CN114367279B - Low-temperature poisoning-resistant hydrolysis catalyst for blast furnace gas fine desulfurization and preparation method thereof - Google Patents
Low-temperature poisoning-resistant hydrolysis catalyst for blast furnace gas fine desulfurization and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 32
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 31
- 231100000572 poisoning Toxicity 0.000 title claims abstract description 20
- 230000000607 poisoning effect Effects 0.000 title claims abstract description 20
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 18
- 230000023556 desulfurization Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 9
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical group [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 229920002472 Starch Polymers 0.000 claims abstract description 4
- 239000008107 starch Substances 0.000 claims abstract description 4
- 235000019698 starch Nutrition 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 34
- 239000011259 mixed solution Substances 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical group CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 230000006837 decompression Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000006229 carbon black Substances 0.000 abstract description 3
- 235000019241 carbon black Nutrition 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 abstract 1
- 239000000428 dust Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 229910010038 TiAl Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 4
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/485—Sulfur compounds containing only one sulfur compound other than sulfur oxides or hydrogen sulfide
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a low-temperature poisoning-resistant hydrolysis catalyst for blast furnace gas fine desulfurization and a preparation method thereof, wherein the catalyst comprises the following components in percentage by mass: 75-80% of carrier, 5-20% of active component, 1-5% of auxiliary agent and 100% of sum of the above components by mass percent. Wherein the carrier is aluminum-titanium composite oxide, the active component is one or more of alkali metal oxides, and the auxiliary agent is one or more of carboxymethyl cellulose, starch and carbon black. The invention also relates to a preparation method of the hydrolysis catalyst. The catalyst has the advantages of lower hydrolysis reaction temperature, wider catalytic hydrolysis desulfurization activity temperature window, stronger poisoning resistance and long service life, and can be directly arranged after the blast furnace gas dust removal step, thereby reducing energy consumption and cost.
Description
Technical Field
The invention belongs to the technical field of blast furnace gas fine desulfurization catalysis, and particularly relates to a low-temperature poisoning-resistant hydrolysis catalyst for blast furnace gas fine desulfurization and a preparation method thereof.
Background
The blast furnace gas is one of main byproducts generated in the iron-making process, contains abundant carbon monoxide resources, can be enriched and recycled, but contains a large amount of organic sulfur compounds and inorganic sulfur compounds, wherein the organic sulfur compounds mainly comprise carbonyl sulfide, but due to the chemical stability, the effective removal is difficult to realize by adopting a conventional removal method. In view of increasingly stringent environmental regulations and catalytic specifications, removal of COS is not yet acceptable.
COS can be removed by hydroconversion, oxidation, adsorption, physicochemical absorption, etc., but these methods have high operating temperature, high energy consumption, and are prone to side reactions.
Another method is the catalytic hydrolysis method (cos+h 2O→H2S+CO2), which has become a widely accepted COS conversion removal technology in the steel industry due to its mild reaction conditions, low operating temperature and high removal efficiency, wherein the choice of catalyst is critical for the removal of COS.
Chinese patent CN112619648A has studied a copper-cobalt-based catalyst, and a high-pressure reaction kettle is required by adopting a hydrothermal synthesis method, so that the operation requirement is high. Chinese patent CN112439409a discloses an organic sulfur hydrolysis catalyst which supports a bi-component transition metal oxide on Al 2O3, but has lower conversion activity for low COS feed gas.
In Chinese patent CN113578329A, a hydrolysis catalyst for removing carbonyl sulfide from blast furnace gas and a preparation method thereof are disclosed, the hydrolysis conversion rate of the modified catalyst reaches more than 80% under the condition of 100-150 ℃, and the reaction temperature is still higher; secondly, the source of the raw materials is still not wide enough, is limited to the inorganic field, and is not related to the organic field; secondly, the preparation method still has an optimized room, the preparation of the catalyst carrier is carried out firstly, after the preparation of the carrier by a precipitation method is finished, the active component solution is prepared and added into the catalyst carrier, and the impregnation method is carried out to prepare the catalyst, so that two-stage operation is required.
Disclosure of Invention
The invention aims to solve the technical problems: in order to overcome the defects of the prior art, the invention provides a low-temperature poisoning-resistant hydrolysis catalyst for blast furnace gas fine desulfurization and a preparation method thereof.
