CN107774278A - A kind of preparation method of flue gas reduction and desulfurization catalyst - Google Patents
A kind of preparation method of flue gas reduction and desulfurization catalyst Download PDFInfo
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- CN107774278A CN107774278A CN201610773546.XA CN201610773546A CN107774278A CN 107774278 A CN107774278 A CN 107774278A CN 201610773546 A CN201610773546 A CN 201610773546A CN 107774278 A CN107774278 A CN 107774278A
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- carbon powder
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- ultrasonic disperse
- flue gas
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 239000003546 flue gas Substances 0.000 title claims abstract description 25
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 24
- 230000023556 desulfurization Effects 0.000 title claims abstract description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 230000009467 reduction Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 32
- 239000010703 silicon Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000001125 extrusion Methods 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000004898 kneading Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000003292 glue Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000002803 maceration Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000012545 processing Methods 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000003570 air Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 239000011148 porous material Substances 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000003009 desulfurizing effect Effects 0.000 abstract description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 16
- 230000008569 process Effects 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 235000019241 carbon black Nutrition 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 235000015165 citric acid Nutrition 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000016507 interphase Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 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
- 230000014233 sulfur utilization Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- -1 while reaming 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a kind of preparation method of flue gas reduction and desulfurization catalyst.This method includes：（1）Carbon powder is added in the ethanol solution containing silicon source, is well mixed under the conditions of ultrasonic disperse, processing is dried in separation of solid and liquid, solid phase, obtains the carbon powder of silicon source modification；（2）By step（1）Obtained carbon powder, boehmite dry glue powder, extrusion aid, peptizing agent and water kneading extrusion molding, hydro-thermal process is then carried out, material is filtered, dries, and is then calcined in oxygen-containing atmosphere, obtains silicon-containing alumina carrier；（3）Silicon-containing alumina carrier is impregnated with the maceration extract containing active component, by drying, roasting, obtains flue gas reduction and desulfurization catalyst.Catalyst prepared by the inventive method has larger pore volume and intensity simultaneously, and active component and carrier effect is weak, and catalyst desulfurizing effect is good, and preparation technology is simple.
Description
Technical field
The present invention relates to a kind of preparation method of flue gas reduction and desulfurization catalyst.
Background technology
SO2It is Air Pollutants, is the main reason for acid rain is formed, seriously pollutes environment, harm to the human body is serious,
Coal-fired flue-gas discharge is SO2Main source.Traditional flue gas desulfurization is wet desulphurization, and this method complex process, investment cost is big,
And secondary pollution is produced, dry desulfurizing process is simple, but desulfurization degree is relatively low, and catalytic desulfurization greatly improves dry desulfurization efficiency.
SO in flue gas2Catalytic reduction technique is current flue gas desulfurization technique advanced in the world, can be applied to coal-fired or combustion
The desulfurization of oil cauldron kiln gas, have operating cost it is low, accessory substance (sulphur) using the advantages that.By SO2Directly urged from flue gas
Change is reduced to sulphur, compared with traditional sulfur removal technology, shortens flow, simplifies technique, and also improves desulfurized effect,
Desulfurization can be combined with the sulphur utilization of resources.
Reducing agent used in catalysis reduction and desulfurization mainly has CH4, CO and H2Deng gas.Presently the most common catalyst one
As be with aluminum oxide, ceria, silica, titanium dioxide etc. for carrier, with the transition such as Co, Ni, Mo, W, Fe, Cu, Zn gold
Category, rare earth oxide and its sulfide are the loaded catalyst of active component.Active component is using dipping or the method for kneading
Load on carrier, catalyst then is made by drying, being calcined.In roasting process, active metal component easily with oxidation
Alumina supporter has an effect to form very strong M-O-Al keys, causes active component to form Spinel and lose activity, or activity
Component can not complete cure so as to reducing catalyst activity.
CN1298755A discloses a kind of catalyst and its application process for being used to handle SO 2 in waste gas, catalysis
The each component weight ratio of agent is activated coke 80-98%, Co1-10%, Mo1-10%.Catalyst selects after vulcanizing treatment for hydrogen
Selecting property catalysis reduction SO2For elemental sulfur, reaction temperature is 250-400 DEG C, H2/SO2Mol ratio is 2：1-4：1,85% can be obtained
Sulphur yield.But catalyst different activities component interphase interaction prepared by this method forms new compound, is unfavorable for activity
Component dispersed and active further raising on carrier, in addition, sulphur yield is also up for improving.
