CN114558622A - Desulfurization catalyst for synergistically removing hydrogen sulfide and carbonyl sulfide and preparation method thereof - Google Patents
Desulfurization catalyst for synergistically removing hydrogen sulfide and carbonyl sulfide and preparation method thereof Download PDFInfo
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- CN114558622A CN114558622A CN202210284695.5A CN202210284695A CN114558622A CN 114558622 A CN114558622 A CN 114558622A CN 202210284695 A CN202210284695 A CN 202210284695A CN 114558622 A CN114558622 A CN 114558622A
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- hydrogen sulfide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 title claims abstract description 56
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 34
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 32
- 230000023556 desulfurization Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000002131 composite material Substances 0.000 claims abstract description 59
- 229910052742 iron Inorganic materials 0.000 claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 45
- 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 26
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 230000000536 complexating effect Effects 0.000 claims abstract description 8
- 238000007865 diluting Methods 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 230000001105 regulatory effect Effects 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
- 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 9
- 238000000034 method Methods 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- 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
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 4
- 235000015110 jellies Nutrition 0.000 claims description 4
- 239000008274 jelly Substances 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
- 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
- 239000002244 precipitate Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 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
- 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
- 239000006228 supernatant Substances 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 claims 8
- 238000004090 dissolution Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 21
- 230000000694 effects Effects 0.000 description 7
- 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
- 238000012360 testing method Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N carbon disulfide Substances S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 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
- 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
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229940032296 ferric chloride Drugs 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect 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
- DLNUHLNXAUGFKN-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;iron Chemical group [Fe].OCCN(CCO)CCO DLNUHLNXAUGFKN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000003044 adaptive effect Effects 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
- 230000007547 defect Effects 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
- 230000002779 inactivation 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
- 239000011259 mixed solution Substances 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
- 230000001590 oxidative effect Effects 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
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000005406 washing Methods 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a desulfurization catalyst for synergistically 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: 0.01-0.5 mol/L; organic complexing agent: 0.01-0.2 mol/L; auxiliary agent: 10-30 g/L; and the balance: water; adjusting pH of the alkaline solution to 8.0-10.0. The preparation method comprises the following steps: step 1, solution preparation: preparing an active component solution; preparing an organic complexing agent solution; preparing an alkaline solution; step 2, complexing: mixing the prepared active component solution and the organic complexing agent solution in proportion, diluting with water, uniformly stirring, and standing for 2 hours for complexing reaction to obtain a complex reactant solution; and 3, regulating the pH of the complex reaction solution by using an alkaline solution, fixing the volume, and standing to obtain the base composite complex 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 synergistically removing hydrogen sulfide and carbonyl sulfide and a preparation method thereof.
Background
The energy conservation and emission reduction in the steel industry is an optimized economic structure and is an important ring for promoting high-quality development. The blast furnace gas is used as a combustible gas byproduct in the blast furnace ironmaking process of iron and steel enterprises, and the total sulfur content of the blast furnace gas is about 100-200 mg/Nm3Mainly represented by H2S, COS and CS2Mainly comprises the following steps. In order to achieve better policy-based emission requirements, it is necessary to remove inorganic sulfur from blast furnace gas simultaneously with the removal of organic sulfur. The organic sulfur is relatively stable and difficult to directly remove by a conventional method, the removal of COS in blast furnace gas at present usually adopts the steps of hydrolyzing COS to convert the COS into hydrogen sulfide and then removing the hydrogen sulfide, but a plurality of side reactions exist in the COS hydrolysis process, the hydrolysis activity temperature is high, sulfate poisoning is easy to occur under the micro-oxygen atmosphere of the blast furnace gas to cause the inactivation phenomenon of the catalyst, and in addition, the problems of high energy consumption, high investment, non-adaptive temperature condition and the like exist, so the development of the desulfurization catalyst for cooperatively removing the hydrogen sulfide and carbonyl sulfide can efficiently and stably remove H in the blast furnace gas at the same time2S and COS appear to be of vital importance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a desulfurization catalyst for synergistically 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 purpose, the technical scheme adopted by the invention is as follows:
the first technical scheme is as follows:
a desulfurization catalyst for synergistically 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: 0.01-0.5 mol/L;
organic complexing agent: 0.01-0.2 mol/L;
auxiliary agent: 10-30 g/L;
and the balance: water;
adjusting pH of the alkaline solution 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 ethylene diamine tetracetate, sodium tartrate and sodium citrate.
Further, the auxiliary agent is a titanium-aluminum composite oxide.
