CN102091616B - Preparation method of ruthenium-containing composite catalyst used for catalytic oxidation of zero-valent mercury - Google Patents
Preparation method of ruthenium-containing composite catalyst used for catalytic oxidation of zero-valent mercury Download PDFInfo
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- CN102091616B CN102091616B CN 201010568759 CN201010568759A CN102091616B CN 102091616 B CN102091616 B CN 102091616B CN 201010568759 CN201010568759 CN 201010568759 CN 201010568759 A CN201010568759 A CN 201010568759A CN 102091616 B CN102091616 B CN 102091616B
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- ruthenium
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- catalytic oxidation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 56
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 28
- 230000003647 oxidation Effects 0.000 title claims abstract description 27
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000007598 dipping method Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003891 oxalate salts Chemical class 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- PIDXZFLNYVHZCP-UHFFFAOYSA-N carbonic acid;ruthenium Chemical compound [Ru].OC(O)=O PIDXZFLNYVHZCP-UHFFFAOYSA-N 0.000 claims description 2
- 230000001413 cellular effect Effects 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- SJIJPHKXALISMQ-UHFFFAOYSA-N oxalic acid;ruthenium Chemical compound [Ru].OC(=O)C(O)=O SJIJPHKXALISMQ-UHFFFAOYSA-N 0.000 claims description 2
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 18
- 239000003546 flue gas Substances 0.000 abstract description 18
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 22
- 229910010413 TiO 2 Inorganic materials 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 13
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 13
- 239000002245 particle Substances 0.000 description 10
- 239000011572 manganese Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000012717 electrostatic precipitator Substances 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- 229910000474 mercury oxide Inorganic materials 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006213 oxygenation reaction Methods 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910017309 Mo—Mn Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 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
- 238000003915 air pollution Methods 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of a ruthenium-containing composite catalyst used for catalytic oxidation of zero-valent mercury. The ruthenium-containing composite catalyst with high efficiency is prepared by using titanium dioxide and other porous materials as carriers, selecting elements, such as manganese, cobalt, copper and the like as catalyst main components, and adopting a ruthenium element as a catalysis enhancing component and molybdenum and cerium elements as auxiliary components. The catalyst prepared in the invention is used for catalytically oxidizing Hg<0> in flue gas into Hg<2+> under the action of HCl or less other oxidizing agents to ensure that the Hg<2+> can be absorbed and removed by a wet desulphurization system at the downstream, thus the purpose of controlling emission of mercury in the flue gas is achieved.
Description
Technical field
What the present invention relates to is a kind of Preparation of Catalyst of smoke catalytic technical field, specifically is a kind of preparation method who contains the ruthenium composite catalyst who is used for the nonvalent mercury catalytic oxidation.
Background technology
Mercury is a kind of toxic pollutant, and is because it has characteristics such as bioaccumulation property and difficult degraded, also very big to the harm of environment.In recent years, the mercury pollution problem receives increasing concern.In February, 2009, whole world council of United Nations Environment Programme holds in Nairobi, and participant various countries minister agrees to negotiate with regard to drafting the international treaties of administering mercury pollution, and international community has reached unprecedented height to the concern of global mercury pollution problem.Mercury emissions source in the environment generally is divided into natural source and artificial source, and the anthropogenic discharge who causes mercury pollution mainly is the burning of fossil fuel, mercury ore and the smelting of other metals and the application in the electrical equipment industry etc.Wherein, the discharge capacity of mercury accounts for the very big proportion of artificial mercury emission in the coal-fired flue-gas, so the mercury emissions in the control coal-fired flue-gas is very crucial.
Mercury in the coal-fired flue-gas mainly exists with three kinds of forms: nonvalent mercury (Hg
0), mercury oxide (Hg
2+) and particle mercury (Hg
p).Wherein, Hg
2+And Hg
pCan pass through existing Air Pollution Control Board control equipment (APCDs), like electrostatic precipitator (ESP), the removals such as (WFGD) of wet desulphurization equipment.At present, ESP, WFGD equipment have obtained in China coal-burning power plant using widely, if can effectively utilize existing APCDs to carry out fume mercury-removing, just need not increase extra removal of mercury equipment, thereby significantly reduce the cost of fume mercury-removing.Yet the Hg0 in the flue gas is volatile, is insoluble in water, is not easy by effective removal.And, according to coal-fired different in kind, Hg
0Ratio in the flue gas total mercury is generally 20～80%, therefore finds one Hg0 is converted into Hg fast
2+Or Hg
pEffective way, the removal of mercury ability of giving full play to existing APCDs is very crucial, this also becomes the focus of current research.