CN102962064A discloses a kind of γ types alumina load metal oxide catalyst, preparation method and its answered
With.The γ type aluminium oxide catalysts have adjustable pore structure, specific surface area are big, absorption property is good, high mechanical strength, surface tool
Have the advantages that acid and heat endurance is good.The catalyst is used for flue gas and desulfurizing and denitrifying, using CO as reducing agent, to flue gas
In the nitric oxide that contains and sulfur dioxide carry out catalysis reduction, specifically in fluid catalytic cracking FCC flue gases, power station pot
In the fume treatment field of stove.But there is also active component and carrier interphase interaction is strong, it is unfavorable for active component in carrier
Upper dispersed, vulcanization and activity further improve.
It is usually carbon black that prior art, which prepares the physics expanding agent used during macropore and/or double-hole alumina support,
Powder, carbon powder dosage are 3-10wt%, preferably 6-8wt%（In terms of carrying alumina body weight）.In roasting process, carbon powder warp
Oxidation, burning, are finally translated into gas and escape, larger " cavity " is thus formd in carrier body phase, so as to generate
Macroporous aluminium oxide.If causing very much final carrier pore size distribution disperse greatly using dosage during carbon powder reaming, not concentrating, machinery is strong
Degree is poor.If dosage is too small and preferable reaming effect is not reached.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of preparation method of flue gas reduction and desulfurization catalyst.The present invention
Catalyst prepared by method has larger pore volume and intensity simultaneously, and active component and carrier effect is weak, and catalyst desulfurizing effect is good,
Preparation technology is simple.
The preparation method of the flue gas reduction and desulfurization catalyst of the present invention, including：
（1）Carbon powder is added in the ethanol solution containing silicon source, is well mixed under the conditions of ultrasonic disperse, separation of solid and liquid,
Processing is dried in solid phase, obtains the carbon powder of silicon source modification；
（2）By step（1）Obtained carbon powder, boehmite dry glue powder, extrusion aid, peptizing agent and water kneading extrusion molding,
Then hydro-thermal process is carried out, filtering, is dried, is calcined in oxygen-containing atmosphere, obtains silicon-containing alumina carrier；
（3）Silicon-containing alumina carrier is impregnated with the maceration extract containing active component, by drying, roasting, obtains flue gas reduction and desulfurization
Catalyst.
In the inventive method, step（1）Described silicon source is methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester or just
One or more in butyl silicate.
In the inventive method, step（1）Described carbon powder can be selected from commercial goods, as acetylene carbon black, N330 carbon blacks,
FW200 carbon blacks etc..
In the inventive method, step（1）The solid-liquid mass ratio of described carbon powder and the ethanol solution containing silicon source is 1：5~
1：30.
In the inventive method, step（1）Described silicon source is counted with the mass ratio of carbon powder as 5 using silica：1~1：1.
In the inventive method, step（1）Described ultrasonic disperse condition is：The energy density of ultrasonic disperse is 0.2 ~ 4kW/
L, ultrasonic disperse temperature are 15 ~ 80 DEG C, and the ultrasonic disperse time is 0.5 ~ 10 hour.
In the inventive method, step（1）Described separation of solid and liquid can use the usual manners such as filtering, centrifugation.
In the inventive method, step（1）Described drying condition is：30 ~ 100 DEG C of drying temperature, drying time be 0.1 ~
10 hours.
In the inventive method, step（2）The addition for the carbon powder that described silicon source is modified is calculated as 5% with carbon powder weight ~
20%, preferably 8% ~ 15%, on the basis of boehmite dry glue powder weight.
In the inventive method, step（2）Described extrusion aid, peptizing agent are that kneading method is prepared in alumina process and commonly used
Material, such as sesbania powder, starch, methylcellulose extrusion aid, and the medium peptization of formic acid, acetic acid, citric acid, phosphoric acid, nitric acid
One or more in agent.Extrusion aid addition is generally 3% ~ 5%, and the addition of peptizing agent is generally 3% ~ 10%, to intend thin water
On the basis of aluminium stone dry glue powder weight；Wherein the addition of extrusion aid, peptizing agent and water with can kneading formed plastic carry out
Depending on extrusion molding.