The technical scheme of the invention is as follows: the invention relates to a low-temperature poisoning-resistant hydrolysis catalyst for blast furnace gas fine desulfurization, which comprises the following components in percentage by mass: 75-80% of carrier, 5-20% of active component, 1-5% of auxiliary agent, and 100% of sum of the above components by mass percent; the carrier is titanium-aluminum composite oxide, wherein the molar ratio of titanium to aluminum element is (0.2-0.6): (0.4-1); in the titanium-aluminum composite oxide, a precursor of titanium is tetrabutyl titanate; the precursor of aluminum is aluminum isopropoxide. Further, the active component is one or more of oxides of the first main group alkali metal element.
Further, the active component comprises at least one of oxides of sodium and potassium, wherein the molar ratio of the alkali metal, titanium and aluminum elements is (0.05-0.4): (0.1-0.5): 1.
Further, the precursor of the active component comprises any one of sodium carbonate, sodium nitrate, sodium acetate, sodium bicarbonate, sodium chloride or potassium carbonate, potassium nitrate, potassium acetate, potassium bicarbonate and potassium chloride.
Further, the auxiliary agent is one or more of carboxymethyl cellulose, starch and carbon black.
The invention also discloses a preparation method of the low-temperature poisoning-resistant hydrolysis catalyst for the blast furnace gas fine desulfurization, which comprises the following implementation steps:
Sequentially adding a titanium precursor and an aluminum precursor into deionized water according to a certain molar ratio, and stirring under an ice water bath until the titanium precursor and the aluminum precursor are completely dissolved to obtain a mixed solution A;
Step two, adding the precursor of the active component into the mixed solution A according to a certain molar ratio, and stirring until the solution is clear to obtain a mixed solution B;
step three, adding an auxiliary agent into the mixed solution B according to a certain mass ratio, and stirring until the auxiliary agent is completely dissolved to obtain a mixed solution C;
Step four, dropwise adding alkali liquor into the mixed solution C, stirring and adjusting the pH value until ion precipitation is complete, and obtaining a mixed solution D;
And fifthly, sealing the mixed solution D, aging, washing, suction filtering, drying, grinding, calcining, and cooling to obtain the low-temperature poisoning-resistant hydrolysis catalyst.
Further, the stirring can be performed by adopting ultrasonic waves, mechanical stirring or a combination thereof, wherein the ultrasonic frequency is 50-100 Hz, and the ultrasonic time is 0.5-2 h; the mechanical stirring speed is 200-600 r/min, and the stirring time is 0.5-2 h.
Further, in the fourth step, the alkali solution includes any one of ammonia water, sodium hydroxide and potassium hydroxide, and the pH is controlled to be 8-10.
Further, in the fifth step, the aging temperature is 25-40 ℃ and the aging time is 24-48 hours.
Further, in the fifth step, centrifugal washing can be adopted, the rotation speed of a centrifugal machine is 3000-6000 r/min, and the centrifugal time of each group is 8-15 min; the suction filtration can adopt a decompression suction filter to carry out solid-liquid separation, and the vacuum degree of a vacuum pump is kept at 0.03-0.07 Mpa; the drying is carried out for 10 to 16 hours at the temperature of 105 to 120 ℃; the calcination is performed in an air atmosphere at 500-700 ℃ for 4-6 h.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention uses the novel materials of tetrabutyl titanate and aluminum isopropoxide in the organic field as the precursors of the titanium-aluminum composite oxide, so that the selection of the precursor materials of the titanium aluminum element is not limited in the inorganic field any more; meanwhile, the element composition of tetrabutyl titanate is C, H, O, ti, the element composition of aluminum isopropoxide is C, H, O, al, and no impurity ions are contained; for example, the inorganic precursor titanium tetrachloride contains impurity Cl, the inorganic precursor titanium tetrachloride needs to be removed by repeated washing in the preparation process of the catalyst, and the operation can be completely omitted by using tetrabutyl titanate, thus the preparation method has the advantages in the preparation link; in addition, the organic precursor has a certain molecular structure, and after mutual dissolution, the two molecular structures are mutually built, are uniformly arranged, and have innovation on the molecular structure of the catalyst compared with the uniform dispersion of ions in the solution.
2. The invention adopts alkali metal element as active component, and utilizes the characteristic that alkali metal element can provide a large amount of alkaline reaction sites, and simultaneously, the addition of auxiliaries such as carboxymethyl cellulose and the like can increase the aperture and the specific surface area, and the low-temperature activity is improved through the two aspects, so that COS removal effect of more than 95% can be realized at 75 ℃.
