CN114367279A - Low-temperature poisoning-resistant hydrolysis catalyst for fine desulfurization of blast furnace gas and preparation method thereof - Google Patents
Low-temperature poisoning-resistant hydrolysis catalyst for fine desulfurization of blast furnace gas and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 34
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 32
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 21
- 230000023556 desulfurization Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 231100000572 poisoning Toxicity 0.000 title claims abstract description 11
- 230000000607 poisoning effect Effects 0.000 title claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 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
- 239000006229 carbon black Substances 0.000 claims abstract description 4
- 235000019241 carbon black Nutrition 0.000 claims abstract description 4
- 239000008107 starch Substances 0.000 claims abstract description 4
- 235000019698 starch Nutrition 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 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
- 238000001816 cooling Methods 0.000 claims description 7
- 230000006837 decompression Effects 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000007789 sealing Methods 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
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims 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 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
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 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
- 238000001556 precipitation Methods 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
- 239000011734 sodium Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 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
- 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
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 2
- 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 32
- 239000007789 gas Substances 0.000 description 15
- 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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 6
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- 229910010038 TiAl Inorganic materials 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 150000002898 organic sulfur compounds Chemical class 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 229910052739 hydrogen 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
- 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
- 230000001105 regulatory effect Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 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
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011368 organic material Substances 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
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—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)
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- General Chemical & Material Sciences (AREA)
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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 and 1-5% of auxiliary agent, wherein the sum of the mass percentages of the components is 100%. The carrier is an 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 low hydrolysis reaction temperature, wide catalytic hydrolysis desulfurization activity temperature window, strong poisoning resistance and long service life, and can be directly arranged after the blast furnace gas dust removal step, thereby reducing the energy consumption and the 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
Blast furnace gas is one of main byproducts generated in the iron-making process, contains rich 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 are mainly carbonyl sulfide, but the effective removal is difficult to realize by adopting a conventional removal method due to the chemical stability of the organic sulfur compounds. In view of increasingly stringent environmental regulations and catalytic specifications, COS removal is not nearly as slow.
COS can be removed by a hydroconversion process, an oxidation process, an adsorption process, a physicochemical absorption process, and the like, but these processes have high operation temperature, large energy consumption, and are prone to side reactions.
Another method is catalytic hydrolysis (COS + H)2O→H2S+CO2) Due to the mild reaction conditions, the low operation temperature and the high removal efficiency, the catalyst has become a COS conversion and removal technology widely accepted by the steel industry, wherein the selection of the catalyst is crucial to the removal effect of COS.
Chinese patent CN112619648A researches a copper-cobalt-based catalyst, and a hydrothermal synthesis method needs a high-pressure reaction kettle and has higher operation requirement. Chinese patent CN112439409A discloses an organic sulfur hydrolysis catalyst in Al2O3The double-component transition metal oxide is loaded on the catalyst, but the conversion activity of the catalyst is lower for the raw gas with low COS.
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 at 100-150 ℃ is up to more than 80%, and the reaction temperature is still high; secondly, the raw material sources are still not wide enough, and are limited to the inorganic field and are not related to the organic field; secondly, the preparation method still has an optimized space, the preparation of the catalyst carrier is firstly carried out, after the carrier is prepared by a precipitation method, 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 the two-stage operation is needed.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: in order to overcome the defects of the prior art, the invention provides a low-temperature anti-poisoning 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 and 1-5% of auxiliary agent, wherein the sum of the mass percentages of the components is 100%; the carrier is a titanium-aluminum composite oxide, wherein the molar ratio of titanium to aluminum elements is (0.2-0.6): (0.4 to 1); in the titanium-aluminum composite oxide, a precursor of titanium is tetrabutyl titanate; the precursor of the aluminum is aluminum isopropoxide. Further, the active component is one or more of oxides of alkali metal elements of the first main group.