Take suitable ancillary method to realize Hg
0To Hg
2+Efficient conversion, to make full use of desulfurizer efficient absorption Hg
2+Method be to control Hg at present
0Most economical feasible approach, and become the research focus gradually.But Hg
0To Hg
2+Efficient conversion be key and the difficult point place of high-efficiency mercury removal, the researcher does not obtain maturation method for transformation efficiently as yet at present.Confirmed that at present (Selective catalytic reduction, SCR) catalyst can promote significantly that HCl is to Hg in the flue gas to SCR
0Oxidation, thereby help to improve the clearance of mercury.Through changing each operational factor of SCR such as NO concentration, NH
3Discoveries such as/NO, temperature and coal: during chlorinity 400～600ppm, it is best that the oxygenation efficiency of mercury can reach; But sulfide can significantly reduce the mercury oxidation rate, because SO
2And SO
3Cause the oxygenation efficiency of mercury to reduce with the active sites of chloride competition catalyst surface; SO in addition
2And SO
3Can make the catalyst poisoning inactivation with the sulphate form deposition at catalyst surface.The catalyst that for this reason, must combine the oxidation characteristics developing special of nonvalent mercury.
The catalyst of the nonvalent mercury of research catalysis at present oxidation has been obtained certain progress, and wherein the SCR catalyst has obtained paying attention to the transformation of nonvalent mercury.When HCl content was higher in the flue gas, this type catalyst strengthened the effect of nonvalent mercury catalyzed conversion, and the product that is produced is (like HgCl
2) will be by carried away by air movement.But the existence of sulfur dioxide in flue gas has the obvious suppression effect to general transition-metal catalyst, and single metal oxides is difficult to bring into play effective catalytic action mostly, and the temperature range of reacting required is high and narrow, generally need be higher than 250 ℃.One Chinese patent application 200510024939.2 (flue gas hydrargyrum-removing method by catalytic oxidation) has proposed to utilize transition metal oxides such as iron, cobalt, nickel, copper as active component catalytic oxidation nonvalent mercury; This method considers to utilize oxygen or the Lattice Oxygen of catalyst in the flue gas to be converted into mercury oxide to nonvalent mercury, and is adsorbed on catalyst surface.But, do not consider the influence of factor such as hydrogen chloride and sulfur dioxide in the flue gas in this patent.Generally contain a certain amount of HCl in the actual flue gas, the catalytic oxidation product of nonvalent mercury is mainly HgCl when HCl exists
2And, when sulfur dioxide exists this type activity of such catalysts is suppressed highly significant.In addition, patents such as U.S. Patent application US2003170159, PCT patent application WO2006009079 are reported part noble metal or catalyst of transition metal oxide, but these patents are paid close attention to seldom the sulfur resistance of catalyst.Research shows that the oxide with certain ruthenium that mixes in the catalyst can significantly improve the transformation of catalyst to nonvalent mercury, and the anti-sulfur dioxide effect of catalyst is significantly improved.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists; A kind of preparation method who contains the ruthenium composite catalyst who is used for the nonvalent mercury catalytic oxidation is provided; With ruthenium element as the catalysis enhancement component; Molybdenum and Ce elements are helper component, process efficient composite catalyst through the method for doping treatment, make it under different temperature, be equipped with advantages of high catalytic activity and sulfur resistance.This catalyst is under the effect of HCl or other small amounts agent, with the Hg in the flue gas
0Catalytic oxidation is Hg
2+, make it to be absorbed and remove by the wet desulfurization system in downstream, realize the purpose of mercury emissions control in the flue gas.
The present invention realizes that through following technical scheme it is carrier that the present invention adopts titanium dioxide and other porous material, and selecting elements such as manganese, cobalt, copper for use is the catalyst major constituent; Ruthenium element is as the catalysis enhancement component, and molybdenum and Ce elements are helper component, process efficient composite catalyst.
