CN108479744A - A kind of preparation method and applications of desulphurization catalyst - Google Patents
A kind of preparation method and applications of desulphurization catalyst Download PDFInfo
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- CN108479744A CN108479744A CN201810399358.4A CN201810399358A CN108479744A CN 108479744 A CN108479744 A CN 108479744A CN 201810399358 A CN201810399358 A CN 201810399358A CN 108479744 A CN108479744 A CN 108479744A
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- gangue
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- metal salt
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 16
- 230000004913 activation Effects 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000023556 desulfurization Effects 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000003245 coal Substances 0.000 claims abstract description 8
- 239000003546 flue gas Substances 0.000 claims abstract description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000012360 testing method Methods 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 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 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- -1 rare earth metal salt Chemical class 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical group [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- KKSAZXGYGLKVSV-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO KKSAZXGYGLKVSV-UHFFFAOYSA-N 0.000 claims description 5
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- YQXQWFASZYSARF-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC YQXQWFASZYSARF-UHFFFAOYSA-N 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000377 silicon dioxide Substances 0.000 abstract description 7
- 229910052681 coesite Inorganic materials 0.000 abstract description 6
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 6
- 229910052682 stishovite Inorganic materials 0.000 abstract description 6
- 229910052905 tridymite Inorganic materials 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 229910000831 Steel Inorganic materials 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000005272 metallurgy Methods 0.000 abstract 1
- 238000010248 power generation Methods 0.000 abstract 1
- 239000010959 steel Substances 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 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 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910001416 lithium ion Inorganic materials 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
- 239000001301 oxygen Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01D53/8609—Sulfur oxides
-
- B01J35/30—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
Abstract
The present invention provides a kind of preparation method and applications of desulphurization catalyst, belong to field of environment protection.The catalyst is using gangue as raw material, by obtaining porous C Al to calcined coal gangue, steam activation, reaming, carbon skeleton framework2O3‑SiO2Then active component is loaded to carrier surface by complex carrier, the specific surface area of catalyst is big, and cheap, and test finds that desulfuration efficiency is maintained at 89.2% or more, and the duration is more than 220min；The catalyst can be widely used for the catalytic desulfurization of the large-scale flue gas emission such as iron and steel enterprise, coal power generation factory, metallurgy industry enterprise；The method for preparing catalyst provides a kind of new way for the comprehensive utilization of gangue.
Description
Technical field
The present invention relates to a kind of preparation method and applications of desulphurization catalyst, belong to field of environment protection.
Technical background
In recent years, people are more and more stronger for the consciousness of environmental protection, the requirement to air quality is also higher and higher.Two
Sulfur oxide is one of the major pollutants in air, and the most important source of sulfur dioxide is mainly burnt by sulphur-containing substances such as fire coals
Generate, pollution formd to air later wherein in sulfur dioxide (SO2) emissions to air, and bring secondary pollution --- acid rain.
Therefore, controlling the discharge of sulfur dioxide becomes the most pressing project of field of environment protection.
Industrial process for desulfurizing gas mainly has two kinds of dry desulfurization and wet desulphurization at present.Dry desulfurization mainly passes through
Iron oxide or activated carbon are adsorbed and are aoxidized to the hydrogen sulfide in gas, to achieve the purpose that remove hydrogen sulfide.Wet desulphurization
The characteristics of absorbing hydrogen sulfide using adsorbent, there is the methods of chemical absorbing, Physical Absorption, due to technical operation simplicity, adapts to
Property it is stronger, in China coal chemical industry and other desulfurization industries be always an important sulfur removal technology technology and obtain adequately
Development and application.
But both the above desulfurization method more or less be there are problems that in application process, such as dry-desulphurizer regeneration
Difficulty is big, and replacement frequency is high, and labor intensity is big, and sulphur and the desulfurizing agent of formation are merged, and are unable to get product sulphur；
Wet desulphurization generation rate of by-product salt is high, and raffinate amount is big and recycling is difficult, and corrosion of device and piping, system resistance is big, power consumption height etc..