Further, the active component comprises at least one of sodium oxide and potassium oxide, wherein the molar ratio of the alkali metal, the titanium and the aluminum 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 anti-poisoning hydrolysis catalyst for blast furnace gas fine desulfurization, which comprises the following implementation steps:
step one, sequentially adding a precursor of titanium and a precursor of aluminum into deionized water according to a certain molar ratio, and stirring in an ice-water bath until the titanium and the aluminum are completely dissolved to obtain a mixed solution A;
secondly, adding a precursor of an 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;
adding the 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 until ion precipitation is complete to obtain a mixed solution D;
and step five, sealing the mixed solution D, aging, washing, filtering, drying, grinding, calcining and cooling to obtain the low-temperature poisoning-resistant hydrolysis catalyst.
Further, the stirring can be carried out 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 liquor comprises 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 for washing, the rotating speed of a centrifugal machine is 3000-6000 r/min, and the centrifugal time of each group is 8-15 min; the vacuum filtration can adopt a decompression 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 10-16 h at 105-120 ℃; the calcination is carried out for 4-6 h at 500-700 ℃ in an air atmosphere.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention uses new materials of tetrabutyl titanate and aluminum isopropoxide in the organic field as the precursor of the titanium-aluminum composite oxide, so that the selection of the precursor material of titanium-aluminum element is not limited in the inorganic field any more; meanwhile, the element composition of tetrabutyl titanate is only C, H, O, Ti, the element composition of aluminum isopropoxide is only C, H, O, Al, and impurity ions are not contained; for example, an inorganic precursor titanium tetrachloride contains impurity Cl, and needs to be repeatedly washed and removed in the preparation process of the catalyst, while the operation can be completely omitted by using tetrabutyl titanate, which belongs to the advantage of the preparation link; in addition, the organic precursor has a certain molecular structure, and the two molecular structures are mutually built after mutual dissolution, are uniformly arranged, and have more innovation on the molecular structure of the catalyst than the uniform dispersion of ions in a solution.
2. The invention adopts alkali metal elements as active components, utilizes the characteristic that the alkali metal elements can provide a large amount of alkaline reaction sites, simultaneously increases the aperture and the specific surface area by adding auxiliaries such as carboxymethyl cellulose and the like, improves the low-temperature activity by the two aspects, and can realize the removal effect of COS of more than 95 percent at 75 ℃.
3. According to the invention, organic materials such as carboxymethyl cellulose, starch and carbon black are used as pore-enlarging additives, so that the pore-enlarging additives 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 pore-enlarging of the catalyst is facilitated, and the specific surface area is increased.
4. Compared with the common preparation process of preparing the catalyst carrier first and then preparing the catalyst by an impregnation method in the prior art, the preparation method of the low-temperature poisoning-resistant hydrolysis catalyst for blast furnace gas fine desulfurization disclosed by the invention prepares the precursor of the catalyst carrier element and the active component into a mixed solution at the same time, and then adds alkali liquor to perform simultaneous precipitation to obtain the catalyst, so that the impregnation link is omitted, and the preparation process is greatly simplified.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of catalysts prepared in examples 1-4 of the present invention and comparative example;
FIG. 2 is an electron micrograph of the catalysts prepared in comparative example (a) and example (b);
FIG. 3 is a graph showing desulfurization performance of catalysts prepared in examples 1 to 4 and a comparative example;
FIG. 4 is a plot of the hydrogen sulfide yield for the catalysts prepared in examples 1-4 and comparative example.
Detailed Description
For the understanding of the present invention, the following detailed description will be given with reference to the accompanying drawings, which are provided for the purpose of illustration only and are not intended to limit the scope of the present invention.
