/L;
organic complexing agent: 0.02mol/L of sodium ethylenediamine tetraacetate;
auxiliary agent: 12g/L of titanium-aluminum composite oxide;
the balance of water;
the pH value of the base composite complex iron catalyst is regulated to 8.5-9.0 by alkaline solution;
the alkaline solution is prepared by alkaline reagent sodium carbonate,
the preparation method of the titanium-aluminum composite oxide comprises the following steps: according to the mole ratio of 4:1, weighing all raw materials, dissolving aluminum nitrate with deionized water, adding titanium tetrachloride into the solution, stirring the solution until the solution is completely dissolved, regulating the pH value to 9 with ammonia water, standing the solution to precipitate for 6 hours after jelly appears, filtering out supernatant, drying the precipitate at 105 ℃ for 12 hours, grinding the precipitate, and calcining the precipitate at 550 ℃ for 5 hours in a muffle furnace to obtain the titanium-aluminum composite oxide.
The preparation method of the base composite complex iron catalyst comprises the following steps:
step 1, preparing a solution: dissolving the active component with water to prepare 0.2mol/L active component solution;
dissolving an organic complexing agent in water, stirring and dissolving at 50-70 ℃ and 40-60 r/s, and cooling to room temperature after dissolving to prepare 0.2mol/L organic complexing agent solution;
dissolving an alkaline reagent with water to prepare 0.2mol/L alkaline solution;
step 2, complexation: respectively measuring 25mL of active ingredient solution and 25mL of organic complexing agent solution according to the volume ratio of 1:1, diluting with water until the volume of the solution is 100mL, uniformly stirring, and standing for 2 hours under normal temperature and normal pressure to carry out complexation reaction to obtain a complex reactant solution;
step 3, regulating the pH value of the complexing reaction solution to 8.5-9.0 by using an alkaline solution, fixing the volume to 250mL, and standing for 24 hours under the sealed condition of the solution to obtain a base compound complexing iron solution;
and step 4, adding an auxiliary agent into the base composite complexing iron solution to obtain the base composite complexing iron catalyst.
Example 2
A desulfurization catalyst for cooperatively removing hydrogen sulfide and carbonyl sulfide adopts a base composite complex iron catalyst, wherein the base composite complex iron catalyst is a tartaric acid-iron base wet desulfurization catalyst; the base composite complex iron catalyst comprises the following raw materials in concentration:
active components: ferric chloride hexahydrate 0.02mol/L;
organic complexing agent: sodium tartrate 0.02mol/L;
auxiliary agent: 12g/L of titanium-aluminum composite oxide;
the balance: water;
and adjusting the pH value of the base composite complex iron catalyst to 8.5-9.0 by an alkaline solution.
The alkaline solution is prepared from alkaline reagent sodium hydroxide;
the preparation method of the titanium-aluminum composite oxide comprises the following steps: as in example 1.
The preparation method of the base composite complex iron catalyst is the same as in example 1.
Example 3
A desulfurization catalyst for cooperatively removing hydrogen sulfide and carbonyl sulfide adopts a base composite complex iron catalyst, wherein the base composite complex iron catalyst is a citric acid-iron base wet desulfurization catalyst; the citric acid-iron base wet desulfurization catalyst comprises the following raw materials in concentration:
active components: ferric chloride hexahydrate 0.02mol/L;
organic complexing agent: sodium citrate 0.02mol/L;
auxiliary agent: 12g/L of titanium-aluminum composite oxide;
the balance: water;
and adjusting the pH value of the base composite complex iron catalyst to 8.5-9.0 by an alkaline solution.
The alkaline solution is prepared from alkaline reagent sodium carbonate;
the preparation method of the titanium-aluminum composite oxide comprises the following steps: as in example 1.
The preparation method of the base composite complex iron catalyst is the same as in example 1.
