CN101733127B - Catalyst for treating organic waste gas and preparation method thereof - Google Patents
Catalyst for treating organic waste gas and preparation method thereof Download PDFInfo
- Publication number
- CN101733127B CN101733127B CN2009102346910A CN200910234691A CN101733127B CN 101733127 B CN101733127 B CN 101733127B CN 2009102346910 A CN2009102346910 A CN 2009102346910A CN 200910234691 A CN200910234691 A CN 200910234691A CN 101733127 B CN101733127 B CN 101733127B
- Authority
- CN
- China
- Prior art keywords
- oxide
- catalyst
- carrier
- preparation
- roasting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention relates to a catalyst for treating organic waste gas and a preparation method thereof, belonging to the control technology of atmospheric pollution and the field of environment protection materials. In the catalyst, copper oxide, manganese oxide and titanium oxide are used as active ingredients, and a catalyst carrier is self-made; based on the mass of the carrier, the active ingredients are mixed in the molar ratio of copper oxide, manganese oxide to titanium oxide being 1-4: 1-4: 0.5-1; and the mass percentage of the capacity of the active ingredient is 1-20%. The self-made carrier is prepared by using silicon oxide, aluminum oxide, magnesium oxide and ferric oxide as components which are baked at high temperature, wherein the mass percentage of the material is 28-55% of silicon oxide, 20-40% of aluminum oxide, 10-30% of magnesium oxide and 0.5-2% of ferric oxide; and the carrier is modified or modified through an aluminum oxide coating by using 5-20% acid in mass percentage. The catalyst can completely catalyze toluene at 250 DEG C, and the complete catalysis temperature is reduced by about 20 DEG C compared with the same kind of catalysts.
Description
Technical field
The present invention relates to a kind of processing organic exhaust gas Catalysts and its preparation method, belong to air contaminant treatment technology and environment protection catalytic field of materials.
Background technology
Organic exhaust gas is one of main atmosphere pollution, can get into human body through respiratory tract and skin, causes temporary and permanent pathology to system such as people's breathing, blood, liver and organ.Contain a large amount of pernicious gases like the PTA oxidized tail gas, as: benzene,toluene,xylene, methyl acetate, CO etc., its index causes serious harm all above discharging standards to environment.For preventing to pollute, except that reducing oil loss, reducing consumption of organic solvent with the generation and discharging that reduce organic exhaust gas, exhaust gas purification is present practicable governance way.Processing to organic exhaust gas both at home and abroad generally is divided into recovery technology and destruction technology.Recovery technology mainly contains absorption, absorption, condensation and film separation etc.; Disclose a kind of organic exhaust gas absorption, desorption, purifier like Chinese patent CN101209390A, improved operating efficiency, can directly apply in the commercial production of handling organic exhaust gas; But technology is comparatively complicated, and investment is big; The destruction technology mainly contains direct firing method, catalytic combustion, photocatalytic degradation, biodegradation, plasma technique etc.Catalytic combustion does not receive the restriction of hydrocarbon concentration, can not cause secondary pollution and equipment simpler because of it has the temperature of initial combustion, the burning that reduce organic exhaust gas, small investment, characteristics such as instant effect and receiving much concern.The catalyst for catalytic combustion of China's application at present all needs import; There is Engelhard in main supplier; Johnson Matthey; Allied Signal and UOP four companies, and be that active component, ceramic honey comb are the catalyst of carrier with noble metals such as Pt, Pd all, CN101204654A discloses a kind of noble metal catalyst of low-temperature catalytic oxidation benzene series thing; This type of catalyst has very high oxidation activity and is prone to advantage such as recovery, but exists resource scarcity, costs an arm and a leg and shortcoming such as mithridatism difference.Research and develop efficient cheapness, eco-friendly transition metal oxide and composite oxide catalysts and substitute research focus and the application trend that noble metal catalyst has become current domestic and international catalyst for catalytic combustion.CN101367045A relates to a kind of Cu-Mn complex oxide catalyst of catalytic combustion ethene; The catalytic combustion temperature can be reduced to 205 ℃ fully; But this kind catalyst is carried on the self-control carrier with the copper/manganese/titanium of patent of the present invention and compares, the mantoquita of 100% content and manganese salt, and cost is higher; Industrial organic exhaust gas is handled in unsuitable scale; And this patent can reach and above-mentioned same catalytic effect under the state of the copper/manganese/titanium active component of load 10%, and is with low cost.It is active component with copper/manganese/silver-colored composite oxides that CN101474566A discloses a kind of, with cordierite surface-coated γ-Al
2O
3Be carrier, handle a kind of organic exhaust gas, in the complete catalysis of 275 ℃ of realizations toluene; But it is 5～15% silver oxides that this kind catalyst adds mass fraction; Cost is comparatively expensive, and this test employed copper/manganese/titanium catalyst can be in the complete catalysis of 250 ℃ of realizations to toluene, initiation temperature is lower; Price is more cheap, and application is advanced wide.
