CN105478136A - Industrial organic waste gas catalytic degradation catalyst cooperated with low-temperature plasma, and preparation method and application of catalyst - Google Patents

Industrial organic waste gas catalytic degradation catalyst cooperated with low-temperature plasma, and preparation method and application of catalyst Download PDF

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CN105478136A
CN105478136A CN201510988931.1A CN201510988931A CN105478136A CN 105478136 A CN105478136 A CN 105478136A CN 201510988931 A CN201510988931 A CN 201510988931A CN 105478136 A CN105478136 A CN 105478136A
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catalyst
oxide
carrier
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earth oxide
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CN105478136B (en
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吴忠标
赵业红
刘越
王海强
翁小乐
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Zhejiang Tianlan Environmental Protection Technology Co Ltd
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Zhejiang University ZJU
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Abstract

The invention discloses an industrial organic waste gas catalytic degradation catalyst cooperated with low-temperature plasma, and a preparation method and application of the catalyst. The catalyst comprises a carrier, a main active ingredient and a catalyst promotion ingredient, wherein the carrier is SiC; the main active ingredient is a mixture of at least one kind of noble metal and at least one of transition metal oxide or at least one kind of noble metal or at least one kind of transition metal oxide; the catalyst promotion ingredient is a mixture of at least one kind of rare-earth oxide and alkaline earth oxide or at least one kind of rare-earth oxide or at least one kind of alkaline earth oxide; the main active ingredient accounts for 0.1 to 5 percent of the total mass of the catalyst; the catalyst promotion ingredient accounts for 0.1 to 5 percent of the total mass of the catalyst. The catalyst provided by the invention has the advantages that the preparation is simple; the price is low; the service life is long; the performance is good; the catalyst can be used for high-efficiency removal of industrial VOCs waste gas at room temperature after being combined with plasma; in addition, the discharge of low byproducts is guaranteed.

Description

A kind of Catalysts and its preparation method of cooperating with low-temperature plasma-catalytic degraded industrial organic exhaust gas and application
Technical field
The invention belongs to technical field of waste gas treatment, be specifically related to Catalysts and its preparation method and the application of a kind of cooperating with low-temperature plasma-catalytic degraded industrial organic exhaust gas.
Background technology
In recent years, there is extensive severe haze weather in the multiple city of China, its essence is that atmospheric aerosol concentration is too high, and volatile organic contaminant (VOCs) is important predecessor.In addition, VOCs also can cause the atmospheric issues such as photochemical fog, depletion of the ozone layer, global warming, and to the toxic effect of people and animals.And industrial source, if organic chemical industry, petrochemical industry, Coal Chemical Industry, pharmacy, printing, spraying etc. are main emission sources, there is the generation of millions of tons every year.
At present, the method processing industrial volatile organic matter mainly contains absorption, absorption, catalytic combustion, photocatalysis etc., but these conventional arts are generally applicable to process high-concentration waste gas, and has that energy consumption is high, operating cost is high and the problem of secondary pollution.Lower temperature plasma technology is a kind of new technology, is considered to the effective ways processing VOCs, has the advantages such as efficiency is high, energy consumption is low, structure is simple, cost is low, applicable process large-wind-volume low-concentration waste gas.But single lower temperature plasma technology limited efficiency.So plasma is combined with catalyst by more researcher, its synergy can realize the deep oxidation of VOCs, and the small organic molecule, the O that produce in decomposition reaction process 3, NO x, the accessory substance such as aerosol.
Low temperature plasma is coupled with catalyst one-part form and catalyst more can be combined closely with discharging, and the ferroelectric media material wherein can strengthening discharging has better performance, and as Mn, Co, Ag etc., the catalyst that specific area is large in addition, particularly carrier is as Al 2o 3, TiO 2, molecular sieve etc. increases time of staying of VOCs, improves the dispersiveness of catalyst.But often incomplete to the degraded of VOCs, have small organic molecule and remain, accessory substance O in addition 3, NO xdo not obtain efficiency utilization and decomposition, in tail gas, content is still very large.