Example 1
41.2643g of aluminum nitrate nonahydrate and 6.044mL of titanium tetrachloride are sequentially added into 50mL of deionized water, the mixture is mechanically stirred for 30min under ice-water bath at 300r/min until the mixture is completely dissolved, then 1.1662g of anhydrous sodium carbonate is added into the solution, the mixture is mechanically stirred for 30min at 300r/min until the solution is clarified, 0.5g of carboxymethyl cellulose is added, the mixture is fully stirred for 1 hour in 60Hz ultrasound, ammonia water is dropwise added into the mixed solution, and the mixture is stirred and the pH value is adjusted to 10; sealing the mixture, aging at 25 ℃ for 36h, taking out, transferring to a centrifugal tank, performing centrifugal washing with deionized water, wherein the rotation speed of the centrifugal machine is 3600r/min, each group is centrifuged for 12min until no white precipitate is generated after titration of supernatant with silver nitrate solution, performing solid-liquid separation on the washed mixture by using a decompression filter, the vacuum degree of a vacuum pump is 0.07Mpa, drying the solid in an oven at 105-120 ℃ for 15h to constant weight, crushing and grinding, placing the obtained solid powder in a muffle furnace, heating and calcining at 600 ℃ in air for 6h, and cooling to obtain Na/TiAl2O5Catalyst, denoted catalyst a;
example 2
41.2643g of aluminum nitrate nonahydrate and 6.044mL of titanium tetrachloride are sequentially added into 50mL of deionized water, the mixture is mechanically stirred for 30min under ice-water bath at 300r/min until the mixture is completely dissolved, then 1.7492g of anhydrous sodium carbonate is added into the solution, the mixture is mechanically stirred for 30min at 300r/min until the solution is clarified, 0.5g of carboxymethyl cellulose is added, the mixture is subjected to ultrasonic stirring at 60Hz for 1 hour, ammonia water is dropwise added into the mixed solution, and the pH value is regulated to 10 through stirring; sealing the mixture, aging at 25 ℃ for 36h, taking out, transferring to a centrifugal tank, performing centrifugal washing with deionized water, wherein the rotation speed of the centrifugal machine is 3600r/min, each group is centrifuged for 12min until no white precipitate is generated after titration of supernatant with silver nitrate solution, performing solid-liquid separation on the washed mixture by using a decompression filter, the vacuum degree of a vacuum pump is 0.07Mpa, drying the solid in an oven at 105-120 ℃ for 15h to constant weight, crushing and grinding, placing the obtained solid powder in a muffle furnace, heating and calcining at 600 ℃ in air for 6h, and cooling to obtain Na/TiAl2O5The hydrolysis catalyst, denoted as catalyst B;
example 3
41.2643g of aluminum nitrate nonahydrate and 6.044mL of titanium tetrachloride are sequentially added into 50mL of deionized water, the mixture is mechanically stirred for 30min under ice-water bath at 300r/min until the mixture is completely dissolved, then 1.520g of anhydrous potassium carbonate is added into the solution, the mixture is mechanically stirred for 30min at 300r/min until the solution is clear, 0.5g of carboxymethyl cellulose is added and fully stirred for 1 hour in 60Hz ultrasound, ammonia water is dropwise added into the mixed solution, and the mixture is stirred and the pH value is adjusted to 10; sealing the mixture, aging at 25 ℃ for 36h, taking out, transferring to a centrifugal tank, performing centrifugal washing with deionized water, wherein the rotation speed of the centrifugal machine is 3600r/min, each group is centrifuged for 12min until no white precipitate is generated after titration of supernatant with silver nitrate solution, performing solid-liquid separation on the washed mixture by using a decompression filter, the vacuum degree of a vacuum pump is 0.07Mpa, drying the solid in an oven at 105-120 ℃ for 15h to constant weight, crushing and grinding, placing the obtained solid powder in a muffle furnace, heating and calcining at 600 ℃ in air for 6h, and cooling to obtain K/TiAl2O5The hydrolysis catalyst, denoted as catalyst C;
example 4