Summary of the invention
The purpose of this invention is to provide a kind of processing organic exhaust gas Catalysts and its preparation method; This catalyst efficient is high, can compare with similar catalyst in the complete catalysis of 250 ℃ of realizations to toluene; The temperature of catalytic combustion toluene reduces about 20 ℃ fully; And be active constituent loading on the self-control carrier with copper/manganese/titanium, the mass fraction of active component is 1～20%, cost is more cheap.Another object of the present invention provides above-mentioned Preparation of catalysts method, adopts this catalyst of immersion process for preparing, and preparation technology is more simple, is fit to handle industrial organic exhaust gas more.
A kind of processing organic exhaust gas of the present invention Catalysts and its preparation method is to take following technical scheme to realize:
A kind of processing organic exhaust gas catalyst is characterized in that said catalyst is an active component with cupric oxide, manganese oxide and titanium oxide, and the self-control catalyst carrier is a benchmark with the quality of carrier, and the quality percentage composition of activity component load quantity is 1～20%.
Said active component is to be 1～4: 1～4 with cupric oxide, manganese oxide and titanium oxide mol ratio: 0.5～1 allocates, and forming with cupric oxide, manganese oxide, titanium oxide is active component.
Said self-control carrier is to be constituent with silica, aluminium oxide, magnesia and iron oxide; Wherein the raw materials quality per distribution ratio is silica 28～55%, aluminium oxide 20～40%, magnesia 10～30%, iron oxide 0.5～2%; Mix by above-mentioned quality per distribution ratio, form through high-temperature roasting, using mass percent again is that 5～20% acid treatment is to support modification; The carrier crystalline form is complete, and stability better.
Said mass percent is that oxalic acid or acetate are selected in 5～20% acid for use.
The present invention also provides above-mentioned Preparation of catalysts method, and its concrete steps are following:
(1) preparation and the processing of self-control carrier
Silica, aluminium oxide, magnesia and iron oxide are mixed by the quality per distribution ratio, and wherein the raw materials quality per distribution ratio is silica 28～55%, aluminium oxide 20～40%, magnesia 10～30%, iron oxide 0.5～2%, and raw material mixes after 1300～1400 ℃ of high-temperature roastings make catalyst carrier; Insulation 4～6h, and to use mass percent be that 5～20% oxalic acid or acetate boil, boiling the processing time is 2～3h; Again through 80～120 ℃ of temperature; Time is the drying of 1～2h, carries out roasting after the drying, and roasting is 400～600 ℃ of temperature; Time is 4～6h, obtains modified support through roasting;
Above-mentioned modified support is carried out the aluminum oxide coating layer modification; Through 80～120 ℃, the drying of 1～2h and 500～600 ℃, 2～4h roasting; Process the new modified carrier of aluminum oxide coating layer modification; Being alumina modified carrier, is benchmark with the modified support, and activated alumina load capacity quality percentage composition is 1～10% in the alumina modified carrier.
(2) preparation of activity component impregnation liquid
Cu salt and Mn salting liquid are dissolved in the titanium glue, and described Cu salt and Mn salt are oxalates, carbonate or phosphate etc., and preparation Cu salt, Mn salt and titanium oxide mol ratio are 1～4: 1～4: 0.5～1 titanium glue.
(3) load of active component
With modified support in the step (1) or alumina modified carrier impregnation in the solution of step (2) preparation; Dip time is 4～8h; Through the drying naturally and in drying box 80～120 ℃ of 12～24h, the forced air drying of 1～4h is again through 300～650 ℃ then; The roasting of 2～5h; Perhaps repeated impregnations, drying and roasting are with the catalyst of preparation certain negative carrying capacity, and the quality percentage composition that makes the load capacity of cupric oxide, manganese oxide and titanium oxide is 1～20%, promptly processes a kind of processing organic exhaust gas catalyst.
Beneficial effect of the present invention:
The prepared catalyst of the present invention has carried out performance evaluation to the toluene catalytic oxidation reaction of low concentration, and the toluene of turnover reactor is by gas chromatographic analysis.This catalyst is under the situation of 1000～10000ppm in toluene concentration, is 1.0 * 10 in the gas volume air speed
4～1.4 * 10
4h
-1The time, 150～500 ℃ of reaction temperatures, can be CO with toluene catalytic oxidation
2And H
2O.