3. According to the invention, organic materials such as carboxymethyl cellulose, starch, carbon black and the like are used as reaming aids, so that the organic materials can be better mutually dissolved in an organic precursor, and in addition, a large amount of gas can be generated by high-temperature calcination, so that the reaming aids can help to ream and increase the specific surface area.
4. Compared with the conventional preparation process of preparing the catalyst carrier firstly and preparing the catalyst by an impregnation method, the preparation method of the low-temperature poisoning-resistant hydrolysis catalyst for blast furnace gas fine desulfurization disclosed by the invention has the advantages that the precursor of the catalyst carrier element and the active components are simultaneously prepared into a mixed solution, then alkali liquor is added for simultaneous precipitation to obtain the catalyst, the impregnation link is omitted, and the preparation process is greatly simplified.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of the catalysts prepared in examples 1-4 and comparative examples of the present invention;
FIG. 2 is an electron microscope scan of the catalysts prepared in comparative example (a) and example (b);
FIG. 3 is a graph showing desulfurization performance curves of the catalysts prepared in examples 1 to 4 and comparative examples;
FIG. 4 is a graph showing hydrogen sulfide yields for the catalysts prepared in examples 1-4 and comparative examples.
Detailed Description
In order to enhance the understanding of the present invention, the present invention will be further described in detail with reference to the drawings, which are provided for the purpose of illustrating the present invention only and are not to be construed as limiting the scope of the present invention.
Example 1
Sequentially adding 41.2643g of aluminum nitrate nonahydrate and 6.044mL of titanium tetrachloride into 50mL of deionized water, mechanically stirring for 30min under ice water bath for complete dissolution, then adding 1.1662g of anhydrous sodium carbonate into the solution, mechanically stirring for 30min under 300r/min for clarifying the solution, adding 0.5g of carboxymethyl cellulose, fully stirring in 60Hz ultrasonic for 1 hour, dropwise adding ammonia water into the mixed solution, stirring and regulating the pH to 10; aging the mixture for 36 hours at 25 ℃, taking out and transferring the mixture to a centrifugal tank, carrying out centrifugal washing with deionized water, centrifuging for 12 minutes in each group until no white precipitate is generated after the supernatant is titrated with a silver nitrate solution, namely washing is completed, carrying out solid-liquid separation on the washed mixture by a decompression suction filter, drying the solid in an oven at 105-120 ℃ for 15 hours to constant weight under the vacuum degree of a vacuum pump of 0.07Mpa, crushing and grinding, placing the obtained solid powder in a muffle furnace, heating and calcining for 6 hours at the temperature of 600 ℃ in the air atmosphere, and cooling to obtain the Na/TiAl 2O5 catalyst, namely the catalyst A;
Example 2
Sequentially adding 41.2643g of aluminum nitrate nonahydrate and 6.044mL of titanium tetrachloride into 50mL of deionized water, mechanically stirring for 30min under ice water bath for complete dissolution, then adding 1.7492g of anhydrous sodium carbonate into the solution, mechanically stirring for 30min under 300r/min for clarifying the solution, adding 0.5g of carboxymethyl cellulose, stirring for 1h in 60Hz ultrasonic medium, dropwise adding ammonia water into the mixed solution, stirring and regulating the pH to 10; aging the mixture for 36 hours at 25 ℃, taking out and transferring the mixture to a centrifugal tank, carrying out centrifugal washing with deionized water, centrifuging for 12 minutes in each group until no white precipitate is generated after the supernatant is titrated with a silver nitrate solution, namely washing is completed, carrying out solid-liquid separation on the washed mixture by a decompression suction filter, drying the solid in an oven at 105-120 ℃ for 15 hours to constant weight under the vacuum degree of a vacuum pump of 0.07Mpa, crushing and grinding, placing the obtained solid powder in a muffle furnace, heating and calcining for 6 hours at the temperature of 600 ℃ in the air atmosphere, and cooling to obtain the Na/TiAl 2O5 hydrolysis catalyst, which is denoted as a catalyst B;
Example 3