41.2643g of aluminum nitrate nonahydrate and 6.044mL of titanium tetrachloride are sequentially added into 50mL of deionized water, the mixture is mechanically stirred for 30min under ice-water bath at 300r/min until the mixture is completely dissolved, then 2.280g of anhydrous potassium carbonate is added into the solution, the mixture is mechanically stirred for 30min at 300r/min until the solution is clarified, 0.5g of carboxymethyl cellulose ammonium is added, the mixture is fully stirred for 1 hour under 60Hz ultrasound, ammonia water is dropwise added into the mixed solution, and the pH value is regulated to 10 through stirring; sealing the mixture, aging at 25 ℃ for 36h, taking out, transferring to a centrifugal tank, performing centrifugal washing with deionized water, wherein the rotation speed of the centrifugal machine is 3600r/min, each group is centrifuged for 12min until no white precipitate is generated after titration of supernatant with silver nitrate solution, performing solid-liquid separation on the washed mixture by using a decompression filter, the vacuum degree of a vacuum pump is 0.07Mpa, drying the solid in an oven at 105-120 ℃ for 15h to constant weight, crushing and grinding, placing the obtained solid powder in a muffle furnace, heating and calcining at 600 ℃ in air for 6h, and cooling to obtain K/TiAl2O5Hydrolysis catalysts, noteA catalyst D;
comparative example
41.2643g of aluminum nitrate nonahydrate and 6.044mL of titanium tetrachloride are sequentially added into 50mL of deionized water, the mixture is mechanically stirred for 30min under ice-water bath at 300r/min until the mixture is completely dissolved, ammonia water is dropwise added into the mixed solution, and the mixture is stirred and the pH value is adjusted to 10; sealing the mixture, aging at 25 ℃ for 36h, taking out, transferring to a centrifugal tank, performing centrifugal washing with deionized water, wherein the rotation speed of the centrifugal machine is 3600r/min, each group is centrifuged for 12min until no white precipitate is generated after titration of supernatant with silver nitrate solution, performing solid-liquid separation on the washed mixture by using a decompression filter, the vacuum degree of a vacuum pump is 0.07Mpa, drying the solid in an oven at 105-120 ℃ for 15h to constant weight, crushing and grinding, placing the obtained solid powder in a muffle furnace, heating and calcining at 600 ℃ in air for 6h, and cooling to obtain TiAl2O5The hydrolysis catalyst, denoted as catalyst E;
as shown in FIG. 1, the X-ray powder diffraction patterns of the catalysts prepared in examples 1 to 4 and comparative example, wherein the centers of diffraction peaks observed at 25.281 °, 37.800 °, 48.049 ° and 53.890 ° correspond to the (101), (044), (200) and (105) planes, are typical of TiO2A diffraction peak; the diffraction peak centers observed at 19.347 °, 45.666 ° and 66.600 ° in the figure correspond to the (110), (400) and (440) planes, and are γ -Al2O3The diffraction peak of (1).
As can be seen from the XRD patterns of the comparative example and the comparative example, TiAl is not affected by the doping of the active component2O5The structure of (1).
FIG. 2 is an electron micrograph of the catalysts prepared in example 4 and comparative example. As can be seen from the figure, TiAl prepared by comparative example2O5Is an agglomerated block structure; K/TiAl prepared in the examples2O5The morphology is nano needle-shaped, and the strength is obviously reduced by combining with the (101) surface of D in figure 1, which shows that the potassium and the titanium have interaction in the preparation process.
The catalysts obtained in examples 1 to 4 and comparative example were analyzed and tested accordingly, the activity and stability results of the catalysts were expressed as COS removal rate, and the COS concentration was measured by on-line gas chromatography.
The test conditions were: and (3) carrying out activity test of COS catalytic hydrolysis in a fixed bed quartz tube reactor, wherein the loading amount of the catalyst is 0.5mL, the granularity is 40-60 meshes, the reaction temperature is 50-150 ℃, each reaction temperature is continuously detected for 2h, and the test temperature points are separated by 25 ℃. The concentration of COS in the feed gas is 200mg/m3，O2Volume concentration of 1%, N2The total smoke gas is 200mL/min as balance gas; the gases are gradually mixed by a mass flow meter, then added with water vapor by a water saturator and finally enter 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 present invention has a lower activation temperature and a wider activation temperature window, wherein the catalyst D prepared in example 4 has the best catalytic performance, which is obviously superior to TiAl2O5The catalyst D improves the removal efficiency of COS by 40% at 50 ℃, the removal efficiency of COS is gradually improved along with the temperature rise, and the removal efficiency can reach 100% at 75 ℃.