In the inventive method, step（2）Described hydro-thermal process is typically carried out in closed pressure vessel, hydro-thermal process
Condition is：Temperature is 120 ~ 200 DEG C, and preferably 140 ~ 170 DEG C, the time is 5 ~ 30 hours, preferably 8 ~ 20 hours.Described drying
Condition is：30 ~ 100 DEG C of drying temperature, drying time are 0.1 ~ 10 hour.In the inventive method, step（2）Described is oxygenous
Atmosphere is generally one kind in the mixture or the mixture of oxygen and inert gas of air, oxygen and nitrogen, and oxygen is in the gas phase
Volume fraction be 20% ~ 40%.Described sintering temperature is 350~800 DEG C, and preferably 500~700 DEG C, roasting time is 2~8
Hour, preferably 3~5 hours.
In the inventive method, step（3）Described active component is in Co, Ni, Mo, W, Fe, Cu, Mn, Zn, La, Ce
A kind of combination in one or more in one or more, preferably Co, Ni, Mo, W, more preferably Ni and W, Co and Mo；Impregnated
Journey adopts the methods of used volume impregnation, incipient impregnation or spray dipping, and dip time is 1-5 hours, preferably crosses volume impregnation.
Wherein, the soluble compound of active component is chosen in the preparation of maceration extract, and the specific concentration of maceration extract can be according to final catalysis
Depending on active metallic content in agent.
In the inventive method, step（3）Described drying temperature is 40~200 DEG C, preferably 60~150 DEG C；Drying time
For 1~5 hour, preferably 2~4 hours；Described sintering temperature be 350~800 DEG C, preferably 500~700 DEG C, roasting time 2
~6 hours, preferably 2~4 hours.
The inventive method has the following advantages that compared with prior art：
In the prior art by the property of Si modification alumina carrier surface, can not typically there is the spy to alumina support of target
Determine duct to be modified, in modifying process, Ludox micelle is easily penetrated into aluminum oxide major part duct（It is macropore, mesoporous）In, cause
The pore volume of carrier is greatly lowered.The present invention prepares alumina support process by wrapping up silicon source on carbon black powder surface in kneading
In, pass through hydro-thermal process so that silicon source fully contacts with aluminum oxide, and silicon source hydrolyzes and is converted into silica, further passes through
Calcination process, remove carbon powder particle, while reaming, SiO2The big hole surface of carbon powder particle formation is remained stuck to, plays branch
Support acts on, and enhances the intensity of alumina support, while SiO2Modifying function, reduce active component and carrying alumina body surface
The interaction in face and the acidity for improving macroporous aluminium oxide surface, the activity of catalyst is improved, additionally, due to SiO2's
Supporting role ensure that the intensity of aluminum oxide macropore so that alumina support is not easy to cave in, and in preparation process, can add and compare
The more carbon powders of prior art, so as to form more macropores, so as to improve the mass-transfer efficiency of flue gas desulfurization, catalyst pores
Road is not easily blocked, and extends the life-span of catalyst.Hydro-thermal process can further improve pore volume and the aperture of aluminum oxide simultaneously, change
The property and heat endurance of kind oxidation aluminium surface.
Embodiment
The preparation method of the flue gas reduction and desulfurization catalyst carrier of the present invention is carried out below by specific embodiment more detailed
Thin description.
The carbon powder used in the embodiment of the present invention and comparative example is acetylene carbon black, technical grade, purchased from Tianjin gold autumn realification
Work Co., Ltd.
Flue gas reduction and desulfurization catalyst prepared by the present invention is used for catalytic reducing smoke desulphurization reaction, general technology condition
For：With H2Exemplified by also Primordial Qi（Can also be CH4, the reducibility gas such as CO）, H2/SO2Mol ratio be 1-5, preferably 1.5-
3.5, entrance SO2Volume fraction is 0.1%-0.5%, preferably 0.2%-0.4%, 350-500 DEG C of reaction temperature, preferably 400-450 DEG C,
Reaction velocity 5000-25000h-1, preferably 8000-15000h-1。
Embodiment 1
（1）Carbon powder is added in the ethanol solution containing tetraethyl orthosilicate（Wherein solid-liquid mass ratio is 1：8, positive silicic acid second
Ester is with SiO2The mass ratio of meter and carbon powder is 2：1）, under the conditions of ultrasonic disperse（The energy density of ultrasonic disperse is 0.6kW/
L, ultrasonic disperse temperature are 40 DEG C, and the ultrasonic disperse time is 1 hour）It is well mixed, filter, dried 2 hours at 50 DEG C of solid phase, done
Dry processing, obtain the carbon powder of silicon source modification；
（2）By step（1）Obtained carbon powder 54g（In terms of carbon powder weight）, boehmite dry glue powder 600g（Alumina dry
Base 65wt%）6g nitric acid, 3g citric acids, 3g sesbania powders and 360g pure water kneading extrusion moldings are added, is then put into material instead
Answer and hydro-thermal process is carried out in kettle, hydrothermal conditions are：Temperature is 130 DEG C, and the time is 10 hours, is then filtered, and is dried, in sky
500 DEG C are calcined 5 hours in gas atmosphere, obtain silicon-containing alumina carrier；
（3）Silicon-containing alumina carrier, which is used, contains cobalt and molybdenum（Cobalt nitrate and ammonium molybdate）Maceration extract impregnate above-mentioned carrier 3 hours, filter
Redundant solution, dried 8 hours at 110 DEG C, dried material is calcined 5 hours at 550 DEG C in air atmosphere, is made and is urged
Agent C1, catalyst property are shown in Table 1.