Sequentially adding 41.2643g of aluminum nitrate nonahydrate and 6.044mL of titanium tetrachloride into 50mL of deionized water, mechanically stirring for 30min under ice water bath for complete dissolution, then adding 1.520g of anhydrous potassium carbonate into the solution, mechanically stirring for 30min under 300r/min until the solution is clear, adding 0.5g of carboxymethyl cellulose, fully stirring in 60Hz ultrasonic for 1 hour, dropwise adding ammonia water into the mixed solution, stirring and regulating the pH to 10; aging the mixture for 36 hours at 25 ℃, taking out and transferring the mixture to a centrifugal tank, carrying out centrifugal washing with deionized water, centrifuging for 12 minutes in each group until no white precipitate is generated after the supernatant is titrated with a silver nitrate solution, namely washing is completed, carrying out solid-liquid separation on the washed mixture by a decompression suction filter, drying the solid in an oven at 105-120 ℃ for 15 hours to constant weight under the vacuum degree of a vacuum pump of 0.07Mpa, crushing and grinding, placing the obtained solid powder in a muffle furnace, heating and calcining for 6 hours at the temperature of 600 ℃ in the air atmosphere, and cooling to obtain the K/TiAl 2O5 hydrolysis catalyst, which is denoted as a catalyst C;
Example 4
Sequentially adding 41.2643g of aluminum nitrate nonahydrate and 6.044mL of titanium tetrachloride into 50mL of deionized water, mechanically stirring for 30min under ice water bath for complete dissolution, then adding 2.280g of anhydrous potassium carbonate into the solution, mechanically stirring for 30min under 300r/min for clarifying the solution, adding 0.5g of ammonium carboxymethylcellulose, fully stirring in 60Hz ultrasonic for 1 hour, dropwise adding ammonia water into the mixed solution, stirring and regulating the pH to 10; aging the mixture for 36 hours at 25 ℃, taking out and transferring the mixture to a centrifugal tank, carrying out centrifugal washing with deionized water, centrifuging for 12 minutes in each group until no white precipitate is generated after the supernatant is titrated with a silver nitrate solution, namely washing is completed, carrying out solid-liquid separation on the washed mixture by a decompression suction filter, drying the solid in an oven at 105-120 ℃ for 15 hours to constant weight under the vacuum degree of a vacuum pump of 0.07Mpa, crushing and grinding, placing the obtained solid powder in a muffle furnace, heating and calcining for 6 hours at the temperature of 600 ℃ in the air atmosphere, and cooling to obtain the K/TiAl 2O5 hydrolysis catalyst, which is denoted as a catalyst D;
Comparative example
Sequentially adding 41.2643g of aluminum nitrate nonahydrate and 6.044mL of titanium tetrachloride into 50mL of deionized water, mechanically stirring for 30min under 300r/min in an ice water bath until the aluminum nitrate nonahydrate and the titanium tetrachloride are completely dissolved, dropwise adding ammonia water into the mixed solution, stirring and regulating the pH to 10; aging the mixture for 36 hours at 25 ℃, taking out and transferring the mixture to a centrifugal tank, carrying out centrifugal washing with deionized water, centrifuging for 12 minutes in each group until no white precipitate is generated after the supernatant is titrated with a silver nitrate solution, namely washing is completed, carrying out solid-liquid separation on the washed mixture by a decompression suction filter, drying the solid in an oven at 105-120 ℃ for 15 hours to constant weight under the vacuum degree of a vacuum pump of 0.07Mpa, crushing and grinding, placing the obtained solid powder in a muffle furnace, heating and calcining for 6 hours at the temperature of 600 ℃ in the air atmosphere, and cooling to obtain TiAl 2O5 hydrolysis catalyst, namely catalyst E;
As shown in fig. 1, the X-ray powder diffraction patterns of the catalysts prepared in examples 1 to 4 and comparative examples, in which diffraction peak centers observed at 25.281 °, 37.800 °, 48.049 °, 53.890 ° correspond to (101), (044), (200), (105) planes, are typical TiO 2 diffraction peaks; in the figure, diffraction peaks observed at 19.347 °, 45.666 °, and 66.600 ° correspond to the (110), (400), and (440) planes, and are diffraction peaks of γ -Al 2O3.
As can be seen from the XRD patterns of the comparative examples and comparative examples, the active component doping did not affect the structure of TiAl 2O5.
FIG. 2 is an electron microscope scan of the catalysts prepared in example 4 and comparative example. As can be seen from the figure, the TiAl 2O5 prepared in the comparative example has an agglomerated block structure; the K/TiAl 2O5 prepared in the embodiment has a nano needle shape, and the strength of the (101) surface combined with D in figure 1 is obviously reduced, which indicates that the interaction exists between potassium and titanium in the preparation process.