As can be seen from FIG. 4, the hydrolysis catalyst prepared by the present invention has a very high H2S yield, in which H of catalyst D prepared in example 42Optimum S yield, H at 75 ℃2The S yield can reach 100%. High H2S yield indicates catalyst and H2S has weak interaction and is beneficial to H2S diffuses away from the surface in time to reduce H2S is adsorbed and oxidized on the surface of the catalyst to generate sulfur species, so that the catalyst is poisoned, and the service life of the catalyst is prolonged.
The above embodiments are merely illustrative of the technical concept and structural features of the present invention, and are intended to be implemented by those skilled in the art, but the present invention is not limited thereto, and any equivalent changes or modifications made according to the spirit of the present invention should fall within the scope of the present invention.
Claims (10)
1. The low-temperature poisoning-resistant hydrolysis catalyst for fine desulfurization of blast furnace gas comprises the following components in percentage by mass: 75-80% of carrier, 5-20% of active component and 1-5% of auxiliary agent, wherein the sum of the mass percentages of the components is 100%; the method is characterized in that: the carrier is a titanium-aluminum composite oxide, wherein the molar ratio of titanium to aluminum elements is (0.2-0.6): (0.4 to 1); in the titanium-aluminum composite oxide, a precursor of titanium is tetrabutyl titanate; the precursor of the aluminum is aluminum isopropoxide.
2. The low-temperature anti-poisoning hydrolysis catalyst for blast furnace gas fine desulfurization according to claim 1, characterized in that: the active component is one or more of oxides of alkali metal elements of the first main group.
3. The low-temperature anti-poisoning hydrolysis catalyst for blast furnace gas fine desulfurization according to claim 1, characterized in that: the active component comprises at least one of oxides of sodium and potassium, wherein the molar ratio of alkali metal, titanium and aluminum elements is (0.05-0.4): (0.1-0.5): 1.
4. the low-temperature anti-poisoning hydrolysis catalyst for blast furnace gas fine desulfurization according to claim 3, characterized in that: 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.
5. The low-temperature anti-poisoning hydrolysis catalyst for blast furnace gas fine desulfurization according to claim 1, characterized in that: the auxiliary agent is one or more of carboxymethyl cellulose, starch and carbon black.
6. A preparation method of a low-temperature poisoning-resistant hydrolysis catalyst for blast furnace gas fine desulfurization is characterized by comprising the following implementation steps:
step one, sequentially adding a precursor of titanium and a precursor of aluminum into deionized water according to a certain molar ratio, and stirring in an ice-water bath until the titanium and the aluminum are completely dissolved to obtain a mixed solution A;
secondly, adding a precursor of an 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;
adding the 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 until ion precipitation is complete to obtain a mixed solution D;
and step five, sealing the mixed solution D, aging, washing, filtering, drying, grinding, calcining and cooling to obtain the low-temperature poisoning-resistant hydrolysis catalyst.
7. The preparation method of the low-temperature anti-poisoning hydrolysis catalyst for blast furnace gas fine desulfurization according to claim 6, wherein the stirring can be performed by ultrasonic wave, 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.
8. The preparation method of the low-temperature anti-poisoning hydrolysis catalyst for blast furnace gas fine desulfurization according to claim 6, characterized in that: 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.
9. The preparation method of the low-temperature anti-poisoning hydrolysis catalyst for blast furnace gas fine desulfurization according to claim 6, characterized in that: in the fifth step, the aging temperature is 25-40 ℃, and the aging time is 24-48 h.
10. The preparation method of the low-temperature anti-poisoning hydrolysis catalyst for blast furnace gas fine desulfurization according to claim 6, characterized in that: in the fifth step, centrifugal washing can be adopted for washing, the rotating speed of a centrifugal machine is 3000-6000 r/min, and the centrifugal time of each group is 8-15 min; the vacuum filtration can adopt a decompression 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 10-16 h at 105-120 ℃; the calcination is carried out for 4-6 h at 500-700 ℃ in an air atmosphere.
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