CN107774278B - 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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- CN107774278B CN107774278B CN201610773546.XA CN201610773546A CN107774278B CN 107774278 B CN107774278 B CN 107774278B CN 201610773546 A CN201610773546 A CN 201610773546A CN 107774278 B CN107774278 B CN 107774278B
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- carbon black
- black powder
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- silicon
- flue gas
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 239000003546 flue gas Substances 0.000 title claims abstract description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 24
- 230000023556 desulfurization Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000009467 reduction Effects 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 54
- 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 47
- 239000006229 carbon black Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 35
- 239000010703 silicon Substances 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 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
- 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
- 150000001721 carbon Chemical class 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000003570 air Substances 0.000 claims description 8
- 239000007789 gas 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
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000000203 mixture Substances 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
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 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 compound 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
- 235000019441 ethanol Nutrition 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 13
- 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 14
- 238000006243 chemical reaction Methods 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 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
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 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
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite 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
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation 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
- 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
- 230000015572 biosynthetic process 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
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation 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
- 230000003993 interaction 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
- 239000011148 porous material 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
- 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
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 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
- 230000007812 deficiency Effects 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
- 150000002431 hydrogen Chemical class 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 238000012545 processing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid 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
Classifications
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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
- B01J23/002—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 methods of flue gas reduction and desulfurization catalyst.This method comprises: carbon black powder is added in the ethanol solution containing silicon source by (1), it is uniformly mixed, is separated by solid-liquid separation under the conditions of ultrasonic disperse, solid phase is dried, and obtains the modified carbon black powder of silicon source；(2) carbon black powder, boehmite dry glue powder, extrusion aid, peptizing agent and the water kneading extrusion molding obtained step (1), then carries out hydro-thermal process, and material is filtered, dried, then roasted in oxygen-containing atmosphere, and silicon-containing alumina carrier is obtained；(3) silicon-containing alumina carrier is impregnated with the maceration extract containing active component, by drying, roasting, obtains flue gas reduction and desulfurization catalyst.The catalyst of the method for the present invention preparation has large hole appearance and intensity simultaneously, and active component and carrier effect is weak, and catalyst desulfurizing effect is good, and preparation process is simple.
Description
Technical field
The present invention relates to a kind of preparation methods of flue gas reduction and desulfurization catalyst.
Background technique
SO2The main reason for being Air Pollutants, being acid rain formation, environment seriously being polluted, harm to the human body is serious,
Coal-fired flue-gas discharge is SO2Main source.Traditional flue gas desulfurization is wet desulphurization, this method complex process, investment cost is big,
And secondary pollution is generated, dry desulfurizing process is simple, but desulfurization degree is lower, 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 has many advantages, such as that operating cost is low, by-product (sulphur) using.By SO2It is directly urged from flue gas
Change is reduced to sulphur, compared with traditional sulfur removal technology, shortens process, simplifies technique, and also improve desulfurization effect,
Desulfurization can be combined with the sulphur utilization of resources.
Reducing agent used in catalysis reduction and desulfurization mainly has CH4, CO and H2Equal gases.Presently the most common catalyst one
As be with aluminium 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
It loads on carrier, catalyst then is made by dry, roasting.In roasting process, active metal component is easy and oxidation
Alumina supporter has an effect to form very strong M-O-Al key, and active component is caused to form Spinel and lose activity, or activity
Component can not complete cure to reducing catalyst activity.
CN1298755A discloses a kind of for handling the catalyst and its application method of 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/SO2Molar ratio is 2:1-4:1, can get 85%
Sulphur yield.But interaction forms new compound between the catalyst different activities component of this method preparation, is unfavorable for activity
Component on carrier it is evenly dispersed and it is active further increase, in addition, sulphur yield also up for improve.