The present invention is with metal oxide CuO, the MnO of different mol ratio
2And TiO
2The cupric oxide, manganese oxide and the titanium oxide that form are active component, and self-control catalyst carrier (silica, aluminium oxide, magnesia and iron oxide are main composition) adopts such catalyst of immersion process for preparing, reach high-strength combination the between active component and the carrier.The present invention compares with existing transition-metal catalyst, can be that the toluene of 6000ppm is being lower than under 250 ℃ with content, realizes complete catalysis, has reduced about 20 ℃ with intra-class correlation.Catalyst all is greatly improved and the processing of suitable more industrial organic exhaust gas through the 48h stability test simultaneously.
Compared with present technology, the present invention has following characteristics:
1. the catalyst that makes of the present invention does not adopt noble metal, adopts such catalyst of immersion process for preparing, and preparation technology is more simple, and is easy to operate, with low cost, is convenient to enlarged reproduction.
2. low, the efficient (T of catalyst initial temperature that makes of the present invention
100%=250 ℃), active temperature windows wideer (150 ℃～1000 ℃).
3. the catalyst that makes of the present invention has good stability through the 48h stability test; In course of reaction, produce under a large amount of steam situation simultaneously, catalyst still keeps very high catalytic activity, and anti-steam ability is strong; And this catalyst environmental protection is nontoxic;
Description of drawings
Below will combine accompanying drawing that the present invention is made further specifies:
Fig. 1 is the activity figure of the prepared catalyst toluene of embodiment 2, and this catalyst is 100% at 250 ℃ of catalytic efficiencies to toluene, and in 250 ℃～1000 ℃ scopes, it is good that catalyst stability keeps.
Fig. 2 is the activity figure of the prepared catalyst toluene of embodiment 4, and this catalyst is 96% at 250 ℃ of catalytic efficiencies to toluene, but after reaction temperature was higher than 300 ℃, catalytic efficiency descended.
Fig. 3 is the activity figure of the prepared catalyst toluene of embodiment 8, and this catalyst is 96% at 250 ℃ of catalytic efficiencies to toluene.This catalyst is simultaneously at 300 ℃ of active testings that carry out 48h, and catalyst keeps the conversion ratio to toluene 96%, and (200 ℃～1000 ℃) keep very high activity in the temperature range of broad.
The specific embodiment
Below further specify the present invention through instance:
(1) preparation and the modification of self-control carrier
Get 28g silica, 40g aluminium oxide, 30g magnesia and 2g iron oxide and mix, mixture is through 1300 ℃ of roastings, and temperature retention time is controlled at 6h; The self-control carrier boils on electric furnace and is incubated 2h through the modification of 5wt% oxalic acid solution, 80 ℃ of baking temperatures, and be 2h drying time; 400 ℃ of sintering temperatures, roasting time are 6h, obtain modified support through roasting;
(2) preparation of activity component impregnation liquid
Get 64.7g solid CuC
2O
4.1/2H
2O, 71.6g solid MnC
2O
4.2H
2O and 181.7g distilled water are mixed with Cu
2+And Mn
2+Mol ratio is 1: 1 a mixed solution, mixes with the titanium glue that contains 12.0g titanium dioxide again, makes cupric oxide, manganese oxide and titanium oxide mol ratio and be 1: 1: 0.5 maceration extract.
(3) load of active component
Get 4h in the solution that homemade 100g support samples in the step (1) is immersed in step (2) preparation; Soaked carrier is dried the 80 ℃ of dryings of common bellows with 4h naturally through 12h's; Roasting through 300 ℃ of insulations of Muffle furnace 5h promptly makes the catalyst that active component is cupric oxide manganese oxide and titanium oxide again, generates a spot of Cu-Mn complex oxide simultaneously, and active component is a benchmark with the quality of carrier; Its quality percentage composition is 12.9%, promptly processes a kind of processing organic exhaust gas catalyst.
(4) catalyst performance evaluation
By the evaluation method of implementing 1, this catalyst is 96% at 250 ℃ of catalytic efficiencies to toluene.
Embodiment 2
(1) preparation and the modification of self-control carrier
Get 50g silica, 35g aluminium oxide, 14g magnesia and 1g iron oxide and mix, mixture is through 1350 ℃ of roastings, and temperature retention time is controlled at 5h; The self-control carrier is through the modification of 10wt% oxalic acid solution, on electric furnace, boils and is incubated 2h; 100 ℃ of baking temperatures, be 1h drying time; 500 ℃ of sintering temperatures, roasting time are 5h, obtain modified support through roasting.
(2) preparation of activity component impregnation liquid
Get 40.0g solid CuC
2O
4.1/2H
2O, 89.5g solid MnC
2O
4.2H
2O and 192.5g distilled water are mixed with Cu
2+And Mn
2+Mol ratio is 1: 2 a mixed solution, mixes with the titanium glue that contains 11.3g titanium dioxide again, makes cupric oxide, manganese oxide and titanium oxide mol ratio and be 1: 2: 0.75 maceration extract.