Example 4
A desulfurization catalyst for cooperatively removing hydrogen sulfide and carbonyl sulfide adopts a base composite complex iron catalyst, wherein the base composite complex iron catalyst is a triethanolamine-iron base wet desulfurization catalyst; the triethanolamine-iron base wet desulfurization catalyst comprises the following raw materials in concentration:
active components: ferric chloride hexahydrate 0.02mol/L;
organic complexing agent: triethanolamine 0.02mol/L;
auxiliary agent: 12g/L of titanium-aluminum composite oxide;
the balance: water;
and adjusting the pH value of the base composite complex iron catalyst to 8.5-9.0 by an alkaline solution.
The alkaline solution is prepared from a mixture of alkaline reagent sodium carbonate and sodium hydroxide, and the molar ratio of the sodium carbonate to the sodium hydroxide in the alkaline solution is 1:1;
the preparation method of the titanium-aluminum composite oxide comprises the following steps: as in example 1.
The preparation method of the base composite complex iron catalyst is the same as in example 1.
Example 5
A desulfurization catalyst for cooperatively removing hydrogen sulfide and carbonyl sulfide adopts a base composite complex iron catalyst, wherein the base composite complex iron catalyst is a sodium hexametaphosphate-iron base wet desulfurization catalyst; the sodium hexametaphosphate-iron base wet desulfurization catalyst comprises the following raw materials in concentration:
active components: ferric chloride hexahydrate 0.02mol/L;
organic complexing agent: sodium hexametaphosphate 0.02mol/L;
auxiliary agent: 12g/L of titanium-aluminum composite oxide;
the balance: water;
and adjusting the pH value of the base composite complex iron catalyst to 8.5-9.0 by an alkaline solution.
The alkaline solution is prepared from alkaline reagent sodium carbonate and sodium hydroxide, and the molar ratio of the sodium carbonate to the sodium hydroxide in the alkaline solution is 1:1;
the preparation method of the titanium-aluminum composite oxide comprises the following steps: as in example 1.
The preparation method of the base composite complex iron catalyst is the same as in example 1.
Example 6
A desulfurization catalyst for cooperatively removing hydrogen sulfide and carbonyl sulfide adopts a base composite complex iron catalyst, wherein the base composite complex iron catalyst is base composite DETA, CA is that Fe is 1:1:1, a complex iron wet desulfurization catalyst; 250mL of the base composite DETA, CA: fe is 1:1:1 comprises the following raw materials in concentration:
active components: ferric chloride hexahydrate 0.02mol/L;
organic complexing agent: triethanolamine 0.02mol/L;
organic complexing agent: 0.02mol/L of sodium ethylenediamine tetraacetate;
organic complexing agent: sodium citrate 0.02mol/L;
organic complexing agent: sodium tartrate 0.02mol/L;
auxiliary agent: 12g/L of titanium-aluminum composite oxide;
the balance: water;
and adjusting the pH value of the base composite complex iron catalyst to 8.5-9.0 by an alkaline solution.
The alkaline solution is prepared from alkaline reagent sodium carbonate and sodium hydroxide, and the molar ratio of the sodium carbonate to the sodium hydroxide in the alkaline solution is 1:1;
the preparation method of the titanium-aluminum composite oxide comprises the following steps: as in example 1.
The preparation method of the base composite complex iron catalyst is the same as in example 1.
Effect example 1
H was carried out on the catalyst obtained in each example 2 S, COS and the effect comparison was carried out with a simple deionized water and a simple test sodium hydroxide solution as controls, and the results are shown in Table 1.
Each test group was subjected to H 2 The methods adopted in the simultaneous removal of S, COS are the same;
the activity and stability of the catalyst are both determined by H 2 S, COS removal rate shows that the concentration of sulfur at the inlet and outlet of blast furnace gas is detected by using online gas chromatography;
the detection conditions are as follows: and (3) testing the activity of the base composite complex iron catalyst in a fixed reactor, wherein the catalyst is 250ml of liquid, the reaction condition is normal temperature differential pressure, the continuous detection is carried out for 2-8h under each concentration, and the test time points are spaced for 10min. H in the raw material gas 2 S concentration is 100mg/m 3 COS concentration of 150mg/m 3 ，N 2 For balancing the gas, the total smoke amount is 200mL/min; each path of gas is determined to be mixed through a small-sized flowmeter, and then is dried after liquid phase reaction, so that accurate experimental values are measured. The reactor was a 500ml gas wash bottle with a precision flow meter control system to ensure a stable inlet gas concentration.