CN102962064A discloses a kind of γ type alumina load metal oxide catalyst, preparation method and its answers
With.The γ type aluminium oxide catalyst has good adjustable pore structure, large specific surface area, absorption property, high mechanical strength, surface tool
Have the advantages that acid and thermal stability 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 gas, power station pot
In the fume treatment field of furnace.But it is strong there is also interacting between active component and carrier, it is unfavorable for active component in carrier
Upper evenly dispersed, vulcanization and activity further increase.
Physics expanding agent used in prior art preparation macropore and/or double-hole alumina support process is usually carbon black
Powder, carbon black powder dosage are 3-10wt%, and preferably 6-8wt%(is with carrying alumina weight).In roasting process, carbon black powder warp
Oxidation, burning, are finally translated into gas and escape, thus form in carrier body phase in biggish " cavity ", to generate
Macroporous aluminium oxide.It is mechanical strong if leading to very much final carrier pore size distribution disperse greatly using dosage when carbon black powder reaming, not concentrating
It is poor to spend.If dosage is too small and ideal reaming effect is not achieved.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of flue gas reduction and desulfurization catalyst.The present invention
The catalyst of method preparation has large hole appearance and intensity simultaneously, and active component and carrier effect is weak, and catalyst desulfurizing effect is good,
Preparation process is simple.
The preparation method of flue gas reduction and desulfurization catalyst of the invention, comprising:
(1) carbon black powder is added in the ethanol solution containing silicon source, is uniformly mixed under the conditions of ultrasonic disperse, solid-liquid point
From solid phase is dried, and obtains the modified carbon black powder of silicon source；
(2) carbon black powder, boehmite dry glue powder, extrusion aid, peptizing agent and water kneading that step (1) obtains are extruded into
Type, then carries out hydro-thermal process, and filtering, drying roast in oxygen-containing atmosphere, obtain 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
Desulphurization catalyst.
In the method for the present invention, silicon source described in step (1) is methyl orthosilicate, ethyl orthosilicate, positive silicic acid propyl ester or just
One or more of butyl silicate.
In the method for the present invention, carbon black powder described in step (1) can be selected from commercial goods, as acetylene carbon black, N330 carbon black,
FW200 carbon black etc..
In the method for the present invention, the solid-liquid mass ratio of carbon black powder described in step (1) and the ethanol solution containing silicon source be 1:5 ~
1:30.
In the method for the present invention, silicon source described in step (1) is 5:1~1:1 with the mass ratio of carbon black powder in terms of silica.
In the method for the present invention, ultrasonic disperse condition described in step (1) are as follows: 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 method for the present invention, separation of solid and liquid described in step (1) can be using usual manners such as filtering, centrifugations.
In the method for the present invention, drying condition described in step (1) are as follows: 30 ~ 100 DEG C of drying temperature, drying time be 0.1 ~
10 hours.
In the method for the present invention, the additional amount of the modified carbon black powder of silicon source described in step (2) is calculated as 5% with carbon black powder weight ~
20%, preferably 8% ~ 15%, on the basis of boehmite dry glue powder weight.
In the method for the present invention, extrusion aid described in step (2), peptizing agent are that kneading method is prepared in alumina process commonly
Substance, 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 of agent.Extrusion aid additional amount is generally 3% ~ 5%, and the additional amount of peptizing agent is generally 3% ~ 10%, to intend thin water
On the basis of aluminium stone dry glue powder weight；Wherein the additional amount of extrusion aid, peptizing agent and water with can kneading formed plastic carry out
Depending on extrusion molding.
In the method for the present invention, hydro-thermal process described in step (2) is generally carried out in closed pressure vessel, hydro-thermal process
Condition are as follows: temperature is 120 ~ 200 DEG C, and preferably 140 ~ 170 DEG C, the time is 5 ~ 30 hours, preferably 8 ~ 20 hours.The drying
Condition are as follows: 30 ~ 100 DEG C of drying temperature, drying time is 0.1 ~ 10 hour.It is oxygenous described in step (2) in the method for the present invention
Atmosphere is generally the mixture or one of oxygen and the mixture of inert gas of air, oxygen and nitrogen, and oxygen is in the gas phase
Volume fraction be 20% ~ 40%.The maturing temperature is 350~800 DEG C, and preferably 500~700 DEG C, calcining time is 2~8
Hour, preferably 3~5 hours.