Embodiment 2
（1）Carbon powder is added in the ethanol solution containing tetraethyl orthosilicate（Wherein solid-liquid mass ratio is 1：15, positive silicic acid second
Ester is with SiO2The mass ratio of meter and carbon powder is 3：1）, under the conditions of ultrasonic disperse（The energy density of ultrasonic disperse is 1kW/L,
Ultrasonic disperse temperature is 50 DEG C, and the ultrasonic disperse time is 0.5 hour）It is well mixed, filter, dried 2 hours at 50 DEG C of solid phase, done
Dry processing, obtain the carbon powder of silicon source modification；
（2）By step（1）Obtained carbon powder 160g（In terms of carbon powder weight）, boehmite dry glue powder 1000g（Aluminum oxide
Butt 65wt%）, add 10g nitric acid, 4g citric acids, 4g sesbania powders and 350g pure water kneading extrusion moldings, material is put into instead
Answer and hydro-thermal process is carried out in kettle, hydrothermal conditions are：Temperature is 150 DEG C, and the time is 12 hours, is then filtered, and is dried, in sky
500 DEG C are calcined 5 hours in gas atmosphere, obtain silicon-containing alumina carrier；
（3）Silicon-containing alumina carrier, which is used, contains cobalt and molybdenum（Cobalt nitrate and ammonium molybdate）Maceration extract impregnate above-mentioned carrier 3 hours, filter
Redundant solution, dried 6 hours at 120 DEG C, dried material is calcined 4 hours at 550 DEG C in air atmosphere, is made and is urged
Agent C2, catalyst property are shown in Table 1.
Embodiment 3
（1）Carbon powder is added in the ethanol solution containing tetraethyl orthosilicate（The wherein solid mass ratio of liquid is 1：25, positive silicic acid second
Ester is with SiO2The mass ratio of meter and carbon powder is 4：1）, under the conditions of ultrasonic disperse（The energy density of ultrasonic disperse is 2kW/L,
Ultrasonic disperse temperature is 30 DEG C, and the ultrasonic disperse time is 0.5 hour）It is well mixed, filter, dried 2 hours at 50 DEG C of solid phase, done
Dry processing, obtain the carbon powder of silicon source modification；
（2）By step（1）Obtained carbon powder 160g（In terms of carbon powder weight）, boehmite dry glue powder 800g（Aluminum oxide
Butt 65wt%）, add 7g nitric acid, 3g citric acids, 3g sesbania powders and 350g pure water kneading extrusion moldings, material is put into instead
Answer and hydro-thermal process is carried out in kettle, hydrothermal conditions are：Temperature is 160 DEG C, and the time is 15 hours, is then filtered, and is dried, in sky
500 DEG C are calcined 5 hours in gas atmosphere, obtain silicon-containing alumina carrier；
（3）The nickeliferous and tungsten of silicon-containing alumina carrier（Nickel nitrate and ammonium metatungstate）Maceration extract impregnate above-mentioned carrier 3 hours, filter
Fall redundant solution, dried 8 hours at 110 DEG C, dried material is calcined 5 hours at 550 DEG C in air atmosphere, is made
Catalyst C3, catalyst property are shown in Table 1.
Comparative example 1
With embodiment 2, simply step（2）Carbon powder without step（1）Processing, catalyst C4 is made.
Comparative example 2
With embodiment 2, simply step（2）There is no hydrothermal treatment process, catalyst C5 is made.
The catalyst property of table 1.