TABLE 1
As can be seen from Table 1, the hydrolysis catalyst prepared by the present invention has excellent H 2 S removing effect and better COS removing effect are achieved at the same timeThe emission requirement of the blast furnace gas fine desulfurization can be met at normal temperature and pressure and only by one step.
The above described embodiments are only preferred examples of the invention and are not exhaustive of the possible implementations of the invention. Any obvious modifications thereof, which would be apparent to those skilled in the art without departing from the principles and spirit of the present invention, should be considered to be included within the scope of the appended claims.
Claims (7)
1. The desulfurization catalyst for cooperatively removing hydrogen sulfide and carbonyl sulfide is characterized in that the desulfurization catalyst adopts a base composite complex iron catalyst, and the base composite complex iron catalyst comprises the following raw materials in percentage by weight:
active components: 0.01-0.5mol/L;
organic complexing agent: 0.01-0.2mol/L;
auxiliary agent: 10-30 g/L;
the balance: water;
the pH value of the alkaline solution is adjusted to 8.0-10.0;
the active component adopts ferric chloride;
the auxiliary agent is titanium aluminum composite oxide;
the preparation method comprises the following steps:
step 1, preparing a solution: dissolving active components with water to prepare an active component solution;
dissolving an organic complexing agent with water to prepare an organic complexing agent solution;
dissolving an alkaline reagent with water to prepare an alkaline solution;
step 2, complexation: mixing the prepared active ingredient solution and the organic complexing agent solution in proportion, diluting with water, uniformly stirring, and standing for 2 hours to carry out a complexing reaction to obtain a complex reactant solution;
step 3, regulating the pH value of the complexing reaction solution by using an alkaline solution, fixing the volume, and standing to obtain a base compound complexing iron solution;
and step 4, adding an auxiliary agent into the base composite complexing iron solution to obtain the base composite complexing iron catalyst.
2. A desulfurization catalyst for the synergistic removal of hydrogen sulfide and carbonyl sulfide as claimed in claim 1, wherein,
the alkaline solution is prepared by dissolving an alkaline reagent with water; the alkaline reagent comprises one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide.
3. A desulfurization catalyst for the synergistic removal of hydrogen sulfide and carbonyl sulfide as claimed in claim 1, wherein,
the organic complexing agent comprises one or more of sodium hexametaphosphate, triethanolamine, sodium ethylenediamine tetraacetate, sodium tartrate and sodium citrate.
4. A desulfurization catalyst for the synergistic removal of hydrogen sulfide and carbonyl sulfide as claimed in claim 1, wherein,
the preparation method of the titanium-aluminum composite oxide comprises the following steps: the molar ratio of aluminum nitrate to titanium tetrachloride is 2-4:1, weighing all raw materials, dissolving aluminum nitrate with deionized water, adding titanium tetrachloride into the solution, stirring the solution until the solution is completely dissolved, adjusting the pH value to 9 with ammonia water, standing the solution to precipitate after jelly appears, filtering supernatant, drying the precipitate, grinding the precipitate, and calcining the precipitate in a muffle furnace to obtain the titanium-aluminum composite oxide.
5. The desulfurization catalyst for the synergistic removal of hydrogen sulfide and carbonyl sulfide as claimed in claim 1, wherein the standing in step 2 is performed under normal temperature and pressure conditions.
6. The desulfurization catalyst for the synergistic removal of hydrogen sulfide and carbonyl sulfide as claimed in claim 1, wherein the standing in step 3 is performed under solution-tight conditions, and the standing time in step 3 is 24 hours.
7. The desulfurization catalyst for cooperatively removing hydrogen sulfide and carbonyl sulfide according to claim 1, wherein in the step 1, the organic complexing agent solution is prepared by stirring and dissolving at 50-70 ℃ and 40-60 r/s rotation speed, and cooling to room temperature after dissolving.
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