Therefore research novel desulphurization technology is imperative, since the reaction condition of oxidation sweetening is mild, can be carried out under normal pressure, operates
Flow is relatively easy, and can remove the higher sulphur of content, has obtained the approval of numerous researchers.Currently, numerous researchers
The R＆D work for having carried out oxidation-desulfurizing catalyst, due to being rich in the metal oxygens such as aluminium oxide, silica, iron oxide in gangue
Compound wherein many components all can serve as the active component of desulphurization catalyst, therefore is that raw material prepares desulfurization using gangue
Catalyst can not only realize the comprehensive utilization of gangue, improve the utility value of gangue, while can be made efficient, cheap
Desulphurization catalyst.Have no that document report directly prepares desulphurization catalyst using gangue at present.
Invention content
That the purpose of the present invention is to provide a kind of desulfuration efficiencies is high, life time is long and cheap, simple for process
The preparation method of desulphurization catalyst, while providing a kind of new way for the comprehensive utilization of the gangue of gangue.
A kind of preparation method of desulphurization catalyst, the method are lived by calcining, vapor using gangue as raw material
Change, reaming, carbon skeleton framework, active component load, obtain high-efficiency desulfurization catalyst, specific method is to follow these steps to carry out
's：
（1）Calcining
It pulverizes coal gangue and is milled to granularity as 10 mesh hereinafter, adding sodium carbonate, be uniformly mixed and be placed in tube furnace,
N2、CO2、O2It is calcined under mixed atmosphere, calcination temperature is 700 ~ 1200 DEG C, and calcination time is 20 ~ 30min, wherein gangue and carbon
Sour sodium mass ratio is（3~4）:1；
（2）Steam activation
By step（1）Obtained sample is added in pyroreaction kettle, the temperature of reaction kettle is increased to 300 ~ 400 DEG C, control
The pressure of reaction kettle is 22.4MPa, then passes to water, reaches supercriticality, reacts 10 ~ 15min；
（3）Reaming
By step（2）Obtained sample is added in expanding agent aqueous solution, then stirs 1 ~ 3h in a heated condition, is filtered, 110
Dry at ~ 130 DEG C, wherein expanding agent is lithium metal salt；
（4）Carbon skeleton framework
By step（3）Obtained drying sample is added in ultrasonic reactor, adds organic titanium solution, control supersonic frequency, temperature
Degree and ultrasonic time, after the completion of ultrasonic reaction, by sample at 110 ~ 120 DEG C dry 2 ~ 3h, then 800 ~ 900 in Muffle furnace
DEG C roasting, roasting time be 1 ~ 2h；
（5）Active component loads
By step（4）Obtained sample is immersed in the mixed solution that active component is rare earth metal salt and alkali metal salt, ultrasound
20 ~ 80min is impregnated, is filtered, is put into 110 DEG C of baking ovens and dries to constant weight, roasts 2 ~ 3h at 600 ~ 1000 DEG C in a nitrogen atmosphere,
Obtain catalyst.
Further, Al in the raw material gangue2O3Content be more than 25%.
Further, the step（1）N in middle gaseous mixture2、CO2、O2Volume ratio be 1：（2~3）：（4~8）.
Further, the step（3）Middle heating temperature is 20 ~ 50 DEG C, while expanding agent lithium metal salt is lithium nitrate, sulphur
One kind in sour lithium, lithium carbonate, lithium hypochlorite or arbitrary several mixture.
Further, the step（4）Middle organic titanium is any one in methanol titanium, titanium ethanolate or butanol titanium, and
Supersonic frequency is 17.5-22KHz, and temperature is 50 ~ 80 DEG C, and the time is 5 ~ 20min.
Further, the step（5）Middle rare earth metal salt is any one in lanthanum nitrate, cerous nitrate or yttrium nitrate,
And mass concentration is 1 ~ 12%；Alkali metal salt is potassium nitrate, and mass concentration is 0.3 ~ 1.2%.
Calcination processing：Gangue is mixed with sodium carbonate, in mixed gas N2、CO2、O2Middle calcining, institute wherein in gangue
It is carbon containing to be detached from from gangue under carbon dioxide, oxygen effect, it is detached from the carbon dioxide generated in the process and promotes gangue
The formation of sample micropore.
Steam activation：Sample reacts in supercritical water medium, and the metal of sample surfaces is oxidized to form metal oxidation
Object, while vapor is during high speed exercise, can be connected to the hole not being connected in sample, further increase the hole body of sample
Product.