China Patent Publication No. is that CN1451477 discloses " the Foamed Nickel Catalysts and its preparation method of purifying industrial waste gases and application ", its carrier is Foamed Nickel and component percentages is 40 ~ 80, active component contains metal oxide and component percentages is 15 ~ 60, catalyst performance is excellent, the purified treatment to industrial waste gas can be realized after combining with plasma at normal temperatures and pressures, the resistance of reactor can not be caused again to increase.Just whether unknown the solution of accessory substance problem is.
In sum, lower temperature plasma technology coupling one-part form situ catalytic is effective, but the depth degradation problem of accessory substance problem and VOCs has to be solved.
Summary of the invention
The invention provides Catalysts and its preparation method and the application of a kind of cooperating with low-temperature plasma-catalytic degraded industrial waste gas, this kind catalyst preparing is simple, cheap, the life-span is long, performance is good, be combined with plasma and high efficiency can remove industrial VOCs waste gas under normal temperature, and ensured the discharge of low accessory substance.
A catalyst for cooperating with low-temperature plasma-catalytic degraded industrial waste gas, comprises carrier, main active component and co catalysis composition; Described carrier is SiC; Described main active component is at least one in the mixture of at least one at least one and transition metal oxide in noble metal, noble metal or at least one in transition metal oxide; Co-catalyst component is at least one in the mixture of at least one at least one and alkaline earth oxide in rare-earth oxide, rare-earth oxide or at least one in alkaline earth oxide; Main active component accounts for 0.1 ~ 5% of catalyst gross mass, and co-catalyst component accounts for 0.1 ~ 5% of catalyst gross mass.
Manganese oxide catalyst is at O 3under atmosphere, effectively can promote the degraded of VOCs, serve synchronous degradation O 3with the effect of VOCs, the O of metal oxide degraded simultaneously 3time, except manganese oxide, the oxide of iron, cobalt, nickel also has good degraded O 3effect; And for the rare-earth oxide (as cerium oxide and lanthana) of rich surface containing electronics, it is easily at absorption O 3process in, provide an electronics to O 3form O 3 -group, this group can promote the degraded of VOCs greatly.The present invention utilizes the characteristic of the metal oxides such as manganese, iron, cobalt, nickel, cerium, lanthanum, adopts suitable carrier and load one or more oxides above-mentioned obtain catalyst, under lower temperature conditions, can reach synchronous degradation O 3with the effect of VOCs.
The present invention adopts carborundum as carrier, and SiC has high specific resistance, and its value is greater than 1 × 10 7Ω cm, this makes the valence electron of material be not easy migration, not easy conductive in the high electric field of region of discharge; SiC is the semiconductor between metallic conductor and insulator in addition, there is special nature, easy generation electron hole also interacts with active material, it has nucleophobic acid centre, the organic compound having pi-electron can be attracted, particularly when with metal-doped after can be with and can rank all change, activation energy may be caused to change; Its dielectric constant can suddenly change under certain electric-field intensity in addition, strengthens electric-field intensity, also just adds the clearance to pollutant.
The present invention adopts suitable catalyst activity component and carrier not only can decompose O 3and NO xsolve accessory substance problem, the further degradation of organic substances of synergy can also be utilized.The present invention is by MnO x, CoO xload on SiC carrier Deng composite reactive component, prepare ideal type catalyst that is efficient, no coupling product.
Further preferably, when described main active component is noble metal, it accounts for 0.1 ~ 1wt% of total catalyst weight; When main active component is transition metal oxide, it accounts for 1 ~ 5wt% of total catalyst weight; When main active component is the mixture of noble metal and transition metal oxide, noble metal accounts for 0.2 ~ 0.4wt% of total catalyst weight, and transition metal oxide accounts for 2.5 ~ 3.5wt% of total catalyst weight; Co-catalyst accounts for 1 ~ 4wt% of total catalyst weight.
Still more preferably, when described main active component is noble metal, it accounts for 0.3 ~ 0.6wt% of total catalyst weight; When main active component is transiting metal oxidation, it accounts for 4 ~ 5wt% of total catalyst weight; Co-catalyst accounts for 1 ~ 4wt% of total catalyst weight.