The catalysts obtained in examples 1 to 4 and comparative examples were analyzed and tested accordingly, and the activity and stability of the catalysts were expressed as a removal rate of COS, and the concentration of COS was measured by on-line gas chromatography.
The test conditions were: the activity test of COS catalytic hydrolysis is carried out in a fixed bed quartz tube reactor, the catalyst loading is 0.5mL, the granularity is 40-60 meshes, the reaction temperature is 50-150 ℃, the continuous detection is carried out for 2h at each reaction temperature, and the interval between the test temperature points is 25 ℃. The concentration of COS in the feed gas is 200mg/m 3,O2 volume concentration is 1%, N 2 is balance gas, and the total smoke amount is 200mL/min; each path of gas is gradually mixed through a mass flowmeter, then water vapor is added through a water saturator, and finally the mixture enters an air mixer for full mixing; the reactor is a quartz tube with the inner diameter of 10mm, and a vertical tube type heating furnace with a temperature control system provides a reaction temperature environment.
As shown in FIG. 3, the hydrolysis catalyst prepared by the invention has lower activation temperature and wider activation temperature window, wherein the catalyst D prepared by the example 4 has the best catalytic performance, which is obviously better than that of the TiAl 2O5 catalyst, and the removal efficiency of COS is improved by 40% at 50 ℃, and gradually improved along with the temperature rise, and the removal efficiency of COS can reach 100% at 75 ℃.
As can be seen from FIG. 4, the hydrolysis catalyst prepared in accordance with the present invention has an extremely high H 2 S yield, wherein the H 2 S yield of catalyst D prepared in example 4 is optimal, and the H 2 S yield at 75℃can reach 100%. The high H 2 S yield indicates that the interaction between the catalyst and H 2 S is weak, so that the H 2 S can be diffused away from the surface in time, and the poisoning of the catalyst caused by the adsorption and oxidation of H 2 S on the surface of the catalyst to generate sulfur species is reduced, thereby prolonging the service life of the catalyst.
The foregoing detailed description will set forth only for the purposes of illustrating the general principles and features of the invention, and is not meant to limit the scope of the invention in any way, but rather should be construed in view of the appended claims.
Claims (7)
1. The low-temperature poisoning-resistant hydrolysis catalyst for the fine desulfurization of the blast furnace gas comprises the following components in percentage by mass: 75-80% of carrier, 5-20% of active component, 1-5% of auxiliary agent, and 100% of sum of the above components by mass percent; the method is characterized in that: the carrier is titanium-aluminum composite oxide, wherein the molar ratio of titanium to aluminum element is (0.2-0.6): (0.4-1); in the titanium-aluminum composite oxide, a precursor of titanium is titanium tetrachloride; the precursor of aluminum is aluminum nitrate nonahydrate;
The active component comprises at least one of oxides of sodium and potassium, wherein the molar ratio of alkali metal, titanium and aluminum elements in the active component is (0.05-0.4): (0.1-0.5): 1, a step of;
the auxiliary agent is one or more of carboxymethyl cellulose and starch;
the catalyst is prepared by a process,
Sequentially adding a titanium precursor and an aluminum precursor into deionized water according to a certain molar ratio, and stirring under an ice water bath until the titanium precursor and the aluminum precursor are completely dissolved to obtain a mixed solution A;
Step two, adding the precursor of the active component into the mixed solution A according to a certain molar ratio, and stirring until the solution is clear to obtain a mixed solution B;
step three, adding an auxiliary agent into the mixed solution B according to a certain mass ratio, and stirring until the auxiliary agent is completely dissolved to obtain a mixed solution C;
Step four, dropwise adding alkali liquor into the mixed solution C, stirring and adjusting the pH value until ion precipitation is complete, and obtaining a mixed solution D;
And fifthly, sealing the mixed solution D, aging, washing, suction filtering, drying, grinding, calcining, and cooling to obtain the low-temperature poisoning-resistant hydrolysis catalyst.
2. The low temperature poisoning-resistant hydrolysis catalyst for fine desulfurization of blast furnace gas according to claim 1, wherein: the precursor of the active component comprises any one of sodium carbonate, sodium nitrate, sodium acetate, sodium bicarbonate, sodium chloride or potassium carbonate, potassium nitrate, potassium acetate, potassium bicarbonate and potassium chloride.