The preparation method who the present invention relates to may further comprise the steps:
The first step, add to add deionized water after the ruthenium element presoma is as predecessor and stir and obtain dipping solution that the total content of predecessor is in the dipping solution: 0.01g/mL-0.50g/mL after catalyst major constituent, helper component mixed;
Described catalyst major constituent is meant: a kind of or its combination in the nitrate of manganese, cobalt or copper, carbonate, oxalates or the acetate.
Described helper component is meant: a kind of or its combination in the nitrate of molybdenum or cerium, carbonate, oxalates or the acetate.
Described ruthenium element presoma is meant: a kind of or its combination in nitric acid ruthenium, carbonic acid ruthenium, oxalic acid ruthenium or the ruthenium acetate.
Second goes on foot, catalyst carrier is immersed stir dipping in the dipping solution and after Separation of Solid and Liquid, will carry out preliminary treatment through the catalyst carrier of dipping, after sintering makes catalyst.
Described catalyst carrier is the silicate of titanium dioxide, aluminium oxide, silica, crystalline state or in alumino-silicate, imvite or the active carbon one or more, and this catalyst carrier is spherical, graininess, tabular or cellular.
Described preliminary treatment is meant any one in the following dual mode:
A) under 40 ℃～100 ℃ temperature, dried 5-24 hour;
B) use the mould press forming.
Described sintering is meant: adopt Muffle furnace to be 1～30 ℃/minute with heating rate and rise to 300 ℃ of roasting 0.5～2h; Rise to 400 ℃ of roasting 0.5～4h with 1～30 ℃/minute speed again presoma is fully decomposed, with 1～2 ℃/minute cooldown rate catalyst is cooled to normal temperature at last.
What the present invention relates to that method for preparing obtains contains the ruthenium composite catalyst; Wherein: the mass percentage content of manganese, cobalt or copper is 1%-10%; The mass percentage content of ruthenium element is 0.05%-2%, and the mass percentage content of molybdenum or Ce elements is 0.5%-5%.
Utilize method for preparing contain ruthenium composite type metallic oxide catalyst to the catalytic oxidation ability of nonvalent mercury much larger than single component catalyst; And can be under the temperature (100～450 ℃) of broad and higher sulfur dioxide concentration the efficiently catalyzing and oxidizing nonvalent mercury, prevent the catalyst poisoning inactivation.
The specific embodiment
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1
With Powdered TiO
2Be carrier, utilize immersion process for preparing Mn/TiO
2, Ru/TiO
2And Ru-Mn/TiO
2Catalyst.
Configuration dipping solution: A, get the manganese nitrate solution of 2g 30%, add deionized water and be diluted to 20ml; B, the manganese nitrate solution of getting 2g 30%, 0.2g ruthenic chloride add deionized water and are diluted to 20ml; C, the manganese nitrate solution of getting 2g 30%, 0.2g ruthenic chloride, the 0.5g ammonium molybdate adds deionized water and is diluted to 20ml;
Utilize powdery TiO
2As catalyst carrier, take by weighing 3 parts, every part of 30g; Pour it in above-mentioned 3 kinds of solution dipping and stirring respectively, soak and after 1 hour unnecessary maceration extract is poured out, and with the TiO behind the single-steeping
2Powder is dried in 60-70 ℃ baking oven, it is poured into respectively in the residual dipping solution afterwards again, and fully stirs, and makes maceration extract all by TiO
2Carrier blots.
TiO behind the dipping
2Under 60-80 ℃ temperature, dried 4-6 hour again, rise to 300 ℃ of roasting 1h with 5 ℃/minute of heating rates in the transposition Muffle furnace; Rise to 400 ℃ of roasting 4h with 2 ℃/minute speed again presoma nitrate is fully decomposed, with 2 ℃/minute cooldown rate catalyst is cooled to normal temperature again.Be called catalyst A 1, B1 and C1 successively through the prepared catalyst of said method.A1 is the one pack system Mn catalyst, Mn/TiO
2The B1 catalyst is the Ru-Mn/TiO that mixes with Ru separately
2Composite catalyst; C1 is the Ru-Mo-Mn/TiO that molybdenum mixes
2Composite catalyst.Wherein, catalyst C1 is one of target catalyst proposed by the invention, and catalyst A 1 only is used for the contrast experiment with catalyst B 1.