About main active component, most preferably, when described main active component is the mixture of noble metal and transition metal oxide, noble metal accounts for the 0.3wt% of total catalyst weight, and transition metal oxide accounts for the 2.7wt% of total catalyst weight.
Preferably, described carrier S iC is foam-like or cellular.
Further preferably, the thickness 5 ~ 20mm of foam-like SiC carrier, aperture 15 ~ 25ppi, further, aperture is 20ppi.
Preferably, described noble metal is Ag, Pt or Pd.
Preferably, described transition metal oxide is the oxide of Mn, Co, Ni, Ti, Cr, Cu or Fe.
Preferably, described rare-earth oxide is the oxide of La or Ce.It effectively can adsorb O 3and electronics is provided, make O 3 -group is degraded VOCs further, decomposes O simultaneously 3.
Preferably, described alkaline earth oxide is the oxide of Ca or Ba.
Further, described main active component and co-catalyst component are selected from following combination:
(1) described main active component is the mixture of Mn oxide and cobalt/cobalt oxide, and co-catalyst component is cerium oxide, and Mn oxide accounts for 1% of total catalyst weight, and cobalt/cobalt oxide accounts for 3% of total catalyst weight, and cerium oxide accounts for 1% of total catalyst weight.The catalyst adopting this combination to prepare, for processing organic exhaust gas in plasma-catalytic reaction, can reach 98%, O to the clearance of toluene 3residual 4ppm, NO xresidual 0ppm.
(2) described main active component is the mixture of nickel oxide and cobalt/cobalt oxide, and co-catalyst component is lanthana, and nickel oxide accounts for 2% of total catalyst weight, and cobalt/cobalt oxide accounts for 2% of total catalyst weight, and lanthana accounts for 1% of total catalyst weight.The catalyst adopting this combination to prepare is for processing organic exhaust gas in plasma-catalytic reaction, and the removal efficiency of toluene, dimethylbenzene is respectively 99%, 97%, O 3residual 12ppm, NO xresidual 0ppm.
(3) described main active component is the mixture of Cu oxide and cobalt/cobalt oxide, and co-catalyst component is calcium oxide, and Cu oxide accounts for 1% of total catalyst weight, and cobalt/cobalt oxide accounts for 3% of total catalyst weight, and calcium oxide accounts for 1% of total catalyst weight.The catalyst adopting this combination to prepare is for processing organic exhaust gas in plasma-catalytic reaction, and the removal efficiency of ethyl acetate, acetone is respectively 99%, 96%, O 3residual 5ppm, NO xresidual 0ppm.
(4) described main active component is the mixture of Mn oxide and Cu oxide, and co-catalyst component is barium monoxide, and Mn oxide accounts for 2% of total catalyst weight, and Cu oxide accounts for 3% of total catalyst weight, and barium monoxide accounts for 1% of total catalyst weight.The catalyst adopting this combination to prepare is for processing organic exhaust gas in plasma-catalytic reaction, and the removal efficiency of toluene, ethyl acetate is 96%, 99%, O 3residual 3ppm, NO xresidual 0ppm.
(5) described main active component is silver, and co-catalyst component is cerium oxide, and silver accounts for 0.6% of total catalyst weight, and cerium oxide accounts for 3.4% of total catalyst weight.The catalyst adopting this combination to prepare is for processing organic exhaust gas in plasma-catalytic reaction, and the degradation rate of toluene is 98%, O 3residual 10ppm, NO xresidual 0ppm.
(6) described main active component is platinum, and co-catalyst component is cerium oxide, and platinum accounts for 0.3% of total catalyst weight, and cerium oxide accounts for 3.7% of total catalyst weight.The catalyst adopting this combination to prepare is for processing organic exhaust gas in plasma-catalytic reaction, and the removal efficiency of toluene, ethyl acetate is 96%, 99%, O 3residual 3ppm, NO xresidual 0ppm.