Embodiment 4
The following examples illustrate desulfurization catalyst of flue gas provided by the invention and the catalytic performance of comparative catalyst.Embodiment 1 ~
3 and comparative example 1 ~ 2 prepare catalyst C1-C5 benchmark test selection carried out in atmospheric fixed bed reactor, react
Equipment matter is quartz glass, and internal diameter 10mm, the dosage of catalyst is 0.5g.Catalyst is used for before reacting, at 600 DEG C, 35ml/
Min 0.5% SO2/ 2.5% H2/ N2Presulfurization 2.5h in gaseous mixture.
The reaction temperature of evaluation test is 400 DEG C, reaction velocity 10000h-1, SO2And H2Mixed after being diluted respectively with nitrogen
Conjunction enters reactor, n (H2)/n(SO2) ratio be 3, porch SO2Volume fraction is 0.3%, react generation elemental sulfur and
Vapor is collected by the condenser for being placed in reactor outlet, the SO with flue gas analyzer to exit2On-line analysis is carried out, is calculated
SO2Conversion ratio and simple substance Recovery ratio, evaluation result are shown in Table 2；Under 405 DEG C of reaction temperatures, long-term operation the results are shown in Table 3.
The desulfurization catalyst of flue gas performance comparison of table 2.
3 405 DEG C of long-term operation result of the tests of table.
It can be seen from table 2 and the data of table 3 compared with comparative catalyst, catalyst provided by the invention has higher
Flue gas desulfurization activity and simple substance Recovery ratio.After continuously running 400 hours, SO still remain2High conversion, illustrate the catalyst not
Easily block, there is good stability, service life length.
Claims (10)
- A kind of 1. preparation method of flue gas reduction and desulfurization catalyst, it is characterised in that including：（1）Carbon powder is added to containing silicon In the ethanol solution in source, it is well mixed under the conditions of ultrasonic disperse, processing is dried in separation of solid and liquid, solid phase, obtains silicon source and changes The carbon powder of property；（2）By step（1）Obtained carbon powder, boehmite dry glue powder, extrusion aid, peptizing agent and water kneading is squeezed Go out shaping, then carry out hydro-thermal process, material is filtered, dries, and is then calcined in oxygen-containing atmosphere, obtains silicon-containing alumina load Body；（3）Silicon-containing alumina carrier is impregnated with the maceration extract containing active component, by drying, roasting, flue gas reduction and desulfurization is obtained and urges Agent.
- 2. in accordance with the method for claim 1, it is characterised in that：Step（1）Described silicon source is methyl silicate, positive silicic acid One or more in ethyl ester, positive silicic acid propyl ester or butyl silicate.
- 3. in accordance with the method for claim 1, it is characterised in that：Step（1）Described carbon powder and the ethanol containing silicon source are molten The solid-liquid mass ratio of liquid is 1：5~1：30.
- 4. in accordance with the method for claim 1, it is characterised in that：Step（1）Described silicon source is in terms of silica and carbon black The mass ratio of powder is 5：1~1：1.
- 5. in accordance with the method for claim 1, it is characterised in that：Step（1）Described ultrasonic disperse condition is：Ultrasonic disperse Energy density be 0.2 ~ 4kW/L, ultrasonic disperse temperature is 15 ~ 80 DEG C, and the ultrasonic disperse time is 0.5 ~ 10 hour.
- 6. in accordance with the method for claim 1, it is characterised in that：Step（1）Described drying condition is：Drying temperature 30 ~ 100 DEG C, drying time is 0.1 ~ 10 hour.
- 7. in accordance with the method for claim 1, it is characterised in that：Step（2）The addition for the carbon powder that described silicon source is modified Amount is calculated as 5% ~ 20% with carbon powder weight, on the basis of boehmite dry glue powder weight.
- 8. in accordance with the method for claim 1, it is characterised in that：Step（2）Described hydrothermal conditions are：Temperature is： 120 ~ 200 DEG C, the time is 5 ~ 30 hours.
- 9. in accordance with the method for claim 1, it is characterised in that：Step（2）Described oxygen-containing atmosphere is air, oxygen and nitrogen One kind in the mixture or oxygen of gas and the mixture of inert gas, the volume fraction of oxygen in the gas phase are 20% ~ 40%；Institute The sintering temperature stated is 350~800 DEG C, and roasting time is 2~8 hours.
- 10. in accordance with the method for claim 1, it is characterised in that：Step（3）Described active component be Co, Ni, Mo, W, One or more in Fe, Cu, Mn, Zn, La, Ce.
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