In the method for the present invention, active component described in step (3) is in Co, Ni, Mo, W, Fe, Cu, Mn, Zn, La, Ce
One or more, preferably one or more of Co, Ni, Mo, W, one of more preferable Ni and W, Co and Mo combination；It 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 method for the present invention, drying temperature described in step (3) is 40~200 DEG C, preferably 60~150 DEG C；Drying time
It is 1~5 hour, preferably 2~4 hours；The maturing temperature be 350~800 DEG C, preferably 500~700 DEG C, calcining time 2
~6 hours, preferably 2~4 hours.
The method of the present invention has the advantages that compared with prior art
In the prior art by the property of Si modification alumina carrier surface, can not generally have target to alumina support
Specific duct it is modified, in modifying process, silica solution micelle is easily penetrated into aluminium oxide major part duct (macropore, mesoporous),
The Kong Rong of carrier is caused to be greatly lowered.The present invention prepares alumina support in kneading by wrapping up silicon source on carbon black powder surface
In the process, by hydro-thermal process, so that silicon source comes into full contact with aluminium oxide, silicon source hydrolyzes and is converted into silica, further
By calcination process, carbon powder particle, while reaming, SiO are removed2The big hole surface of carbon powder particle formation is remained stuck to, is risen
To supporting role, the intensity of alumina support, while SiO are enhanced2Modifying function, reduce active component and carrying alumina
The interaction in body surface face and the acidity for improving macroporous aluminium oxide surface, improve the activity of catalyst, additionally, due to
SiO2Supporting role ensure that the intensity of aluminium oxide macropore so that alumina support is not easy to collapse, in preparation process, Ke Yijia
Enter more carbon black powders compared with prior art, to form more macropores, to improve the mass-transfer efficiency of flue gas desulfurization, urges
Agent duct is not easy to plug, and extends the service life of catalyst.Hydro-thermal process simultaneously can be further improved aluminium oxide Kong Rong and
Aperture improves the property and thermal stability of oxidation aluminium surface.
Specific embodiment
It is carried out below by preparation method of the specific embodiment to flue gas reduction and desulfurization catalyst carrier of the invention more detailed
Thin description.
Carbon black powder used in the embodiment of the present invention and comparative example is acetylene carbon black, and technical grade is 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
Are as follows: with H2It (can also be CH as going back for Primordial Qi4, the reducibility gas such as CO), H2/SO2Molar 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 black powder is added in the ethanol solution containing ethyl orthosilicate to (wherein solid-liquid mass ratio is 1:8, positive silicon
Acetoacetic ester is with SiO2Meter is 2:1 with the mass ratio of carbon black powder), (energy density of ultrasonic disperse is under the conditions of ultrasonic disperse
0.6kW/L, ultrasonic disperse temperature are 40 DEG C, and the ultrasonic disperse time is 1 hour) it is uniformly mixed, filtering, dry 2 at 50 DEG C of solid phase
Hour, it is dried, obtains the modified carbon black powder of silicon source；
(2) the carbon black powder 54g(for obtaining step (1) is with carbon black powder poidometer), boehmite dry glue powder 600g(oxidation
Aluminium butt 65wt%) 6g nitric acid, 3g citric acid, 3g sesbania powder and 360g pure water kneading extrusion molding is added, then material is put
Entering and carries out hydro-thermal process, hydrothermal conditions in reaction kettle are as follows: temperature is 130 DEG C, and the time is 10 hours, is then filtered, dry,
It is roasted 5 hours for 500 DEG C in air atmosphere, obtains silicon-containing alumina carrier；
(3) silicon-containing alumina carrier uses the maceration extract containing cobalt and molybdenum (cobalt nitrate and ammonium molybdate) to impregnate above-mentioned carrier 3 hours,
Redundant solution is filtered, 8 hours dry at 110 DEG C, the material after drying roasts 5 hours at 550 DEG C in air atmosphere, makes
Catalyst C1 is obtained, catalyst property is shown in Table 1.