(7) described main active component is palladium and Mn oxide, and co-catalyst component is lanthana, and palladium accounts for 0.3 of total catalyst weight, and Mn oxide accounts for 2.7% of total catalyst weight, and lanthana accounts for 1% of total catalyst weight.The catalyst adopting this combination to prepare is for processing organic exhaust gas in plasma-catalytic reaction, and the removal efficiency of toluene, methyl alcohol is 98%, 99%, O 3residual 2ppm, NO xresidual 0ppm.
The present invention also provides a kind of preparation method of described catalyst, comprises the steps:
(1) SiC carrier is steeped and washing post-drying through peracid bubble, alkali successively; The presoma of the presoma and co catalysis composition that take main active component by proportioning is configured to the aqueous solution;
(2) by dry after carrier impregnation in the aqueous solution of presoma, ultrasonic reaction 0.5 ~ 1.5h;
(3) ultrasonic end post-drying, and then roasting 3.5 ~ 4.5h at 450 ~ 550 DEG C, obtain described catalyst.
Further, dry at 100 DEG C in step (1); The volume of precursor water solution is slightly larger than the volume of carrier in step (2), and the ultrasonic reaction time is preferably 1h; About 12h is dried at 100 DEG C to drying, the preferred 4h of roasting time in step (3).
The present invention also provides a kind of described catalyst in the application of cooperating with low-temperature plasma-catalytic degraded industrial waste gas, is positioned over described in the region of discharge of plasma catalytic reactor.
Shaping catalyst is positioned in the region of discharge of reactor; And select foam or honeycomb SiC loaded catalyst.When corona discharge occurs, catalyst original position produces active particle, and organic matter is decomposed through corona region and catalyst.
Compared with prior art, the present invention has following beneficial effect:
1. preferred take SiC as the loaded catalyst of carrier, and carrier and active component are effectively collaborative, strengthen corona discharge, and the energy density of plasma is increased, and improve, also improve energy efficiency to the degradation rate of pollutant;
2. preferred SiC load composite type metallic oxide, as MnO xand CoO xcompound, under normal temperature, both can improve the degradation rate of pollutant, also can remove O 3, NO xdeng accessory substance, solve the problem of one-part form by-product object height;
3. co-catalyst, utilizes the O of rare earth metal 3trapping ability and alkaline-earth metal strengthen O as electronic auxiliary 3synergistic degradation ability and improve catalyst main active component dispersiveness on a catalyst;
4. the catalyst of foam or alveolate texture solves the large problem of reactor resistance, and raw material of the present invention is cheap, and preparation is simple, is easy to industrial applications.
Detailed description of the invention
The method of application present embodiment process organic exhaust gas is: under the effect of air draught, bubbling bottle, blending tank, with organic matter simulation organic exhaust gas such as toluene, dimethylbenzene, ethyl acetate, concentration is 10 ~ 200ppm, total flow 2L/min; Foam type catalyst is placed between the positive and negative electrode of corona discharge, connects plasma high voltage source, between electrode pair, corona discharge occurs, certain anti-electric-corona discharge also occurs catalyst, and the organic matters such as toluene pass through between electrode pair, by high energy electron, O 3, the pretreatment of OH isoreactivity particle becomes Small molecular organic pollution, then through Catalytic Layer, become CO through synergy by advanced treating 2and H 2o; And Catalytic Layer can to O 3there is decomposition, decompose the active oxygen decomposable asymmetric choice net organic matter produced; Catalyst can trap aerosol and degrade in position in addition; Through the content of gas-chromatography test residual organic matter.
Embodiment 1
Catalyst preparing: catalyst adopts the preparation of dipping calcination method, with 50% manganese nitrate aqueous solution, cobalt nitrate, cerous nitrate, foam silicon carbon for raw material, according to the proportional arrangement solution that Mn oxide, cobalt oxide and cerium oxide load capacity are 1%, 3%, 1%, after being dried by excessive impregnated carbon SiClx, at 450 DEG C of temperature, be placed in Muffle furnace and calcine 4h, namely obtain catalyst.
Application process: catalyst is thickness 20mm, the 1%MnO of aperture 20ppi foam silicon carbon load x3%CoO x1%CeO x/ SiC catalyst.Initial vapor concentration is: [toluene]=100ppm, take air as carrier gas, and flow is 2L/min.Discharge voltage is 18KV positive high voltage, and reaction temperature is room temperature, and the removal efficiency of toluene is 98%, O 3residual 4ppm, NO xresidual 0ppm.