(3) load of active component
Get 6h in the solution that homemade 100g support samples in the step (1) is immersed in step (2) preparation; Soaked carrier is dried the 100 ℃ of dryings of common bellows with 2h naturally through 24h's; Promptly make the catalyst of active component cupric oxide manganese oxide and titanium oxide again through the roasting of 500 ℃ of insulations of Muffle furnace 4h, generate a large amount of Cu-Mn complex oxides simultaneously, active component is a benchmark with the quality of carrier; Its quality percentage composition is 10.7%, promptly processes a kind of processing organic exhaust gas catalyst.
(4) catalyst performance evaluation
By the evaluation method of implementing 2, this catalyst is 100% at 250 ℃ of catalytic efficiencies to toluene, and in 250 ℃～500 ℃ scopes, it is good that catalyst stability keeps.Cu-Mn complex oxide (CuMn is described
2O
4) organic exhaust gas is had high catalytic oxidation performance, and in the temperature range of broad, keep very high stability, the catalytic combustion that is fit to industrial organic exhaust gas is handled.
Embodiment 3
(1) preparation and the modification of self-control carrier
Get 55g silica, 29.5g aluminium oxide, 15g magnesia and 0.5g iron oxide and mix, mixture is through 1350 ℃ of roastings, and temperature retention time is controlled at 6h; The self-control carrier is through the modification of 10wt% oxalic acid solution, on electric furnace, boils and is incubated 2h; 100 ℃ of baking temperatures, be 1h drying time; 500 ℃ of sintering temperatures, roasting time are 5h, obtain modified support through roasting.
(2) preparation of activity component impregnation liquid
Get 25.3g solid CuC
2O
4.1/2H
2O, 114.6g solid MnC
2O
4.2H
2O and 207.8g distilled water are mixed with Cu
2+And Mn
2+Mol ratio is 1: 4 a mixed solution, mixes with the titanium glue that contains 9.6g titanium dioxide again, makes cupric oxide, manganese oxide and titanium oxide mol ratio and be 1: 4: 1 maceration extract.
(3) load of active component
Get 4h in the solution that homemade 100g support samples in the step (1) is immersed in step (2) preparation; Soaked carrier is dried the 120 ℃ of dryings of common bellows with 2h naturally through 24h's; Roasting through 600 ℃ of insulations of Muffle furnace 3h promptly makes the catalyst that active component is cupric oxide manganese oxide and titanium oxide again, generates a spot of Cu-Mn complex oxide simultaneously, and active component is a benchmark with the quality of carrier; Its quality percentage composition is 11.6%, promptly processes a kind of processing organic exhaust gas catalyst.
(4) catalyst performance evaluation
By the evaluation method of implementing 3, this catalyst is 95% at 250 ℃ of catalytic efficiencies to toluene.
Embodiment 4
(1) preparation and the modification of self-control carrier
Get 49g silica, 20g aluminium oxide, 30g magnesia and 1g iron oxide and mix, mixture is through 1400 ℃ of roastings, and temperature retention time is controlled at 4h; The self-control carrier is through the modification of 15wt% oxalic acid solution, on electric furnace, boils and is incubated 2h; 120 ℃ of baking temperatures, be 1h drying time; 500 ℃ of sintering temperatures, roasting time are 5h, obtain modified support through roasting.
(2) preparation of activity component impregnation liquid
Get 72.0g solid CuC
2O
4.1/2H
2O, 40.3g solid MnC
2O
4.2H
2O and 159.4g distilled water are mixed with Cu
2+And Mn
2+Mol ratio is 2: 1 a mixed solution, mixes with the titanium glue that contains 10.1g titanium dioxide again, makes cupric oxide, manganese oxide and titanium oxide mol ratio and be 2: 1: 0.75 maceration extract.
(3) load of active component
Get 6h in the solution that homemade 100g support samples in the step (1) is immersed in step (2) preparation; Soaked carrier is dried the 100 ℃ of dryings of common bellows with 2h naturally through 18h's; Roasting through 650 ℃ of insulations of Muffle furnace 2h promptly makes the catalyst that active component is cupric oxide manganese oxide and titanium oxide again; Active component is a benchmark with the quality of carrier, and its quality percentage composition is 9.8%, promptly processes a kind of processing organic exhaust gas catalyst.
(4) catalyst performance evaluation
By the evaluation method of implementing 4; This catalyst is 96% at 250 ℃ of catalytic efficiencies to toluene, but after reaction temperature was higher than 300 ℃, catalytic efficiency descended; Because cupric oxide and manganese oxide exist with independent oxide state; Electronics shifts and hinders, decrease in efficiency under the catalysis, and active temperature windows narrows down.