Further, the preparation method of the titanium-aluminum composite oxide comprises the following steps: according to the molar ratio of aluminum nitrate to titanium tetrachloride of 2-4: 1, weighing each raw material, dissolving aluminum nitrate in deionized water, adding titanium tetrachloride, stirring until the aluminum nitrate is completely dissolved, adjusting the pH value to 9 by using ammonia water, standing and precipitating after a jelly appears, filtering a supernatant, drying and grinding the precipitate, and calcining in a muffle furnace to obtain the titanium-aluminum composite oxide.
Further, the time for the jelly to settle by standing is 6 h.
Further, the drying temperature is 105 ℃, and the drying time is 12 hours.
Further, the temperature of the calcination treatment was 550 ℃ for 5 hours.
The second technical scheme is as follows:
the preparation method of the desulfurization catalyst for synergistically removing hydrogen sulfide and carbonyl sulfide comprises the following steps:
step 1, solution preparation: dissolving the active component in water to prepare an active component solution;
dissolving an organic complexing agent in water to prepare an organic complexing agent solution;
dissolving an alkaline reagent in water to prepare an alkaline solution;
step 2, complexing: mixing the prepared active component solution and the organic complexing agent solution in proportion, diluting with water, uniformly stirring, and standing for 2 hours for complexing reaction to obtain a complex reactant solution;
step 3, regulating the pH of the complex reaction solution by using an alkaline solution, fixing the volume, and standing to obtain a base composite complex iron solution;
and 4, adding the titanium-aluminum composite oxide into the base composite complex iron solution to obtain the base composite complex iron catalyst.
Further, the standing in the step 2 is performed under normal temperature and pressure conditions.
Further, the standing in the step 3 is performed under a closed condition of the solution, and the standing time in the step 3 is 24 hours.
Further, in the step 1, when preparing the organic complexing agent solution, stirring and dissolving at the temperature of 50-70 ℃ and the rotating speed of 40-60 r/s, and cooling to room temperature after dissolving.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention has wide source of raw materials, low price, simple preparation method and short time consumption; the catalyst can be widely applied to 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 by stages, the prepared catalyst has good stability and high activity, and the used instruments are conventional laboratory instruments, so the method is simple to operate and low in cost;
3. the addition of the titanium-aluminum-based metal oxide as the auxiliary agent is beneficial to improving the sulfur poisoning resistance of the catalyst, and can improve the total desulfurization rate of the catalyst to more than 80% under the conditions of normal temperature and normal pressure.
4. The raw materials used in the invention are nontoxic and harmless, the combination of the organic complexing agent and iron ions has strong complexing effect and strong oxidizing ability, and in addition, the auxiliary agent can increase the reaction time and promote mutual reaction.
5. The base composite complex iron catalyst is a liquid phase catalyst, when the blast furnace gas is desulfurized, the blast furnace gas is directly introduced into the base composite complex iron 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 is large, and the direct operation can be carried out.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1:
a desulfurization catalyst for synergistically 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: 0.02mol/L ferric chloride hexahydrate;
organic complexing agent: 0.02mol/L of sodium ethylene diamine tetracetate;
auxiliary agent: 12g/L of titanium-aluminum composite oxide;
the balance of water;
adjusting the pH value of the base composite complex iron catalyst to 8.5-9.0 by using an 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 molar ratio of aluminum nitrate to titanium tetrachloride of 4: 1, weighing the raw materials, dissolving aluminum nitrate in deionized water, adding titanium tetrachloride, stirring until the aluminum nitrate is completely dissolved, adjusting the pH value to 9 by using ammonia water, standing and precipitating for 6 hours after a jelly appears, filtering out supernate, drying and drying the precipitate at 105 ℃ for 12 hours, grinding, and calcining at 550 ℃ in a muffle furnace for 5 hours to obtain the titanium-aluminum composite oxide.
The preparation method of the base composite complex iron catalyst comprises the following steps:
step 1, solution preparation: dissolving the active component in water to prepare 0.2mol/L active component solution;
dissolving an organic complexing agent in water, stirring and dissolving at the temperature of 50-70 ℃ and the rotating speed of 40-60 r/s, cooling to room temperature after dissolving, and preparing into 0.2mol/L organic complexing agent solution;
dissolving an alkaline reagent in water to prepare 0.2mol/L alkaline solution;
step 2, complexing: respectively measuring 25mL of active component solution and 25mL of organic complexing agent solution according to a volume ratio of 1:1, diluting the mixed solution with water until the volume of the solution is 100mL, uniformly stirring the solution, and standing the solution for 2 hours at normal temperature and pressure to perform a complex reaction to obtain a complex reactant solution;
step 3, regulating the pH of the complex reaction solution to 8.5-9.0 by using an alkaline solution, fixing the volume to 250mL, and standing for 24h under the closed condition of the solution to obtain a base composite complex iron solution;
and 4, adding the auxiliary agent into the base composite complex iron solution to obtain the base composite complex iron catalyst.