The catalyst that present embodiment prepares, manganese, ruthenium and molybdenum element content are respectively 0.60%, 0.32% and 0.88%, and catalyst is worn into 40-60 purpose particle, and its particle diameter is 250-420 μ m, and specific area is 45-47m
2/ g.
The influence of doping molybdenum element: get above-mentioned A1, B1, C1 catalyst 0.5g respectively, it is inserted in the tubular fixed-bed reactor, feeding contains nonvalent mercury 100 μ g/m
3With oxidant HCl concentration be the simulated flue gas of 3ppm, the content of sulfur dioxide is 500ppm.Temperature is that 350 ℃, air speed are 50000h
-1Condition under, when catalyst reaches stably catalyzed stage, utilize the A1 catalyst to the catalytic oxidation efficient of nonvalent mercury be 93%, the B1 catalyst is 97% to the oxidation efficiency of nonvalent mercury, the C1 catalyst reaches 99% to the transformation efficiency of nonvalent mercury.This result shows, compares with the one pack system Mn catalyst, and with Ru, Mn is compound can improve activity of such catalysts to a certain extent, and after molybdenum was doped to the Ru-Mn composite catalyst, activity of such catalysts can significantly improve.
Temperature effect: other condition is constant, only the operating temperature of reactor is reduced to 150 ℃, and catalyst A 1, B1, C1 reduce to 57%, 66% and 92% respectively to the catalytic conversion efficiency of nonvalent mercury at this moment.Thus it is clear that, under lower temperature, have advantages of high catalytic activity equally according to the obtained catalyst C1 of the present invention.
The sulfur dioxide influence: when other condition is constant (operating temperature still is 150 ℃), when in simulated flue gas, adding the sulfur dioxide of 500ppm, then catalyst A 1, B1, C1 reduce to 48%, 61% and 94% respectively to the catalytic conversion efficiency of nonvalent mercury.Thus it is clear that, have extraordinary anti-sulfur dioxide ability according to the obtained catalyst C1 of the present invention.
Embodiment 2
Metallic elements such as 1wt%Ru, Mn, Cu are loaded to titanium dioxide get on, metal oxide precursor is respectively RuCl
3, Cu (NO
3) 3H
2O and Mn (NO
3)
2, and the SCR catalyst and (0.5wt%Ru+1.0wt%V)/TiO
2Catalyst is as reference.Experiment condition is: temperature is 150 ℃, and air speed is 7.96 * 10
5h
-1, the HCl concentration of adding is 3ppm.When adding SO
2When making an experiment, its concentration is 500ppm.Under the situation that does not add sulfur dioxide, catalyst 1%wt Ru/TiO
2, 1%wtMn/TiO
2, 1%wt Cu/TiO
2, (0.5wt%Ru+1.0wt%)/TiO
2And the nonvalent mercury catalytic oxidation efficient of SCR is respectively: 71%, 67%, 63%, 68% and 21%.When adding 500ppm SO
2Situation under, the nonvalent mercury catalytic oxidation efficient of each catalyst is followed successively by: 55%, 23%, 26%, 37% and 29%.
The catalyst that present embodiment prepares is worn into 40-60 purpose particle before test, each metal element content is 1%, and its particle diameter is 250-420 μ m, and specific area is 45-47m
2/ g.
Embodiment 3
Through in the process of dipping, adding different RuCl
3Amount make the Ru/TiO of five kinds of (0.05wt%, 0.2wt%, 0.50wt%, 1.00wt% and 2.00wt%) different Ru load capacity
2Catalyst is put into fixed bed reactors, is 350 ℃ in temperature, and air speed is 7.96 * 10
5h
-1, the HCl concentration of adding is 3ppm.The catalyst of investigating different Ru load capacity is at no SO
2And have 500ppm SO
2Different condition under, the catalytic oxidation efficient of nonvalent mercury, and with blank titanium dioxide as reference.When the load capacity of Ru is 0wt%, 0.05wt%, 0.20wt%, 0.50wt%, 1.00wt% and 2.00wt%; Under the situation that does not add sulfur dioxide, the catalytic oxidation efficient of nonvalent mercury is respectively: 5%, 58%, 86%, 94%, 99% and 99%.After adding 500ppm sulfur dioxide, the catalyst of each load capacity is respectively the catalytic oxidation efficient of nonvalent mercury: 3%, 42%, 72%, 82%, 88% and 94%.