Reaming：Sample is added in lithium nitrate, lithium sulfate, lithium carbonate, lithium hypochlorite aqueous solution, under the conditions of certain temperature
Stirring, the small lithium ion of aqueous solution Ionic Radius displace part ion radius is big in sample calcium ion, barium ions, magnesium from
The aperture of son, iron ion etc., gangue carrier becomes larger.
Carbon skeleton framework：Sample is added to organic titanium（Methanol titanium, titanium ethanolate or butanol titanium）In, by ultrasonic reaction,
Active metal titanium is supported on sample surfaces, simultaneously the sample containing organic titanium by organic molecule by diffusing into the hole of sample
Product pass through high-temperature roasting, form porous C-Al2O3-SiO2The addition of complex carrier, wherein organic carbon further enhances porous load
The microcellular structure of body.
Active component loads：By porous C-Al obtained2O3-SiO2It is rare earth metal that complex carrier, which is immersed in active component,
In salt and alkali metal salt soln, high-performance desulphurization catalyst is formed.
The present invention also provides the applications of above-mentioned catalyst, it is characterised in that：Desulfurization catalyst of flue gas 30g is weighed to be positioned over
In fixed bed reactors, 150 DEG C are then heated to, reactor pressure is 1.3 ~ 1.5MPa, is 600mL/min cigarettes by throughput
Gas, flue gas composition SO2:800~1000ppm、N2：15~30%、O2：5 ~ 10%, test find desulfuration efficiency be maintained at 89.2% with
On, the duration is more than 220min.
Beneficial effects of the present invention：
（1）The present invention loads gangue by calcining, steam activation, reaming, carbon skeleton framework, active component, obtains height
Desulphurization catalyst is imitated, wherein calcining, steam activation, reaming can increase the pore size distribution of gangue, is in addition being surpassed organic titanium
In sound effect is lower gangue sample duct of penetrating into that treated, then roasting forms porous C-Al at high temperature2O3-SiO2It is compound
Carrier, the support strength height, large specific surface area, micropore are evenly distributed, and the activity of catalyst can be improved by active component load；
（2）The present invention prepares desulphurization catalyst by raw material of gangue, and raw material is cheap and easy to get, realizes waste utilization, is bastard coal
The comprehensive utilization of stone provides a new way；
（3）Catalyst desulfurizing prepared by the present invention is efficient, and it is long to continue desulfurization time.
Description of the drawings
Fig. 1 embodiments 1 prepare the SEM figures of catalyst；
Fig. 2 embodiments 2 prepare the SEM figures of catalyst；
Fig. 3 embodiments 3 prepare the SEM figures of catalyst.
Specific implementation mode
The specific implementation mode of the present invention is further illustrated below.
The present invention provides a kind of preparation method of desulphurization catalyst, the method is using gangue as raw material, by forging
Burning, steam activation, reaming, carbon skeleton framework, active component load, obtain high-efficiency desulfurization catalyst, specific method is to press
What row step carried out：
（1）Calcining
It pulverizes coal gangue and is milled to granularity as 10 mesh hereinafter, adding sodium carbonate, be uniformly mixed and be placed in tube furnace,
N2、CO2、O2It is calcined under mixed atmosphere, calcination temperature is 700 ~ 1200 DEG C, and calcination time is 20 ~ 30min, wherein gangue and carbon
Sour sodium mass ratio is（3~4）:1；
（2）Steam activation
By step（1）Obtained sample is added in pyroreaction kettle, the temperature of reaction kettle is increased to 300 ~ 400 DEG C, control
The pressure of reaction kettle is 22.4MPa, then passes to water, reaches supercriticality, reacts 10 ~ 15min；
（3）Reaming
By step（2）Obtained sample is added in expanding agent aqueous solution, then stirs 1 ~ 3h in a heated condition, is filtered, 110
Dry at ~ 130 DEG C, wherein expanding agent is lithium metal salt；
（4）Carbon skeleton framework
By step（3）Obtained drying sample is added in ultrasonic reactor, adds organic titanium solution, control supersonic frequency, temperature
Degree and ultrasonic time, after the completion of ultrasonic reaction, by sample at 110 ~ 120 DEG C dry 2 ~ 3h, then 800 ~ 900 in Muffle furnace
DEG C roasting, roasting time be 1 ~ 2h；
（5）Active component loads
By step（4）Obtained sample is immersed in the mixed solution that active component is rare earth metal salt and alkali metal salt, ultrasound
20 ~ 80min is impregnated, is filtered, is put into 110 DEG C of baking ovens and dries to constant weight, roasts 2 ~ 3h at 600 ~ 1000 DEG C in a nitrogen atmosphere,
Obtain catalyst.