Embodiment 2
Catalyst preparing: catalyst adopts the preparation of dipping calcination method, with nickel nitrate, cobalt nitrate, lanthanum nitrate, foam silicon carbon for raw material, according to the proportional arrangement solution that nickel oxide, cobalt oxide and lanthana load capacity are 2%, 2% and 1%, after being dried by excessive impregnated carbon SiClx, at 450 DEG C of temperature, be placed in Muffle furnace and calcine 4h, namely obtain catalyst.
Application process: catalyst is thickness 20mm, the 2%NiO of aperture 20ppi foam silicon carbon load x2%CoO x1%LaO x/ SiC catalyst.Initial mixing gas concentration is: [toluene]=50ppm, [dimethylbenzene]=50ppm, take air as carrier gas, and flow is 2L/min.Discharge voltage is 18KV positive high voltage, and reaction temperature is room temperature, and the removal efficiency of toluene, dimethylbenzene is respectively 99%, 97%, O 3residual 12ppm, NO xresidual 0ppm.
Embodiment 3
Catalyst preparing: catalyst adopts the preparation of dipping calcination method, with copper nitrate, cobalt nitrate, calcium nitrate, foam silicon carbon for raw material, according to the proportional arrangement solution that cupric oxide, cobalt oxide and calcium oxide load capacity are 1%, 3% and 1%, after being dried by excessive impregnated carbon SiClx, at 450 DEG C of temperature, be placed in Muffle furnace and calcine 4h, namely obtain catalyst.
Application process: catalyst is thickness 20mm, the 1%CuO of aperture 20ppi foam silicon carbon load x3%CoO x1%CaO x/ SiC catalyst.Initial mixing gas concentration is: [ethyl acetate]=50ppm, [acetone]=50ppm, take air as carrier gas, and flow is 2L/min.Discharge voltage is 18KV positive high voltage, and reaction temperature is room temperature, and the removal efficiency of ethyl acetate, acetone is respectively 99%, 96%, O 3residual 5ppm, NO xresidual 0ppm.
Embodiment 4
Catalyst preparing: catalyst adopts the preparation of dipping calcination method, with 50% manganese nitrate aqueous solution, copper nitrate, barium nitrate, foam silicon carbon for raw material, according to the proportional arrangement solution that Mn oxide, cupric oxide and barium monoxide load capacity are 2%, 3% and 1%, after being dried by excessive impregnated carbon SiClx, at 600 DEG C of temperature, be placed in Muffle furnace and calcine 4h, namely obtain catalyst.
Application process: catalyst is thickness 20mm, the 2%MnO of aperture 20ppi foam silicon carbon load x3%CuOx1%BaO x/ SiC catalyst.Initial mixing gas concentration is: [toluene]=50ppm, [ethyl acetate]=50ppm, take air as carrier gas, and flow is 2L/min.Discharge voltage is 18KV positive high voltage, and reaction temperature is room temperature, and the removal efficiency of toluene, ethyl acetate is 96%, 99%, O 3residual 3ppm, NO xresidual 0ppm.
Embodiment 5
Catalyst preparing: catalyst adopts the preparation of dipping calcination method, with silver nitrate, cerous nitrate, foam silicon carbon for raw material, according to the proportional arrangement solution that silver and cerium oxide load capacity are 0.6% and 3.4%, after being dried by excessive impregnated carbon SiClx, at 450 DEG C of temperature, be placed in Muffle furnace and calcine 4h, namely obtain catalyst.
Application process: catalyst is thickness 20mm, the 0.6%Ag3.4%CeO of aperture 20ppi foam silicon carbon load x/ SiC catalyst.Initial vapor concentration is: [toluene]=100ppm, take air as carrier gas, and flow is 2L/min.Discharge voltage is 18KV positive high voltage, and reaction temperature is room temperature, and the degradation rate of toluene is 98%, O 3residual 10ppm, NO xresidual 0ppm.