Embodiment 2
(1) carbon black powder is added in the ethanol solution containing ethyl orthosilicate to (wherein solid-liquid mass ratio is 1:15, positive silicon
Acetoacetic ester is with SiO2Meter is 3:1 with the mass ratio of carbon black powder), (energy density of ultrasonic disperse is under the conditions of ultrasonic disperse
1kW/L, ultrasonic disperse temperature are 50 DEG C, and the ultrasonic disperse time is 0.5 hour) it is uniformly mixed, filtering, dry 2 at 50 DEG C of solid phase
Hour, it is dried, obtains the modified carbon black powder of silicon source；
(2) the carbon black powder 160g(for obtaining step (1) is with carbon black powder poidometer), boehmite dry glue powder 1000g(oxygen
Change aluminium butt 65wt%), 10g nitric acid, 4g citric acid, 4g sesbania powder and 350g pure water kneading extrusion molding is added, material is put
Entering and carries out hydro-thermal process, hydrothermal conditions in reaction kettle are as follows: temperature is 150 DEG C, and the time is 12 hours, is then filtered, dry,
It is roasted 5 hours for 500 DEG C in air atmosphere, obtains silicon-containing alumina carrier；
(3) silicon-containing alumina carrier uses the maceration extract containing cobalt and molybdenum (cobalt nitrate and ammonium molybdate) to impregnate above-mentioned carrier 3 hours,
Redundant solution is filtered, 6 hours dry at 120 DEG C, the material after drying roasts 4 hours at 550 DEG C in air atmosphere, makes
Catalyst C2 is obtained, catalyst property is shown in Table 1.
Embodiment 3
(1) carbon black powder is added in the ethanol solution containing ethyl orthosilicate to (it is 1:25, positive silicon that wherein liquid, which consolidates mass ratio,
Acetoacetic ester is with SiO2Meter is 4:1 with the mass ratio of carbon black powder), (energy density of ultrasonic disperse is under the conditions of ultrasonic disperse
2kW/L, ultrasonic disperse temperature are 30 DEG C, and the ultrasonic disperse time is 0.5 hour) it is uniformly mixed, filtering, dry 2 at 50 DEG C of solid phase
Hour, it is dried, obtains the modified carbon black powder of silicon source；
(2) the carbon black powder 160g(for obtaining step (1) is with carbon black powder poidometer), boehmite dry glue powder 800g(oxygen
Change aluminium butt 65wt%), 7g nitric acid, 3g citric acid, 3g sesbania powder and 350g pure water kneading extrusion molding is added, material is put
Entering and carries out hydro-thermal process, hydrothermal conditions in reaction kettle are as follows: temperature is 160 DEG C, and the time is 15 hours, is then filtered, dry,
It is roasted 5 hours for 500 DEG C in air atmosphere, obtains silicon-containing alumina carrier；
(3) it is small to impregnate above-mentioned carrier 3 for nickeliferous and tungsten (nickel nitrate and ammonium metatungstate) the maceration extract of silicon-containing alumina carrier
When, redundant solution is filtered, 8 hours dry at 110 DEG C, roasting 5 is small at 550 DEG C in air atmosphere for the material after drying
When, catalyst C3 is made, catalyst property is shown in Table 1.
Comparative example 1
With embodiment 2, only catalyst C4 is made without the processing of step (1) in the carbon black powder of step (2).
Comparative example 2
With embodiment 2, only step (2) does not have hydrothermal treatment process, and catalyst C5 is made.
1 catalyst property of table.