Calcination processing in the present invention：Gangue is mixed with sodium carbonate, in mixed gas N2、CO2、O2Middle calcining, wherein coal
Institute is carbon containing in spoil is detached under carbon dioxide, oxygen effect from gangue, is detached from the carbon dioxide generated in the process and promotes
The formation of gangue sample micropore.
Steam activation in the present invention：Sample reacts in supercritical water medium, and the metal of sample surfaces is oxidized to form
Metal oxide, while vapor is during high speed exercise, can be connected to the hole not being connected in sample, further increase sample
The pore volume of product.
Reaming in the present invention：Sample is added in lithium nitrate, lithium sulfate, lithium carbonate, lithium hypochlorite aqueous solution, a constant temperature
It is stirred under the conditions of degree, the small lithium ion of aqueous solution Ionic Radius displaces the calcium ion, barium that part ion radius is big in sample
The aperture of ion, magnesium ion, iron ion etc., gangue carrier becomes larger.
Carbon skeleton framework in the present invention：Sample is added to organic titanium（Methanol titanium, titanium ethanolate or butanol titanium）In, by super
Active metal titanium is supported on sample surfaces by diffusing into the hole of sample, contained simultaneously by phonoresponse, organic molecule
The sample of organic titanium passes through high-temperature roasting, forms porous C-Al2O3-SiO2The addition of complex carrier, wherein organic carbon is further strong
The microcellular structure of porous carrier is changed.
Active component loads in the present invention：By porous C-Al obtained2O3-SiO2Complex carrier is immersed in active component
In rare earth metal salt and alkali metal salt soln, high-performance desulphurization catalyst is formed.
Below by specific embodiment, the present invention is further described, but is not limited to following embodiment.
Embodiment 1
（1）Calcining
The crushing of 40g gangues is milled to granularity as 10 mesh hereinafter, adding 10g sodium carbonate, is uniformly mixed and is placed on tube furnace
In, in N2、CO2、O2It is calcined under mixed atmosphere, wherein N2、CO2、O2Volume ratio be 1：2：8, calcination temperature is 1200 DEG C, calcining
Time is 20min；
（2）Steam activation
By step（1）Obtained sample is added in pyroreaction kettle, the temperature of reaction kettle is increased to 400 DEG C, control reaction
The pressure of kettle is 22.4MPa, then passes to water, reaches supercriticality, reacts 10min；
（3）Reaming
By step（2）Obtained sample is added in lithium nitrate aqueous solution, then stirs 1h under the conditions of 30 DEG C, filtering, 110 DEG C
Lower drying；
（4）Carbon skeleton framework
By step（3）Obtained drying sample is added in ultrasonic reactor, adds ethyl alcohol titanium solution, control supersonic frequency, temperature
Degree and ultrasonic time, after the completion of ultrasonic reaction, dry 2h, then 900 DEG C of roastings in Muffle furnace, roasting at 110 DEG C by sample
The burning time is 1h；
（5）Active component loads
By step（4）It is the nitre that mass concentration is 1% lanthanum nitrate and mass concentration is 0.3% that obtained sample, which is immersed in active component,
In sour potassium mixed solution, ultrasonic immersing 20min is filtered, and is put into 110 DEG C of baking ovens and is dried to constant weight, and in a nitrogen atmosphere 1000
2h is roasted at DEG C, obtains catalyst 37.9g.