Embodiment 5
(1) preparation and the modification of self-control carrier
Get 48g silica, 40g aluminium oxide, 10g magnesia and 2g iron oxide and mix, mixture is through 1300 ℃ of roastings, and temperature retention time is controlled at 6h; The self-control carrier is through the modification of 15wt% oxalic acid solution, on electric furnace, boils and is incubated 2h; 100 ℃ of baking temperatures, be 1h drying time; 400 ℃ of sintering temperatures, roasting time are 6h, obtain modified support through roasting.(2) preparation of activity component impregnation liquid
Get 82.7g solid CuC
2O
4.1/2H
2O, 22.8g solid MnC
2O
4.2H
2O and 148.8g distilled water are mixed with Cu
2+And Mn
2+Mol ratio is 4: 1 a mixed solution, mixes with the colloid that contains 5.7g titanium dioxide again, makes cupric oxide, manganese oxide and titanium oxide mol ratio and be 4: 1: 0.75 maceration extract.
(3) load of active component
Get 6h in the solution that homemade 100g support samples in the step (1) is immersed in step (2) preparation; Soaked carrier is dried the 80 ℃ of dryings of common bellows with 2h naturally through 12h's; Roastings through 500 ℃ of Muffle furnaces insulation 5h promptly make the catalyst that active component is cupric oxide manganese oxide and titanium oxide again, generate a spot of Cu-Mn complex oxide simultaneously, are benchmark with the quality of carrier; Its quality percentage composition is 11.5%, promptly processes a kind of processing organic exhaust gas catalyst.
(4) catalyst performance evaluation
By the evaluation method of implementing 5, this catalyst is 87% at 250 ℃ of catalytic efficiencies to toluene.
Embodiment 6
(1) preparation and the modification of self-control carrier
Get 42g silica, 30g aluminium oxide, 27g magnesia and 1g iron oxide and mix, mixture is through 1350 ℃ of roastings, and temperature retention time is controlled at 5h.The self-control carrier is through the modification of 20wt% oxalic acid solution, on electric furnace, boils and is incubated 2h.80 ℃ of baking temperatures, be 2h drying time; 500 ℃ of sintering temperatures, roasting time are 5h, obtain modified support through roasting.
The preparation of (2) one groups of activity component impregnation liquid
Get Ag solid CuC
2O
4.1/2H
2O, Bg solid MnC
2O
4.2H
2O and Cg distilled water are mixed with Cu
2+And Mn
2+Mol ratio was respectively 1: 1, and 1: 2,1: 4, the mixed solution of 2: 1 and 4: 1 mixed with the titanium glue that contains Dg titanium dioxide again, and making cupric oxide, manganese oxide and titanium oxide mol ratio is 1～4: 1～4: 0.5～1 maceration extract.
| n Cu2+∶n Mn2+ | A(g) | B(g) | C(g) | D(g) |
| 1∶1 | 24.0 | 26.8 | 154.7 | 4.5 |
| 1∶2 | 16.0 | 35.8 | 156.7 | 2.3 |
| 1∶4 | 9.3 | 42.9 | 158.1 | 3.6 |
| 2∶1 | 30.7 | 17.0 | 144.8 | 4.3 |
| 4∶1 | 39.4 | 10.7 | 151.5 | 2.7 |
(3) load of active component
Get 8h in 5 kinds of solution that homemade 100g support samples in the step (1) is immersed in step (2) preparation respectively; Soaked carrier is dried the 100 ℃ of dryings of common bellows with 2h naturally through 16h's, and the roastings through 500 ℃ of insulations of Muffle furnace 3h promptly make the catalyst that active component is cupric oxide, manganese oxide and titanium oxide again, is benchmark with the quality of carrier; Its quality percentage composition is respectively 5.6%; 3.7%, 5.3%, 5.3% and 5.4%.
(4) catalyst performance evaluation
By the evaluation method of implementing 6, this catalyst 250 ℃ to the catalytic efficiency of toluene for not being 85%, 89%, 85%, 88% and 85%.
Embodiment 7
(1) preparation and the modification of self-control carrier
Get 49.5g silica, 30g aluminium oxide, 20g magnesia and 0.5g iron oxide and mix, mixture is through 1400 ℃ of roastings, and temperature retention time is controlled at 4h; The self-control carrier is through the modification of 20wt% oxalic acid solution; On heating furnace, boil and be incubated 2h, 100 ℃ of baking temperatures, be 1h drying time; 500 ℃ of sintering temperatures, roasting time are 5h, obtain modified support through roasting.