Example 2
A desulfurization catalyst for synergistically 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: 0.02mol/L ferric chloride hexahydrate;
organic complexing agent: 0.02mol/L of sodium tartrate;
auxiliary agent: 12g/L of titanium-aluminum composite oxide;
and the balance: water;
and adjusting the pH value of the base composite complex iron catalyst to 8.5-9.0 by using an alkaline solution.
The alkaline solution is prepared by an alkaline reagent sodium hydroxide;
the preparation method of the titanium-aluminum composite oxide comprises the following steps: the same as in example 1.
The preparation method of the base complex iron catalyst is the same as that of example 1.
Example 3
A desulfurization catalyst for synergistically removing hydrogen sulfide and carbonyl sulfide adopts a base composite complex iron catalyst, wherein the base composite complex iron catalyst is a citric acid-ferric base wet desulfurization catalyst; the citric acid-ferric base wet desulphurization catalyst comprises the following raw materials in concentration:
active components: 0.02mol/L ferric chloride hexahydrate;
organic complexing agent: 0.02mol/L of sodium citrate;
auxiliary agent: 12g/L of titanium-aluminum composite oxide;
and the balance: water;
and adjusting the pH value of the base composite complex iron catalyst to 8.5-9.0 by using an alkaline solution.
The alkaline solution is prepared by adopting an alkaline reagent sodium carbonate;
the preparation method of the titanium-aluminum composite oxide comprises the following steps: the same as in example 1.
The preparation method of the base complex iron catalyst is the same as that of example 1.
Example 4
A desulfurization catalyst for synergistically 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-ferric base wet desulphurization catalyst comprises the following raw materials in concentration:
active components: 0.02mol/L ferric chloride hexahydrate;
organic complexing agent: 0.02mol/L triethanolamine;
auxiliary agent: 12g/L of titanium-aluminum composite oxide;
and the balance: water;
and adjusting the pH value of the base composite complex iron catalyst to 8.5-9.0 by using an alkaline solution.
The alkaline solution is prepared from a mixture of alkaline reagents 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: the same as in example 1.
The preparation method of the base complex iron catalyst is the same as that of example 1.
Example 5
A desulfurization catalyst for synergistically removing hydrogen sulfide and carbonyl sulfide adopts a base composite complex iron catalyst, wherein the base composite complex iron catalyst is a sodium hexametaphosphate-ferric base wet desulfurization catalyst; the sodium hexametaphosphate-ferric base wet desulphurization catalyst comprises the following raw materials in concentration:
active components: 0.02mol/L ferric chloride hexahydrate;
organic complexing agent: 0.02mol/L of sodium hexametaphosphate;
auxiliary agent: 12g/L of titanium-aluminum composite oxide;
and the balance: water;
and adjusting the pH value of the base composite complex iron catalyst to 8.5-9.0 by using an alkaline solution.
The alkaline solution is prepared from alkaline reagents 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: the same as in example 1.
The preparation method of the base complex iron catalyst is the same as that of example 1.
Example 6
A desulfurization catalyst for synergistically removing hydrogen sulfide and carbonyl sulfide adopts a base composite complex iron catalyst which is base composite DETA, wherein in the ratio of (1) Fe: 1:1, a complex iron wet desulphurization catalyst; 250mL of the base complex DETA, CA, Fe is 1: 1: the complex iron wet desulphurization catalyst of 1 comprises the following raw materials in concentration:
active components: 0.02mol/L ferric chloride hexahydrate;
organic complexing agent: 0.02mol/L triethanolamine;
organic complexing agent: 0.02mol/L of sodium ethylene diamine tetracetate;
organic complexing agent: 0.02mol/L of sodium citrate;
organic complexing agent: 0.02mol/L of sodium tartrate;
auxiliary agent: 12g/L of titanium-aluminum composite oxide;
and the balance: water;
and adjusting the pH value of the base composite complex iron catalyst to 8.5-9.0 by using an alkaline solution.
The alkaline solution is prepared from alkaline reagents 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: the same as in example 1.
The preparation method of the base complex iron catalyst is the same as that of example 1.
Effect example 1
The catalysts obtained in the examples were subjected to H2S, COS and comparison of the results with deionized water alone and test sodium hydroxide solution alone as controls, are shown in Table 1.