Embodiment 2
（1）Calcining
The crushing of 40g gangues is milled to granularity as 10 mesh hereinafter, adding 12.3g sodium carbonate, is uniformly mixed and is placed on tubular type
In stove, in N2、CO2、O2It is calcined under mixed atmosphere, wherein N2、CO2、O2Volume ratio be 1：2：4, calcination temperature is 700 DEG C, is forged
The burning time is 20min；
（2）Steam activation
By step（1）Obtained sample is added in pyroreaction kettle, the temperature of reaction kettle is increased to 300 DEG C, control reaction
The pressure of kettle is 22.4MPa, then passes to water, reaches supercriticality, reacts 10min；
（3）Reaming
By step（2）Obtained sample is added in lithium nitrate aqueous solution, then stirs 1h under the conditions of 30 DEG C, filtering, 110 DEG C
Lower drying；
（4）Carbon skeleton framework
By step（3）Obtained drying sample is added in ultrasonic reactor, adds ethyl alcohol titanium solution, control supersonic frequency, temperature
Degree and ultrasonic time, after the completion of ultrasonic reaction, dry 2h, then 900 DEG C of roastings in Muffle furnace, roasting at 110 DEG C by sample
The burning time is 1h；
（5）Active component loads
By step（4）It is that mass concentration is 12% cerous nitrate and mass concentration is 1.2% that obtained sample, which is immersed in active component,
In potassium nitrate mixed solution, ultrasonic immersing 20min is filtered, and is put into 110 DEG C of baking ovens and is dried to constant weight, in a nitrogen atmosphere
2h is roasted at 1000 DEG C, obtains catalyst 38.9g.
Embodiment 3
（1）Calcining
The crushing of 40g gangues is milled to granularity as 10 mesh hereinafter, adding 12.3g sodium carbonate, is uniformly mixed and is placed on tubular type
In stove, in N2、CO2、O2It is calcined under mixed atmosphere, wherein N2、CO2、O2Volume ratio be 1：2：6, calcination temperature is 700 DEG C, is forged
The burning time is 20min；
（2）Steam activation
By step（1）Obtained sample is added in pyroreaction kettle, the temperature of reaction kettle is increased to 400 DEG C, control reaction
The pressure of kettle is 22.4MPa, then passes to water, reaches supercriticality, reacts 10min；
（3）Reaming
By step（2）Obtained sample is added in lithium hypochlorite aqueous solution, then stirs 1h under the conditions of 50 DEG C, filtering, and 110
It is dry at DEG C；
（4）Carbon skeleton framework
By step（3）Obtained drying sample is added in ultrasonic reactor, adds butanol titanium solution, control supersonic frequency, temperature
Degree and ultrasonic time, after the completion of ultrasonic reaction, dry 2h, then 900 DEG C of roastings in Muffle furnace, roasting at 110 DEG C by sample
The burning time is 1h；
（5）Active component loads
By step（4）It is that mass concentration is 12% yttrium nitrate and mass concentration is 1.2% that obtained sample, which is immersed in active component,
In potassium nitrate mixed solution, ultrasonic immersing 20min is filtered, and is put into 110 DEG C of baking ovens and is dried to constant weight, in a nitrogen atmosphere
2h is roasted at 1000 DEG C, obtains catalyst 36.3g.
The catalyst 30g that embodiment 1,2,3 obtains is positioned in fixed bed reactors, then heats to 150 DEG C, reaction
Device pressure is 1.3 ~ 1.5MPa, is 600mL/min flue gases, flue gas composition SO by throughput2:800~1000ppm、N2：15%、
O2：5%, test result is as shown in table 1.
Table 1
Description of the drawings：Fig. 1,2,3 are respectively the SEM figures that embodiment 1,2,3 prepares catalyst, from three width it can be seen from the figure thats, profit
The desulphurization catalyst prepared with gangue is porous structure, and can't see apparent Active components distribution in catalyst surface,
Further illustrate that active component is evenly distributed on catalyst surface, to make the activity of catalyst increase.