3. A process for preparing a low temperature poisoning resistant hydrolysis catalyst for fine desulfurization of a blast furnace gas according to any one of claims 1 to 2, comprising the steps of:
Sequentially adding a titanium precursor and an aluminum precursor into deionized water according to a certain molar ratio, and stirring under an ice water bath until the titanium precursor and the aluminum precursor are completely dissolved to obtain a mixed solution A;
Step two, adding the precursor of the active component into the mixed solution A according to a certain molar ratio, and stirring until the solution is clear to obtain a mixed solution B;
step three, adding an auxiliary agent into the mixed solution B according to a certain mass ratio, and stirring until the auxiliary agent is completely dissolved to obtain a mixed solution C;
Step four, dropwise adding alkali liquor into the mixed solution C, stirring and adjusting the pH value until ion precipitation is complete, and obtaining a mixed solution D;
And fifthly, sealing the mixed solution D, aging, washing, suction filtering, drying, grinding, calcining, and cooling to obtain the low-temperature poisoning-resistant hydrolysis catalyst.
4. The method for preparing the low-temperature poisoning-resistant hydrolysis catalyst for the fine desulfurization of the blast furnace gas according to claim 3, wherein the stirring can be performed by adopting ultrasonic waves, mechanical stirring or a combination thereof, wherein the ultrasonic frequency is 50-100 Hz, and the ultrasonic time is 0.5-2 h; the mechanical stirring speed is 200-600 r/min, and the stirring time is 0.5-2 h.
5. A method for preparing a low temperature poisoning resistant hydrolysis catalyst for fine desulfurization of blast furnace gas according to claim 3, wherein: in the fourth step, the alkali liquor comprises any one of ammonia water, sodium hydroxide and potassium hydroxide, and the pH is controlled to be 8-10.
6. A method for preparing a low temperature poisoning resistant hydrolysis catalyst for fine desulfurization of blast furnace gas according to claim 3, wherein: in the fifth step, the aging temperature is 25-40 ℃ and the aging time is 24-48 h.
7. A method for preparing a low temperature poisoning resistant hydrolysis catalyst for fine desulfurization of blast furnace gas according to claim 3, wherein: in the fifth step, centrifugal washing can be adopted, the rotation speed of a centrifugal machine is 3000-6000 r/min, and the centrifugal time of each group is 8-15 min; the suction filtration can adopt a decompression suction filter to carry out solid-liquid separation, and the vacuum degree of a vacuum pump is kept at 0.03-0.07 Mpa; the drying is carried out for 10 to 16 hours at the temperature of 105 to 120 ℃; the calcination is performed in an air atmosphere at 500-700 ℃ for 4-6 h.
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| CN100503034C (en) * | 2007-04-28 | 2009-06-24 | 山东轻工业学院 | Titanium dioxide loading method for catalyst preparation and bifunctional sulfur recovery catalyst prepared by the method |
| CN100493699C (en) * | 2007-07-25 | 2009-06-03 | 太原理工大学 | Medium-temperature carbonyl sulfide hydrolysis catalyst and its preparation method and application |
| JP6147663B2 (en) * | 2013-12-27 | 2017-06-14 | 三菱重工業株式会社 | Catalyst regeneration method for COS conversion catalyst |
| CN108970611B (en) * | 2017-05-31 | 2021-08-10 | 中国石油化工股份有限公司 | Natural gas organic sulfur hydrolysis catalyst and preparation method thereof |
| CN113441124A (en) * | 2021-06-28 | 2021-09-28 | 中晶环境科技股份有限公司 | Carbonyl sulfide hydrolysis catalyst and preparation method thereof |
| CN113731391A (en) * | 2021-08-27 | 2021-12-03 | 江苏朗润环保科技有限公司 | High-antioxidant low-temperature organic sulfur hydrolysis catalyst and preparation method thereof |
| CN113578329A (en) * | 2021-08-27 | 2021-11-02 | 江苏朗润环保科技有限公司 | Hydrolysis catalyst for removing carbonyl sulfide from blast furnace gas and preparation method thereof |
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| CN104039440A (en) * | 2012-02-24 | 2014-09-10 | 三菱重工业株式会社 | Catalyst for hydrolysis of carbonyl sulfide and hydrogen cyanide and use of titanium oxide-based composition |
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