Embodiment 6
Catalyst preparing: catalyst adopts the preparation of dipping calcination method, with chloroplatinic acid, cerous nitrate, foam silicon carbon for raw material, according to the proportional arrangement solution that platinum and cerium oxide load capacity are 0.3% and 3.7%, after being dried by excessive impregnated carbon SiClx, at 500 DEG C of temperature, be placed in Muffle furnace and calcine 4h, namely obtain catalyst.
Application process: catalyst is thickness 20mm, the 0.3%Pt3.7%CeO of aperture 20ppi foam silicon carbon load x/ SiC catalyst.Initial vapor concentration is: [ethyl acetate]=100ppm, take air as carrier gas, and flow is 2L/min.Discharge voltage is 18KV positive high voltage, and reaction temperature is room temperature, and the removal efficiency of ethyl acetate is 99%, O 3residual 6ppm, NO xresidual 0ppm.
Embodiment 7
Catalyst preparing: catalyst adopts the preparation of dipping calcination method, with palladium bichloride, 50% manganese nitrate aqueous solution, lanthanum nitrate foam silicon carbon for raw material, according to the proportional arrangement solution that palladium, Mn oxide and lanthana load capacity are 0.3%, 2.7% and 1%, after being dried by excessive impregnated carbon SiClx, at 500 DEG C of temperature, be placed in Muffle furnace and calcine 4h, namely obtain catalyst.
Application process: catalyst is thickness 20mm, the 0.3%Pd2.7%MnO of aperture 20ppi foam silicon carbon load x1%LaO x/ SiC catalyst.Initial mixing gas concentration is: [toluene]=50ppm, [methyl alcohol]=50ppm, take air as carrier gas, and flow is 2L/min.Discharge voltage is 18KV positive high voltage, and reaction temperature is room temperature, and the removal efficiency of toluene, methyl alcohol is 98%, 99%, O 3residual 2ppm, NO xresidual 0ppm.

Claims (9)

1. a catalyst for cooperating with low-temperature plasma-catalytic degraded industrial waste gas, comprises carrier, main active component and co catalysis composition; It is characterized in that, described carrier is SiC; Described main active component is at least one in the mixture of at least one at least one and transition metal oxide in noble metal, noble metal or at least one in transition metal oxide; Co-catalyst component is at least one in the mixture of at least one at least one and alkaline earth oxide in rare-earth oxide, rare-earth oxide or at least one in alkaline earth oxide; Main active component accounts for 0.1 ~ 5% of catalyst gross mass, and co-catalyst component accounts for 0.1 ~ 5% of catalyst gross mass.
2. catalyst according to claim 1, it is characterized in that, described carrier S iC is foam-like or cellular.
3. catalyst according to claim 2, is characterized in that, the thickness 5 ~ 20mm of foam-like SiC carrier, aperture 15 ~ 25ppi.
4. catalyst according to claim 1, it is characterized in that, described noble metal is Ag, Pt or Pd.
5. catalyst according to claim 1, it is characterized in that, described transition metal oxide is the oxide of Mn, Co, Ni, Ti, Cr, Cu or Fe.
6. catalyst according to claim 1, it is characterized in that, described rare-earth oxide is the oxide of La or Ce.
7. catalyst according to claim 1, it is characterized in that, described alkaline earth oxide is the oxide of Ca or Ba.
8. a preparation method for catalyst as claimed in claim 1, is characterized in that, comprise the steps:
(1) SiC carrier is steeped and washing post-drying through peracid bubble, alkali successively; The presoma of the presoma and co catalysis composition that take main active component by proportioning is configured to the aqueous solution;
(2) by dry after carrier impregnation in the aqueous solution of presoma, ultrasonic reaction 0.5 ~ 1.5h;
(3) ultrasonic end post-drying, then roasting 3.5 ~ 4.5h at 450 ~ 550 DEG C, obtains described catalyst.
9. catalyst, in an application for cooperating with low-temperature plasma-catalytic degraded industrial waste gas, is characterized in that, is positioned in the region of discharge of plasma catalytic reactor by described catalyst as claimed in claim 1.
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