The preparation of (2) one groups of activity component impregnation liquid
Get Ag solid CuC
2O
4.1/2H
2O, Bg solid MnC
2O
4.2H
2O and Cg distilled water are mixed with Cu
2+And Mn
2+Mol ratio was respectively 1: 1, and 1: 2,1: 4, the mixed solution of 2: 1 and 4: 1 mixed with the titanium glue that contains Dg titanium dioxide again, and making cupric oxide, manganese oxide and titanium oxide mol ratio is 1～4: 1～4: 0.5～1 maceration extract.
| n Cu2+∶n Mn2+ | A(g) | B(g) | C(g) | D(g) |
| 1∶1 | 96.7 | 107.4 | 138.8 | 18.0 |
| 1∶2 | 64.0 | 143.2 | 146.1 | 18.0 |
| 1∶4 | 37.4 | 164.7 | 151.7 | 13.8 |
| 2∶1 | 130.7 | 72.5 | 131.1 | 18.2 |
| 4∶1 | 158.1 | 43.9 | 124.8 | 11.0 |
(3) load of active component
Get 8h in 5 kinds of solution that homemade 100g support samples in the step (1) is immersed in step (2) preparation respectively; Soaked carrier is dried the 80 ℃ of dryings of common bellows with 2h naturally through 12h's, promptly makes the catalyst of active component cupric oxide manganese oxide and titanium oxide again through the roasting of 500 ℃ of insulations of Muffle furnace 4h, is benchmark with the quality of carrier; Its quality percentage composition is respectively 17.5%; 18.3%, 19.2%, 17.2% and 19.3%.
(4) catalyst performance evaluation
By the evaluation method of implementing 7, this catalyst for being not 93%, 94%, 92%, 95% and 90%, is explained the raising activity component load quantity at 250 ℃ of catalytic efficiencies to toluene, and catalysis efficiency is carried office to some extent.
Embodiment 8
(1) preparation and the modification of self-control carrier
Get 40g silica, 34g aluminium oxide 24g magnesia and 2g iron oxide and mix, mixture is through 1350 ℃ of roastings, and temperature retention time is controlled at 5h; The self-control carrier is through the modification of 20wt% oxalic acid solution, on electric furnace, boils and is incubated 2h.120 ℃ of baking temperatures, be 1h drying time; 600 ℃ of sintering temperatures, roasting time are 4h; Modified support carries out aluminum oxide coating layer again, with above-mentioned carrier impregnation at alumine hydroxide colloid after 12 hours, again through 24 hours dry naturally, 100 ℃ of baking temperatures, be 2h drying time; 550 ℃ of sintering temperatures, roasting time are 3h, and the process roasting makes the new modified carrier of aluminum oxide coating layer modification, promptly alumina modified carrier.
(2) preparation of activity component impregnation liquid
Get 60.0g solid CuC
2O
4.1/2H
2O, 132.5g solid MnC
2O
4.2H
2O and 289.9g distilled water are mixed with Cu
2+And Mn
2+Mol ratio is 1: 2 a mixed solution, mixes with the colloid that contains 16.7g titanium dioxide again, makes cupric oxide, manganese oxide and titanium oxide mol ratio and be 1: 2: 0.75 maceration extract.
(3) load of active component
Get 6h in the solution that the alumina modified support samples of homemade 100g in the step (1) is immersed in step (2) preparation; Soaked carrier is dried the 100 ℃ of dryings of common bellows with 2h naturally through 20h's; Promptly making the catalyst of active component cupric oxide, manganese oxide and titanium oxide again through the roasting of 500 ℃ of Muffle furnaces insulation 4h, generate Cu-Mn complex oxide simultaneously, is benchmark with the quality of carrier; Aluminum oxide coating layer quality percentage composition is 5.3%, and its active component quality percentage composition is 18.0%.
(4) catalyst performance evaluation
By the evaluation method of implementing 8, this catalyst is 96% at 250 ℃ of catalytic efficiencies to toluene.But having higher specific area through coating modified catalyst, is 130 ℃ to the initiation temperature of toluene.This catalyst is simultaneously at 300 ℃ of active testings that carry out 48h, and catalyst keeps the conversion ratio to toluene 96%, and (200 ℃～1000 ℃) keep very high activity in the temperature range of broad, economic and reliable and be fit to the industrial treatment organic exhaust gas more.
Catalysis toluene active testing instance
The toluene of table 1 embodiment 2,4,8 catalyst is removed efficient
Test condition: quartz tube reactor, inner diameter d are 7mm;
Specific surface area of catalyst: 6.37m
2/ g piles up length: 6.5cm;
Toluene concentration: 6000ppm, O
2: 20.6%;
Air speed: 12000h
-1, catalyst amount: 5g.
Claims (4)
1. handle the organic exhaust gas catalyst for one kind, it is characterized in that said catalyst is an active component with cupric oxide, manganese oxide and titanium oxide, the self-control catalyst carrier is a benchmark with the quality of carrier, and the quality percentage composition of the load capacity of active component is 1～20%;
Said self-control carrier is to be constituent with silica, aluminium oxide, magnesia and iron oxide; Wherein the raw materials quality per distribution ratio is silica 28～55%, aluminium oxide 20～40%, magnesia 10～30%, iron oxide 0.5～2%; Mix by above-mentioned quality per distribution ratio; Form through 1300～1400 ℃ of high-temperature roastings, using mass percent again is 5～20% acid treatment, and carrier is carried out modification.