The catalyst that present embodiment prepares is worn into 40-60 purpose particle before test, its particle diameter is 250-420 μ m, and specific area is 45-47m
2/ g.
Embodiment 4
1wt%Ru/TiO with preparation
2Catalyst and 1wt%Ru/ α-Al
2O
3Catalyst is 150 ℃ and 350 ℃ in temperature respectively, and air speed is 7.96 * 10
5h
-1, make an experiment under the condition of adding 1ppm, 2ppm, 3ppm, 5ppm and 10ppmHCl.When temperature is 150 ℃, 1wt%Ru/ α-Al
2O
3Nonvalent mercury catalytic oxidation efficient under 5 different HCl concentration is followed successively by from low to high: 4%, 7%, 8%, 10% and 15%; 1wt%Ru/TiO
2Nonvalent mercury catalytic oxidation efficient under 5 different HCl concentration is followed successively by from low to high: 35%, 60%, 71%, 80% and 88%.When temperature is 350 ℃, 1wt%Ru/ α-Al
2O
3Nonvalent mercury catalytic oxidation efficient under 5 different HCl concentration is followed successively by from low to high: 21%, 37%, 50%, 58% and 66%; 1wt%Ru/TiO
2Nonvalent mercury catalytic oxidation efficient under 4 different HCl concentration (1ppm, 2ppm, 3ppm and 5ppm) is followed successively by from low to high: 67%, 95%, 99% and 99%.The catalyst that present embodiment prepares is worn into 40-60 purpose particle before test, the titania support catalyst particle size is 250-420 μ m, and specific area is 45-47m
2/ g, alumina carrier catalyst particle size are 250-420 μ m, and specific area is 0.5-1.2m
2/ g.
Claims (4)
1. a preparation method who contains the ruthenium composite catalyst who is used for the nonvalent mercury catalytic oxidation is characterized in that, may further comprise the steps:
The first step, add that the ruthenium element presoma adds deionized water and stirs as predecessor after catalyst major constituent, helper component mixed and obtain dipping solution that the total content of predecessor is in the dipping solution: 0.01g/mL-0.50g/mL;
Second goes on foot, catalyst carrier is immersed stir dipping in the dipping solution and after Separation of Solid and Liquid, will carry out preliminary treatment through the catalyst carrier of dipping, after sintering makes catalyst;
Described catalyst major constituent is meant: a kind of or its combination in the nitrate of manganese, cobalt or copper, carbonate, oxalates or the acetate;
Described helper component is meant: a kind of or its combination in the nitrate of molybdenum or cerium, carbonate, oxalates or the acetate;
Wherein: the mass percentage content of manganese, cobalt or copper is 1%-10%, and the mass percentage content of ruthenium element is 0.05%-2%, and the mass percentage content of molybdenum or Ce elements is 0.5%-5%;
Described preliminary treatment is meant any one in the following dual mode:
A) under 40 ℃～100 ℃ temperature, dried 5-24 hour;
B) use the mould press forming,
Described sintering is meant: adopt Muffle furnace to be 1～30 ℃/minute with heating rate and rise to 300 ℃ of roasting 0.5-2h; Rise to 400 ℃ of roasting 0.5-4h with 1～30 ℃/minute speed again presoma is fully decomposed, with 1～2 ℃/minute cooldown rate catalyst is cooled to normal temperature at last.
2. the preparation method who contains the ruthenium composite catalyst who is used for the nonvalent mercury catalytic oxidation according to claim 1 is characterized in that, described ruthenium element presoma is meant: a kind of or its combination in nitric acid ruthenium, carbonic acid ruthenium, oxalic acid ruthenium or the ruthenium acetate.
3. the preparation method who contains the ruthenium composite catalyst who is used for the nonvalent mercury catalytic oxidation according to claim 1; It is characterized in that; Described catalyst carrier is the silicate of titanium dioxide, aluminium oxide, silica, crystalline state or in alumino-silicate, imvite or the active carbon one or more, and this catalyst carrier is spherical, graininess, tabular or cellular.
4. the said method of one of an employing such as claim 1-3 makes contains the ruthenium composite catalyst; It is characterized in that; Wherein: the mass percentage content of manganese, cobalt or copper is 1%-10%; The mass percentage content of ruthenium element is 0.05%-2%, and the mass percentage content of molybdenum or Ce elements is 0.5%-5%.
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