Each test group was subjected to H2S, COS the method for simultaneous removal is the same;
the activity and stability results of the catalyst are all expressed as H2S, COS removal rate indicates that the sulfur concentration of the gas inlet and outlet of the blast furnace is detected by using an online gas chromatography;
the detection conditions are as follows: and (3) carrying out activity test on the base composite complex iron catalyst in a fixed reactor, wherein the catalyst is 250ml of liquid, the reaction condition is normal temperature and differential pressure, the detection is continuously carried out for 2-8h under each concentration, and the test time point interval is 10 min. H in the feed gas2S concentration is 100mg/m3The concentration of COS is 150mg/m3，N2The total smoke gas is 200mL/min as balance gas; each path of gas is determined to be mixed through a small-sized flowmeter, and then is dried after liquid phase reaction, so that the accurate experimental number is measuredThe value is obtained. The reactor is a 500ml gas washing bottle, and the test bed is provided with a precise flow meter control system to ensure the stability of the inlet gas concentration.
TABLE 1
As can be seen from Table 1, the hydrolysis catalyst prepared by the present invention has very good H2The method has good COS removal effect while achieving the S removal effect, and can meet the emission requirement of blast furnace gas fine desulfurization at normal temperature and normal pressure by only one step.
The embodiments described above are only preferred embodiments of the invention and are not exhaustive of the possible implementations of the invention. Any obvious modifications thereof, which would occur to one skilled in the art without departing from the principles and spirit of the invention, are to be considered as included within the scope of the following claims.
Claims (10)
1. The desulfurization catalyst for synergistically removing hydrogen sulfide and carbonyl sulfide is characterized by adopting a base composite complex iron catalyst, wherein the base composite complex iron catalyst comprises the following raw materials in percentage by weight:
active components: 0.01-0.5 mol/L;
organic complexing agent: 0.01-0.2 mol/L;
auxiliary agent: 10-30 g/L;
and the balance: water;
adjusting pH of the alkaline solution to 8.0-10.0.
2. The desulfurization catalyst for the synergistic removal of hydrogen sulfide and carbonyl sulfide as claimed in claim 1,
the active component adopts ferric chloride.
3. The desulfurization catalyst for the synergistic removal of hydrogen sulfide and carbonyl sulfide as claimed in claim 1,
the alkaline solution is prepared by dissolving an alkaline reagent in water; the alkaline reagent comprises one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide.
4. The desulfurization catalyst for the synergistic removal of hydrogen sulfide and carbonyl sulfide as claimed in claim 1,
the active components comprise one or more of sodium hexametaphosphate, triethanolamine, sodium ethylene diamine tetracetate, sodium tartrate and sodium citrate.
5. The desulfurization catalyst for the synergistic removal of hydrogen sulfide and carbonyl sulfide as claimed in claim 1,
the auxiliary agent is a titanium-aluminum composite oxide.
6. The desulfurization catalyst for the synergistic removal of hydrogen sulfide and carbonyl sulfide as recited in claim 5,
the preparation method of the titanium-aluminum composite oxide comprises the following steps: according to the molar ratio of aluminum nitrate to titanium tetrachloride of 2-4: 1, weighing each raw material, dissolving aluminum nitrate in deionized water, adding titanium tetrachloride, stirring until the aluminum nitrate is completely dissolved, adjusting the pH value to 9 by using ammonia water, standing and precipitating after a jelly appears, filtering a supernatant, drying and grinding the precipitate, and calcining in a muffle furnace to obtain the titanium-aluminum composite oxide.
7. A process for the preparation of a desulfurization catalyst for the synergistic removal of hydrogen sulfide and carbonyl sulfide as set forth in any one of claims 1 to 6, which comprises:
step 1, solution preparation: dissolving the active component in water to prepare an active component solution;
dissolving an organic complexing agent in water to prepare an organic complexing agent solution;
dissolving an alkaline reagent in water to prepare an alkaline solution;
step 2, complexing: mixing the prepared active component solution and the organic complexing agent solution according to a certain proportion, diluting with water, uniformly stirring, standing for 2h for complexing reaction to obtain a complex reactant solution;
step 3, regulating the pH of the complex reaction solution by using an alkaline solution, fixing the volume, and standing to obtain a base composite complex iron solution;
and 4, adding the auxiliary agent into the base composite complex iron solution to obtain the base composite complex iron catalyst.
8. The method for preparing a desulfurization catalyst for the synergistic removal of hydrogen sulfide and carbonyl sulfide as recited in claim 7, wherein said standing in step 2 is performed under normal temperature and pressure conditions.
9. The method for preparing a desulfurization catalyst for the synergistic removal of hydrogen sulfide and carbonyl sulfide as recited in claim 7, wherein said standing in step 3 is performed under a closed condition of the solution, and said standing time in step 3 is 24 hours.
10. The preparation method of the desulfurization catalyst for synergistically removing hydrogen sulfide and carbonyl sulfide as claimed in claim 7, wherein in the step 1, the organic complexing agent solution is stirred and dissolved at a temperature of 50-70 ℃ and a rotating speed of 40-60 r/s, and then the temperature is reduced to room temperature after the dissolution.
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