Embodiment 4
The following examples illustrate desulfurization catalyst of flue gas provided by the invention and the catalytic performance of comparative catalyst.Implement
The benchmark test selection of catalyst C1-C5 prepared by example 1 ~ 3 and comparative example 1 ~ 2 carries out in atmospheric fixed bed reactor,
Reactor material is quartz glass, and internal diameter 10mm, the dosage of catalyst is 0.5g.Before catalyst is for reacting, at 600 DEG C,
0.5% SO of 35ml/min2/ 2.5% H2/ N2Presulfurization 2.5h in gaseous mixture.
The reaction temperature of evaluation test is 400 DEG C, reaction velocity 10000h-1, SO2And H2It is mixed after being diluted respectively with nitrogen
It closes and enters reactor, n (H2)/n(SO2) ratio be 3, inlet SO2Volume fraction is 0.3%, react generation elemental sulfur and
Vapor is collected by the condenser for being placed in reactor outlet, with flue gas analyzer to the SO in 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.
2 desulfurization catalyst of flue gas performance comparison of table.
3 405 DEG C of long-term operation test results of table.
It can be seen from 3 data of table 2 and table compared with comparative catalyst, catalyst provided by the invention is with higher
Flue gas desulfurization activity and simple substance Recovery ratio.After continuously running 400 hours, SO still remain2High conversion illustrates the catalyst not
Easily blocking, has good stability, and service life is long.
Claims (9)
1. a kind of preparation method of flue gas reduction and desulfurization catalyst, characterized by comprising: (1) carbon black powder is added to containing silicon
It in the ethanol solution in source, is uniformly mixed, is separated by solid-liquid separation under the conditions of ultrasonic disperse, solid phase is dried, obtains silicon source and change
The carbon black powder of property；(2) carbon black powder, boehmite dry glue powder, extrusion aid, peptizing agent and the water kneading obtained step (1) is squeezed
It forms out, then carries out hydro-thermal process, material is filtered, dried, then roasted in oxygen-containing atmosphere, and silicon-containing alumina load is obtained
Body；(3) silicon-containing alumina carrier is impregnated with the maceration extract containing active component, by drying, roasting, obtains flue gas reduction and desulfurization and urge
Agent；Silicon source described in step (1) is one of methyl orthosilicate, ethyl orthosilicate, positive silicic acid propyl ester or butyl silicate
Or it is several.
2. according to the method for claim 1, it is characterised in that: carbon black powder described in step (1) and the ethyl alcohol containing silicon source are molten
The solid-liquid mass ratio of liquid is 1:5 ~ 1:30.
3. according to the method for claim 1, it is characterised in that: silicon source described in step (1) is in terms of silica and carbon black
The mass ratio of powder is 5:1~1:1.
4. according to the method for claim 1, it is characterised in that: ultrasonic disperse condition described in step (1) are as follows: ultrasonic disperse
Energy density be 0.2 ~ 4kW/L, ultrasonic disperse temperature be 15 ~ 80 DEG C, the ultrasonic disperse time be 0.5 ~ 10 hour.
5. according to the method for claim 1, it is characterised in that: drying condition described in step (1) are as follows: drying temperature 30 ~
100 DEG C, drying time is 0.1 ~ 10 hour.
6. according to the method for claim 1, it is characterised in that: the addition of the modified carbon black powder of silicon source described in step (2)
Amount is calculated as 5% ~ 20% with carbon black powder weight, on the basis of boehmite dry glue powder weight.
7. according to the method for claim 1, it is characterised in that: hydrothermal conditions described in step (2) are as follows: temperature is
120 ~ 200 DEG C, the time is 5 ~ 30 hours.
8. according to the method for claim 1, it is characterised in that: oxygen-containing atmosphere described in step (2) is air, oxygen and nitrogen
One of mixture or oxygen and the mixture of inert gas of gas, the volume fraction of oxygen in the gas phase are 20% ~ 40%；Institute
The maturing temperature stated is 350~800 DEG C, and calcining time is 2~8 hours.
9. according to the method for claim 1, it is characterised in that: active component described in step (3) be Co, Ni, Mo, W,
One or more of Fe, Cu, Mn, Zn, La, Ce.
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