2. a kind of processing organic exhaust gas catalyst according to claim 1; It is characterized in that said active component is is 1～4: 1～4 with cupric oxide, manganese oxide and titanium oxide mol ratio: 0.5～1 allocates, and forming with cupric oxide, manganese oxide and titanium oxide is the catalyst of active component.
3. a kind of processing organic exhaust gas catalyst according to claim 1 is characterized in that said mass percent is that oxalic acid or acetate are selected in 5～20% acid for use.
4. the described a kind of processing organic exhaust gas Preparation of catalysts method of claim 1 is characterized in that its concrete steps are following:
(1) preparation and the processing of self-control carrier
Silica, aluminium oxide, magnesia and iron oxide are mixed by the quality per distribution ratio, and wherein the raw materials quality per distribution ratio is silica 28～55%, aluminium oxide 20～40%, magnesia 10～30%, iron oxide 0.5～2%, and raw material mixes after 1300～1400 ℃ of high-temperature roastings make catalyst carrier; Insulation 4～6h, and to use mass percent be that 5～20% oxalic acid or acetate boil, boiling the processing time is 2～3h; Again through 80～120 ℃ of temperature; Time is the drying of 1～2h, carries out roasting after the drying, and roasting is 400～600 ℃ of temperature; Time is 4～6h, obtains modified support through roasting;
Get above-mentioned modified support and be immersed in the alumine hydroxide colloid, carry out the aluminum oxide coating layer modification, through 80～120 ℃; The drying of 1～2h and 500～600 ℃; The modified support of aluminum oxide coating layer modification is processed in 2～4h roasting, promptly alumina modified carrier; With the modified support is benchmark, and activated alumina load capacity quality percentage composition is 1～10% in the alumina modified carrier;
(2) preparation of activity component impregnation liquid
Cu salt and Mn salting liquid are dissolved in the titanium glue, and described Cu salt and Mn salt are oxalates, carbonate or phosphate, and preparation Cu salt, Mn salt and titanium oxide mol ratio are 1～4: 1～4: 0.5～1 maceration extract;
(3) load of active component
With modified support in the step (1) or alumina modified carrier impregnation in the solution of step (2) preparation; Dip time is 4～8h; Through the drying naturally and in drying box 80～120 ℃ of 12～24h, the forced air drying of 1～4h is again through 300～650 ℃ then; The roasting of 2～5h; Perhaps repeated impregnations, drying and roasting are with the catalyst of preparation certain negative carrying capacity, and the quality percentage composition that makes the load capacity of cupric oxide, manganese oxide and titanium oxide is 1～20%, promptly processes a kind of processing organic exhaust gas catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102346910A CN101733127B (en) | 2009-11-27 | 2009-11-27 | Catalyst for treating organic waste gas and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102346910A CN101733127B (en) | 2009-11-27 | 2009-11-27 | Catalyst for treating organic waste gas and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101733127A CN101733127A (en) | 2010-06-16 |
| CN101733127B true CN101733127B (en) | 2012-05-23 |
Family
ID=42457457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102346910A Expired - Fee Related CN101733127B (en) | 2009-11-27 | 2009-11-27 | Catalyst for treating organic waste gas and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101733127B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101961653B (en) * | 2010-09-30 | 2012-06-27 | 浙江工业大学 | Composite oxide catalytic combustion catalyst as well as preparation method and application thereof |
| CN104056530A (en) * | 2014-07-01 | 2014-09-24 | 北京建筑材料科学研究总院有限公司 | Contaminated soil thermal decomposition tail gas treatment method |
| CN106466608B (en) * | 2015-08-20 | 2020-10-16 | 中国石油化工股份有限公司 | Catalyst for catalytic reduction of nitrogen oxides by carbon monoxide and preparation method thereof |
| CN107243322A (en) * | 2017-06-07 | 2017-10-13 | 包鑫 | A kind of diatom ore deposit crystalline substance purification particle containing oyster shell whiting and preparation method thereof |
| CN107377004A (en) * | 2017-07-28 | 2017-11-24 | 盐城市龙强机械制造有限公司 | A kind of baking finish for car paint house catalyst for treating waste gas |
| CN109513447B (en) * | 2018-08-01 | 2021-10-22 | 沈炳龙 | Catalyst for removing carbon monoxide and preparation method thereof |
| CN111939889B (en) * | 2019-05-17 | 2023-02-21 | 中国石油化工股份有限公司 | Renewable NO oxidation catalyst, preparation method and application thereof |
| CN111939888B (en) * | 2019-05-17 | 2023-02-17 | 中国石油化工股份有限公司 | Method for preparing carrier material, NO oxidation catalyst and application thereof |