Claims (7)
1. a kind of preparation method of desulphurization catalyst, the method be using gangue as raw material, by calcining, steam activation,
Reaming, carbon skeleton framework, active component load, obtain high-efficiency desulfurization catalyst, and specific method follows these steps to carry out：
Calcining
It pulverizes coal gangue and is milled to granularity as 10 mesh hereinafter, adding sodium carbonate, be uniformly mixed and be placed in tube furnace, in N2、
CO2、O2It is calcined under mixed atmosphere, calcination temperature is 700 ~ 1200 DEG C, and calcination time is 20 ~ 30min, wherein gangue and carbonic acid
Sodium mass ratio is（3~4）:1；
Steam activation
By step（1）Obtained sample is added in pyroreaction kettle, the temperature of reaction kettle is increased to 300 ~ 400 DEG C, control
The pressure of reaction kettle is 22.4MPa, then passes to water, reaches supercriticality, reacts 10 ~ 15min；
Reaming
By step（2）Obtained sample is added in expanding agent aqueous solution, then stirs 1 ~ 3h in a heated condition, is filtered, 110
Dry at ~ 130 DEG C, wherein expanding agent is lithium metal salt；
Carbon skeleton framework
By step（3）Obtained drying sample is added in ultrasonic reactor, adds organic titanium solution, control supersonic frequency, temperature
Degree and ultrasonic time, after the completion of ultrasonic reaction, by sample at 110 ~ 120 DEG C dry 2 ~ 3h, then 800 ~ 900 in Muffle furnace
DEG C roasting, roasting time be 1 ~ 2h；
Active component loads
By step（4）Obtained sample is immersed in the mixed solution that active component is rare earth metal salt and alkali metal salt, ultrasound
20 ~ 80min is impregnated, is filtered, is put into 110 DEG C of baking ovens and dries to constant weight, roasts 2 ~ 3h at 600 ~ 1000 DEG C in a nitrogen atmosphere,
Obtain catalyst.
2. a kind of preparation method of desulphurization catalyst according to claim 1, it is characterised in that：In the raw material gangue
Al2O3Content be more than 25%.
3. a kind of preparation method of desulphurization catalyst according to claim 1, it is characterised in that：The step（1）In mix
Close N in gas2、CO2、O2Volume ratio be 1：（2~3）：（4~8）.
4. a kind of preparation method of desulphurization catalyst according to claim 1, it is characterised in that：The step（3）In plus
Hot temperature is 20 ~ 50 DEG C, while expanding agent lithium metal salt is lithium nitrate, lithium sulfate, lithium carbonate, one kind in lithium hypochlorite or appoints
It anticipates several mixtures.
5. a kind of preparation method of desulphurization catalyst according to claim 1, it is characterised in that：The step（4）In have
Machine titanium is any one in methanol titanium, titanium ethanolate or butanol titanium, and supersonic frequency is 17.5-22KHz, and temperature is 50 ~ 80
DEG C, the time is 5 ~ 20min.
6. a kind of preparation method of desulphurization catalyst according to claim 1, it is characterised in that：The step（5）In it is dilute
Earth metal salt is any one in lanthanum nitrate, cerous nitrate or yttrium nitrate, and mass concentration is 1 ~ 12%；Alkali metal salt is nitre
Sour potassium, mass concentration are 0.3 ~ 1.2%.
7. a kind of application of desulphurization catalyst described in claim 1, it is characterised in that：Desulfurization catalyst of flue gas 30g is weighed to put
It is placed in fixed bed reactors, then heats to 150 DEG C, reactor pressure is 1.3 ~ 1.5MPa, is 600mL/ by throughput
Min flue gases, flue gas composition SO2:800~1000ppm、N2：15~30%、O2：5 ~ 10%, test finds that desulfuration efficiency is maintained at
89.2% or more, the duration is more than 220min.
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| CN112316924A (en) * | 2020-10-20 | 2021-02-05 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Coal gangue-based porous composite material and preparation method and application thereof |
| CN113413741A (en) * | 2021-05-28 | 2021-09-21 | 昆明理工大学 | Method for applying coal gangue and activated slag thereof to tail gas desulfurization |
| CN113499754A (en) * | 2021-06-23 | 2021-10-15 | 国家煤化工产品质量监督检验中心（安徽）（淮南市产品质量监督检验所） | Composite adsorption material based on coal gangue and coal ash and preparation process thereof |
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| CN113499754B (en) * | 2021-06-23 | 2023-06-02 | 国家煤化工产品质量监督检验中心（安徽）（淮南市产品质量监督检验所） | Composite adsorption material based on gangue and fly ash and preparation process thereof |
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