| CN114700083A (en) * | 2022-04-28 | 2022-07-05 | 湖南立泰环境工程有限公司 | Composite catalyst for low-concentration VOC and preparation method thereof |
| CN114870876B (en) * | 2022-06-14 | 2024-01-19 | 北京碧水源膜科技有限公司 | Catalyst and preparation method and application thereof |
| CN115041185B (en) * | 2022-07-01 | 2023-12-29 | 宁夏同德爱心循环能源科技有限公司 | Catalyst for treating organic waste gas and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1830529A (en) * | 2005-03-10 | 2006-09-13 | 浙江师范大学 | Organic waste gas catalytic combustion catalyst and its manufacturing method |
| US20080262114A1 (en) * | 2007-01-18 | 2008-10-23 | Marinus Johannes Reynhout | Fischer-tropsch catalyst support and catalyst |
| CN101298024A (en) * | 2008-01-11 | 2008-11-05 | 深圳市格瑞卫康环保科技有限公司 | Catalyst for purifying volatile organic pollutant and ozone in air under normal temperature as well as preparation and use thereof |
-
2009
- 2009-11-27 CN CN2009102346910A patent/CN101733127B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1830529A (en) * | 2005-03-10 | 2006-09-13 | 浙江师范大学 | Organic waste gas catalytic combustion catalyst and its manufacturing method |
| US20080262114A1 (en) * | 2007-01-18 | 2008-10-23 | Marinus Johannes Reynhout | Fischer-tropsch catalyst support and catalyst |
| CN101298024A (en) * | 2008-01-11 | 2008-11-05 | 深圳市格瑞卫康环保科技有限公司 | Catalyst for purifying volatile organic pollutant and ozone in air under normal temperature as well as preparation and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101733127A (en) | 2010-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101733127B (en) | Catalyst for treating organic waste gas and preparation method thereof | |
| CN102240557B (en) | Catalyst containing nickel-iron-manganese compound oxide for processing industrial waste gas and preparation method thereof | |
| CN102824909B (en) | Catalyst for low-temperature catalytic combustion of volatile organic compounds and preparation method thereof | |
| CN102513123B (en) | Rare-earth perovskite type catalyst for treating industrial waste gas as well as preparation method and application thereof | |
| CN101961653B (en) | Composite oxide catalytic combustion catalyst as well as preparation method and application thereof | |
| CN106268740B (en) | A kind of loaded catalyst and its preparation method and application for low concentration combustible component anoxycausis in liquid nitrogen washing tail-gas | |
| CN102527404B (en) | Medium/low temperature SCR (Selective Catalytic Reduction) denitration catalyst with gamma-Al2O3 as carrier and preparation method thereof | |
| CN101811046B (en) | Noble metal monolithic catalyst for purifying organic waste gas and preparation method thereof | |
| CN101108345A (en) | Cerium basis composite oxides doped precious metal integer catalyzer and method of manufacturing the same | |
| CN106732647A (en) | A kind of perovskite type methyl hydride combustion catalyst and preparation method and application | |
| CN103706374B (en) | A kind of ventilating gas methane oxidation integral catalyzer and preparation method thereof | |
| CN102489305A (en) | Transition metal composite oxide catalyst for catalytic decomposition of N2O and method for preparing catalyst | |
| CN106732579A (en) | Nano-noble metal integer catalyzer for organic exhaust gas low-temperature catalytic burning and preparation method thereof | |
| CN106040247A (en) | Catalyst for ammonia selective catalysis and oxidization and preparation method thereof | |
| CN108114718A (en) | A kind of Ce-Zr-M overall structures combustion catalyst and preparation method | |
| CN109794248A (en) | A kind of low cost catalyst for denitrating flue gas and its preparation, application method | |
| CN112844459B (en) | VOCs catalytic oxidation catalyst and preparation method and application thereof | |
| CN102000600B (en) | Integral normal-temperature micro nitrogen oxide purification material and preparation method thereof | |
| CN101912783B (en) | Catalyst for combustion of ventilation air methane and preparation method thereof | |
| CN110523413A (en) | A kind of preparation method of supported catalyst and the application in the catalytic oxidation of benzene | |
| CN108212145B (en) | Catalytic combustion catalyst containing manganese-cerium-titanium-hafnium composite oxide and preparation method and application thereof | |
| CN106824217A (en) | A kind of cellular integrated catalyst and preparation method thereof | |
| CN101530743A (en) | Oil smoke purifier applicable to downdraft kitchen ventilator and method for preparing catalyst | |
| CN101716511B (en) | Catalyst for catalytic combustion of industrial organic waste gas and preparation method thereof | |
| CN101181681A (en) | Catalyst for purifying asphalt smoke gas and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120523 Termination date: 20151127 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |