CN104998655A - Integral cordierite catalyst and preparation method and application thereof - Google Patents
Integral cordierite catalyst and preparation method and application thereof Download PDFInfo
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- CN104998655A CN104998655A CN201510435541.1A CN201510435541A CN104998655A CN 104998655 A CN104998655 A CN 104998655A CN 201510435541 A CN201510435541 A CN 201510435541A CN 104998655 A CN104998655 A CN 104998655A
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Abstract
The invention provides an integral cordierite catalyst. Cordierite-based honeycomb ceramic is used as a carrier of the catalyst, and the carrier is sequentially coated with a transition coating and an active component; the transition coating comprises conductive black and oxide of the following structure: CemZr(1-m)O2, wherein 0<m<=1; the active component is La(1-x)SrxCoyMn(1-y)O3, wherein 0<=x<=0.2, and 0<=y<=0.2; the mass ratio of the carrier to the transition coating to the active component is 1:(0.01-0.05):(0.01-0.08). According to the catalyst, as the carrier is coated with the transition coating in the mode of gel solution impregnation, the transition coating is coated with the active component, the coating is dispersed evenly, and the active component is tightly combined with the carrier, perovskite is effectively prevented from interacting with the cordierite-based carrier, the high thermal stability and catalytic activity of the catalyst are improved, the service life of the catalyst is prolonged, the preparation technology is simple, and the integral cordierite catalyst is suitable for industrial application.
Description
Technical field
The invention belongs to environment protection catalytic technical field, relate to a kind of cordierite monolithic catalyst and its preparation method and application, particularly relate to cordierite monolithic catalyst of a kind of heat-storage catalytic burning cleaning organic waste gas and its preparation method and application.
Background technology
Many industries in process of production can to a large amount of volatile organic contaminant (the Volatileorganic compounds of airborne release, VOCs), as materials such as the benzene,toluene,xylene of the industry such as petrochemical industry, printing, electron trade, automotive lacquer and coating discharge, styrene, ethyl acetate and n-hexanes.These materials form Secondary Organic aeroge through photochemical effect after entering air, are the one of the main reasons causing atmospheric haze, serious harm human health and animal and plant growth.The processing method of organic exhaust gas mainly contains absorption method, absorption process, plasma method, condensation method, photocatalytic method, directly combustion method and Production by Catalytic Combustion Process etc.Except Production by Catalytic Combustion Process, all there is the problem of secondary pollution in remaining purification method, and Production by Catalytic Combustion Process is current most widely used purification style, be process VOCs the most effectively and the most thoroughly one of mode, this technology is, by catalyst action, organic molecule low temperature conversion is become carbon dioxide and water.
Integral catalyzer relates to the catalyst that in catalytic reaction industry, a class is important, and it is widely used in the catalytic purification of organic exhaust gas.Honeycomb ceramics type integral catalyst is because pressure drop is little, intensity is high and the feature such as easy load active component, it is the catalyst that industrial quarters generally uses, its active component is generally noble metal, based on Pt and Pd etc., cleaning organic waste gas has the advantage that universality is strong, low temperature purification efficiency is high, but the shortcoming such as expensive, poor heat stability, easily poisoning and deactivation restricts it and applies widely simultaneously.And perovskite type composite oxide catalyst has high high-temp stability and the advantage such as cheap, is expected to the alternative materials becoming noble metal active component, as honeycomb ceramics type integral catalyst active component and extensively study.
At present, Ca-Ti ore type ceramic honey comb is catalyst based to be widely used in actual industrial use procedure, but Extruded Monolithic Celluar Ceramics such as the components such as Al, the Mg in cordierite and mullite easily react to each other with the perovskite active component generation heat of area load, and active component is impacted at high-speed and is easily chapped under thermal shock and peel off, catalyst cleaning effect is caused to reduce, even inactivation.Therefore, avoid active component and cordierite substrates direct interaction, and to increase active component and combining closely of matrix be the key that the long-term efficient stable of catalyst runs.
Patent CN 101439290A discloses a kind of cellular ceramic type catalyst for catalytic combustion of perovskite and Synthesis and applications thereof, described catalyst with the ceramic honey comb of coating of metal oxides for carrier, load La
1-xsr
xco
ymn
1-yo
3active component.The load of coating of metal oxides is by getting appropriate r-Al
2o
3and Ce
mzr
1-mo
2form suspension in metal oxide powder and water and organic acid mix and blend, then by cordierite substrates immersion coating, the load of its active component is also adopt the method for similar suspension to prepare.This method avoid active component to contact with the direct of cordierite, but metal oxide or powdered active ingredient dispersion form the problem that coating solution exists dispersed inequality, cause coating and active component easily to come off.
Patent CN 104549253A discloses a kind of catalyst for catalytic combustion and preparation method thereof, this catalyst take cordierite honeycomb ceramic as matrix, surface is silicon-coating aluminized coating, composite coating and noble metal active component successively, with overall catalyst weight gauge, containing cordierite honeycomb ceramic 80 ~ 90wt%, sial coating 2 ~ 9wt%, composite coating 3 ~ 10wt% and active component 0.01 ~ 1wt% in catalyst, active group for Pt, Pd, Rh, Ru and Ir one or more; Containing silica and aluminium oxide in sial coating; Containing titanium dioxide, silica, aluminium oxide and auxiliary agent in composite coating.Nano size Titania wherein needs high shear force just can be uniformly dispersed, coating slurry complicated components, and coat type is many, prepares loaded down with trivial details.
Summary of the invention
For metal oxide in the catalyst existed in above-mentioned prior art or active component dispersion is uneven, coating and active component easily comes off, catalyst coat complicated components and the problem such as preparation process is loaded down with trivial details, the invention provides a kind of cordierite monolithic catalyst and its preparation method and application.In described catalyst, tie coat adopts the mode of coagulant liquid dipping to be coated on carrier, coated active component on tie coat again, coating can be made to be uniformly dispersed, active component and carrier are combined closely, effectively prevent perovskite and cordierite carrier from interacting, improve catalyst high thermal stability, catalytic activity and service life, preparation technology is simple, is applicable to industrial applications.
For reaching this object, the present invention by the following technical solutions:
First aspect, the invention provides a kind of cordierite monolithic catalyst, described catalyst with cordierite-base ceramic honey comb for carrier, coated tie coat and active component successively on carrier;
Tie coat comprises conductive black and has the oxide of following structure: Ce
mzr
1-mo
2, and 0 < m≤1;
Active component is La
1-xsr
xco
ymn
1-yo
3, 0≤x≤0.2,0≤y≤0.2;
The mass ratio of carrier, tie coat and active component is 1:(0.01 ~ 0.05): (0.01 ~ 0.08), if tie coat and active component content are lower than lower limit, then tie coat can not be coated on cordierite uniformly, thus causes surperficial directly contact of active component and cordierite to cause catalytic activity to reduce.If tie coat and active component content exceed the upper limit, then tie coat and active component are easily reunited with coming off and are caused catalytic activity to reduce.
Wherein, Ce
mzr
1-mo
2middle m can be 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9 or 1 etc.; When m is 1, be CeO
2.
Active component is perovskite composite oxide, La
1-xsr
xco
ymn
1-yo
3middle x can be 0,0.05,0.1,0.15 or 0.2 etc., y and can be 0,0.05,0.1,0.15 or 0.2 etc.; When x be 0, y is 0, be LaMnO
3; When x be 0.2, y is 0.2, be La
0.8sr
0.2co
0.2mn
0.8o
3; When x be 0, y is 0.2, be LaCo
0.2mn
0.8o
3; When x be 0.2, y is 0, be La
0.8sr
0.2mnO
3.
The mass ratio of carrier, tie coat and active component can be 1:0.01:0.01,1:0.02:0.02,1:0.01:0.05,1:0.03:0.03,1:0.04:0.04,1:0.05:0.05,1:0.05:0.06,1:0.04:0.07,1:0.05:0.08 or 1:0.05:0.01 etc.
In the present invention, described tie coat comprises following component by mass percentage:
Ce
mZr
1-mO
295～100％
Conductive black 0 ~ 5%
Described Ce
mzr
1-mo
2be 100% with the mass percent sum of conductive black.
Wherein, Ce
mzr
1-mo
2mass percent can be 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99%, 99.5%, 99.9% or 100% etc.; The mass percent of conductive black can be 0,0.01%, 0.1,0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% etc.Namely described tie coat can be only Ce
mzr
1-mo
2, also can be Ce
mzr
1-mo
2with the mixture of conductive black.
Preferably, described Ce
mzr
1-mo
2in 0.2≤m≤0.7, more preferably m=0.5, be Ce
0.5zr
0.5o
2.
In the present invention, described active component La
1-xsr
xco
ymn
1-yo
3in 0.05≤x≤0.1,0.02≤y≤0.08.
Preferably, the mass ratio of described carrier, tie coat and active component is 1:(0.02 ~ 0.04): (0.02 ~ 0.05), more preferably 1:0.02:0.04.
Preferably, described cordierite-base ceramic honey comb is rectangle and/or circle.
Preferably, the perforate on described cordierite-base ceramic honey comb be hexagon, circle or square in any one.
Preferably, described cordierite-base ceramic honey comb is square duration is 5 ~ 15cm, such as 5cm, 8cm, 10cm, 12cm, 14cm or 15cm etc., more preferably 10cm.
Preferably, wide when described cordierite-base ceramic honey comb is square is 5 ~ 15cm, such as 5cm, 8cm, 10cm, 12cm, 14cm or 15cm etc., more preferably 10cm.
Preferably, high when described cordierite-base ceramic honey comb is square is 5 ~ 10cm, such as 5cm, 7cm, 8cm or 10cm etc., more preferably 5cm.
Preferably, the hole count of described cordierite-base ceramic honey comb is 5 ~ 14 holes/cm
2, such as 5 holes/cm
2, 7 holes/cm
2, 8 holes/cm
2, 10 holes/cm
2, 12 holes/cm
2, 13 holes/cm
2or 14 holes/cm
2deng.
Preferably, described tie coat adopts the mode of coagulant liquid dipping to be coated on carrier.
Tie coat is coated on carrier by the mode that the present invention is flooded by coagulant liquid, coating can be made to be uniformly dispersed and incrust.
Second aspect, the invention provides the preparation method of above-mentioned cordierite monolithic catalyst, said method comprising the steps of:
(1) be immersed in through heat treated cordierite-base ceramic honey comb in the gel slurries of tie coat, take out, dry up, dry and roasting, obtain the cordierite-base ceramic honey comb being coated with tie coat;
(2) be immersed in the maceration extract containing active component by the cordierite-base ceramic honey comb being coated with tie coat, then taking-up, dry and roasting, obtain cordierite monolithic catalyst.
In the present invention, in step (1), the heat treatment of cordierite-base ceramic honey comb is:
Cordierite-base ceramic honey comb is placed in drying box, dry 1 ~ 8h at 60 ~ 80 DEG C.
Wherein, baking temperature can be 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C or 80 DEG C etc.; Drying time can be 1h, 2h, 3h, 4h, 5h, 6h, 7h or 8h etc.
In the present invention, in step (1), the preparation method of the gel slurries of tie coat is:
Cerium salt is dissolved in solvent and forms solution A, the alkoxide of zirconium is dissolved in solvent and forms solution B, solution B is dripped in solution A, at 25 ~ 80 DEG C, stir 0.5 ~ 3h, then add conductive black under agitation, obtain the gel slurries of tie coat.
Wherein, at 25 ~ 80 DEG C, the temperature stirred in 0.5 ~ 3h can be 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C or 80 DEG C etc., and the time can be 0.5h, 1h, 1.5h, 2h or 3h etc.
Solution B being dripped in solution A is solution B dripped slowly in solution A, makes the two be uniformly dispersed, forms stable gel.
Preferably, described cerium salt is the combination of any one or at least two kinds in cerous nitrate, cerous acetate, cerous sulfate or cerium chloride, described combination typical case but limiting examples have: the combination of cerous nitrate and cerous acetate, the combination of cerous acetate and cerous sulfate, the combination of cerous sulfate and cerium chloride, the combination of cerous nitrate, cerous acetate and cerous sulfate, the combination etc. of cerous nitrate, cerous acetate, cerous sulfate and cerium chloride.
Preferably, the alkoxide of described zirconium is zirconium-n-propylate and/or zirconium iso-propoxide, such as, can adopt the composition of zirconium-n-propylate and zirconium iso-propoxide, also can to adopt in zirconium-n-propylate and zirconium iso-propoxide any one.
Preferably, described solvent is normal propyl alcohol and/or isopropyl alcohol, such as, can adopt the composition of normal propyl alcohol and isopropyl alcohol, also can to adopt in normal propyl alcohol and isopropyl alcohol any one.
Preferably, stir at 25 ~ 80 DEG C and regulate while 0.5 ~ 3h the pH of solution to be 3 ~ 6, such as, regulate pH to be 3,3.5,4,4.5,5 or 6 etc.
Preferably, the pH of nitre acid-conditioning solution is dripped while stirring 0.5 ~ 3h at 25 ~ 80 DEG C.
Preferably, the concentration of the nitric acid of dropping is 0.5 ~ 1.5mol/L, such as 0.5mol/L, 0.7mol/L, 0.9mol/L, 1.0mol/L, 1.2mol/L, 1.4mol/L or 1.5mol/L etc., is preferably 1mol/L.
Preferably, the particle diameter of the conductive black added is 10 ~ 100nm, such as 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm or 100nm etc.
Preferably, in the gel slurries of tie coat, total concentration of cerium ion and zirconium ion is 0.1 ~ 0.5mol/L, such as 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.45mol/L or 0.5mol/L etc.
In the present invention, 5 ~ 10min in the gel slurries being immersed in tie coat through heat treated cordierite-base ceramic honey comb takes out by step (1) again, and dip time can be 5min, 5.5min, 6min, 6.5min, 7min, 7.5min, 8min, 8.5min, 9min, 9.5min or 10min etc.
Preferably, the baking temperature in step (1) is 60 ~ 80 DEG C, such as 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C or 80 DEG C etc.
Preferably, the drying time in step (1) is 8 ~ 24h, such as 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h etc.
Preferably, the sintering temperature in step (1) is 500 ~ 700 DEG C, such as 500 DEG C, 530 DEG C, 550 DEG C, 570 DEG C, 600 DEG C, 630 DEG C, 670 DEG C or 700 DEG C etc.
Preferably, the roasting time in step (1) is 3 ~ 6h, such as 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h etc.
Preferably, what obtain in step (1) is coated with Ce in the cordierite-base ceramic honey comb of tie coat
mzr
1-mo
2quality be 1 ~ 5%, such as 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% of cordierite-base ceramic honey comb quality etc.
Preferably, the quality being coated with conductive black in the cordierite-base ceramic honey comb of tie coat obtained in step (1) is Ce
mzr
1-mo
20 ~ 5%, such as 0,0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% etc.
In the present invention, the preparation method of the maceration extract containing active component in step (2) is:
By La salt, Sr salt, Mn salt and Co salt ultrasonic disperse in the mixed solvent of water and alcohols solvent, obtain the maceration extract containing active component.
Preferably, described La salt is the combination of any one or at least two kinds in the nitrate of La, sulfate or chlorate, described combination typical case but limiting examples have: the combination of the nitrate of La and the sulfate of La, the sulfate of La and the chlorate of La, the combination etc. of the nitrate of La, sulfate and chlorate.
Preferably, described Sr salt is the combination of any one or at least two kinds in the nitrate of Sr, sulfate or chlorate, described combination typical case but limiting examples have: the combination of the nitrate of Sr and the sulfate of Sr, the sulfate of Sr and the chlorate of Sr, the combination etc. of the nitrate of Sr, sulfate and chlorate.
Preferably, described Mn salt is the combination of any one or at least two kinds in the nitrate of Mn, sulfate or chlorate, described combination typical case but limiting examples have: the combination of the nitrate of Mn and the sulfate of Mn, the sulfate of Mn and the chlorate of Mn, the combination etc. of the nitrate of Mn, sulfate and chlorate.
Preferably, described Co salt is the combination of any one or at least two kinds in the nitrate of Co, sulfate or chlorate, described combination typical case but limiting examples have: the combination of the nitrate of Co and the sulfate of Co, the sulfate of Co and the chlorate of Co, the combination etc. of the nitrate of Co, sulfate and chlorate.
Preferably, the ion mol ratio controlling (La+Sr) and (Mn+Co) in the maceration extract containing active component is 1:1;
Preferably, the ion mol ratio controlling Sr and (La+Sr) in the maceration extract containing active component is (0 ~ 0.2): 1, and such as 0.01:1,0.05:1,0.1:1,0.15:1 or 0.2:1, it also comprises the situation that Sr ion concentration is 0.
Preferably, the ion mol ratio controlling Co and (Mn+Co) in the maceration extract containing active component is (0 ~ 0.2): 1, and such as 0.01:1,0.05:1,0.1:1,0.15:1 or 0.2:1, it also comprises the situation that Co ion concentration is 0.
Preferably, in the mixed solvent of described water and alcohols solvent, the volume ratio of water and alcohols solvent is (0.2 ~ 5): 1, such as 0.2:1,0.5:1,1:1,1.5:1,2:1,2.5:1,3:1,3.5:1,4:1,4.5:1 or 5:1 etc.
Preferably, described alcohols solvent is ethanol and/or propyl alcohol, such as, can be the mixture of ethanol and propyl alcohol, also can to adopt separately in ethanol or propyl alcohol any one.
Preferably, described water is deionized water.
Preferably, described is 0.3 ~ 3mol/L, such as 0.3mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L or 3mol/L etc. containing total concentration of La, Sr, Mn and Co ion in the maceration extract of active component.
In the present invention, temperature dry in step (2) is 60 ~ 80 DEG C, such as 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C or 80 DEG C etc.
Preferably, dry in step (2) time is 8 ~ 24h, such as 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h etc.
Preferably, the temperature of roasting is 500 ~ 700 DEG C in step (2), such as 500 DEG C, 530 DEG C, 550 DEG C, 570 DEG C, 600 DEG C, 630 DEG C, 670 DEG C or 700 DEG C etc.
Preferably, in step (2), the time of roasting is 3 ~ 6h, such as 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h etc.
The third aspect, invention provides the purposes of above-mentioned cordierite monolithic catalyst, it to be applied in benzene,toluene,xylene in industrial organic exhaust gas, ethyl acetate or n-hexane the purification of any one or at least two kinds, described combination typical case but limiting examples have: the purification of Benzene and Toluene in organic exhaust gas, the purification of benzene, toluene and dimethylbenzene in organic exhaust gas, the purification of dimethylbenzene and ethyl acetate in organic exhaust gas, the purification etc. of benzene,toluene,xylene, ethyl acetate and n-hexane in organic exhaust gas.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention adopts the Ce of coagulant liquid preparation catalyst
mzr
1-mo
2tie coat, avoids previously prepared Ce
mzr
1-mo
2composite oxide power stirs again or high speed shear causes dispersion is uneven, thus the problem such as the coating caused is uneven and easily come off; And Ce has and stores the activity that oxygen function can strengthen catalyst.Floating coat of the present invention has high-specific surface area, with basal body binding force jail, can increase the load capacity of active component, the high-temperature hot between active component and substrate can be avoided again to interact.
(2) the catalyst activity component that prepared by the present invention contains the salting liquid one step load perovskite component of active component by dipping, avoid perovskite oxide powder in typical impregnation method and be dispersed into the problem of maceration extract load by stirring or high speed shear again, and one time load capacity is large, with coating binding force jail, preparation is simple, the synergy of coating and active component promotes catalytic effect, the catalyst prepared conversion ratio in catalysis benzene purification process is 10%, the temperature of beds corresponding when 50% and 90% is respectively lower than 250 DEG C, 310 DEG C and 427 DEG C, benzene after purification, the concentration of toluene and paraxylene is all low to moderate 80ppm, obtain good clean-up effect.
Accompanying drawing explanation
Fig. 1 is catalyst sample catalysis benzene heat endurance and influence of moisture result figure in the embodiment of the present invention 3.
Detailed description of the invention
For better the present invention being described, be convenient to understand technical scheme of the present invention, below the present invention is described in more detail.But following embodiment is only simple and easy example of the present invention, and do not represent or limit the scope of the present invention, scope is as the criterion with claims.
Embodiment 1:
(1) heat treatment of cordierite-base ceramic honey comb: cordierite honeycomb ceramic entirety is put into air dry oven heating 80 DEG C, dry 2h.
(2) 8.68g is got, 0.02mol cerous nitrate, 6.55g, 0.02mol zirconium-n-propylate, ultrasonicly respectively be dissolved in 90ml normal propyl alcohol solution, then by containing the solution of zirconium in 25 DEG C of solution be added drop-wise under agitation containing cerium (wherein, total concentration of cerium ion and zirconium ion is 0.22mol/L), drip whipping process and continue 30min, continue to stir 20min and mix rear dropping 5ml, the nitric acid of 1mol/L is 5 ~ 6 to pH, stir 10min ageing again, the pretreated cordierite honeycomb ceramic of heat-obtaining is impregnated in above-mentioned solution, dipping 8min, then take out hair-dryer and dry up raffinate, dry 10h for 80 DEG C, 700 DEG C of calcining 3h, obtain the Ce that load capacity is 2.3%
0.5zr
0.5o
2the cordierite of coating.
(3) get 10ml, the manganese nitrate solution of 0.04mol, 17.32g, 0.04mol lanthanum nitrate is dissolved in (wherein, total concentration of La and Mn ion is 1.3mol/L) in 50ml water jointly, and ultrasonic disperse 30min, gets containing Ce
0.5zr
0.5o
2the cordierite of coating is impregnated in above-mentioned solution, then takes out, dries up raffinate with hair-dryer, dries 20h for 60 DEG C, and 500 DEG C of calcining 6h, obtain the LaMnO that load capacity is 4%
3cordierite-base catalyst.
Embodiment 2:
(1) heat treatment of cordierite-base ceramic honey comb: cordierite honeycomb ceramic entirety is put into air dry oven heating 60 DEG C, dry 8h.
(2) 8.68g is got, 0.02mol cerous nitrate, 6.55g, 0.02mol zirconium-n-propylate, ultrasonicly respectively be dissolved in 90ml aqueous isopropanol, then by containing the solution of zirconium in 25 DEG C of solution be added drop-wise under agitation containing cerium (wherein, total concentration of cerium ion and zirconium ion is 0.22mol/L), drip whipping process and continue 10min, continue to stir 10min and mix rear dropping 5ml, the nitric acid of 1mol/L is 5 ~ 6 to pH, stir 10min ageing again, the pretreated cordierite honeycomb ceramic of heat-obtaining is impregnated in above-mentioned solution, dipping 10min, then take out hair-dryer and dry up raffinate, dry 24h for 80 DEG C, 500 DEG C of calcining 6h, obtain the Ce that load capacity is 2.3%
0.5zr
0.5o
2the cordierite of coating.
(3) get 10ml, the manganese nitrate solution of 0.04mol, 17.32g, 0.04mol lanthanum nitrate is dissolved in (wherein, total concentration of La and Mn ion is 1.3mol/L) in 50ml water jointly, and ultrasonic disperse 30min, gets containing Ce
0.5zr
0.5o
2the cordierite of coating is impregnated in above-mentioned solution, then takes out, dries up raffinate with hair-dryer, dries 20h for 60 DEG C, and 500 DEG C of calcining 6h, obtain the LaMnO that load capacity is 4%
3cordierite-base catalyst.
Embodiment 3:
(1) heat treatment of cordierite-base ceramic honey comb: cordierite honeycomb ceramic entirety is put into air dry oven heating 70 DEG C, dry 1h.
(2) 17.36g is got, 0.04mol cerous nitrate, 13.1g, 0.04mol zirconium-n-propylate, ultrasonicly respectively be dissolved in (volume ratio 1:1) in 90ml normal propyl alcohol and isopropyl alcohol mixture, then by containing the solution of zirconium in 55 DEG C of solution be added drop-wise under agitation containing cerium (wherein, total concentration of cerium ion and zirconium ion is 0.4mol/L), drip whipping process and continue 15min, continue to stir 10min and mix rear dropping 5ml, the nitric acid of 1mol/L is 5 ~ 6 to pH, stir 30min ageing again, the conductive black getting 0.05g 10 ~ 100nm particle diameter is dispersed in above-mentioned coagulant liquid, stir ageing 20min, the pretreated cordierite honeycomb ceramic of heat-obtaining is impregnated in above-mentioned solution, dipping 5min, then take out hair-dryer and dry up raffinate, dry 10h for 80 DEG C, 700 DEG C of calcining 3h, obtain the Ce that load capacity is 4.6%
0.5zr
0.5o
2the cordierite of coating, wherein conductive black accounts for Ce
0.5zr
0.5o
20.5% of coating weight.
(3) get 20ml, the manganese nitrate solution of 0.08mol, 34.64g, 0.08mol lanthanum nitrate is dissolved in (wherein, total concentration of La and Mn ion is 2.6mol/L) in 40ml water jointly, and ultrasonic disperse 30min, gets containing Ce
0.5zr
0.5o
2the cordierite of coating is impregnated in above-mentioned solution, then takes out, dries up raffinate with hair-dryer, dries 20h for 70 DEG C, and once, 700 DEG C of calcining 6h, obtain the LaMnO that load capacity is 8% to repeated impregnations
3cordierite-base catalyst.
Embodiment 4:
(1) heat treatment of cordierite-base ceramic honey comb is in the same manner as in Example 1.
(2) 6.94g is got, 0.016mol cerous nitrate, 1.31g, 0.004mol zirconium-n-propylate, ultrasonicly respectively be dissolved in 90ml normal propyl alcohol solution, then by containing the solution of zirconium in 60 DEG C of solution be added drop-wise under agitation containing cerium (wherein, total concentration of cerium ion and zirconium ion is 0.1mol/L), drip process lasts 30min, continue to stir 40min and mix rear dropping 5ml, the nitric acid of 1mol/L is 5 ~ 6 to pH, stir 40min ageing again, the conductive black getting 0.125g 10 ~ 100nm particle diameter is dispersed in above-mentioned coagulant liquid, stir ageing 50min, the pretreated cordierite honeycomb ceramic of heat-obtaining is impregnated in above-mentioned solution, take out, hair-dryer dries up raffinate, dry 10h for 80 DEG C, 600 DEG C of calcining 3h, obtain the Ce that load capacity is 1.1%
0.8zr
0.2o
2the cordierite of coating, wherein conductive black accounts for Ce
0.8zr
0.2o
25.0% of coating weight.
(3) 2.5ml is got, the manganese nitrate solution of 0.01mol, 3.465g, 0.008mol lanthanum nitrate and 0.423g, 0.002mol strontium nitrate are dissolved in (wherein, total concentration of metal ion is 0.38mol/L) in 50ml water jointly, ultrasonic disperse 30min, gets containing Ce
0.8zr
0.2o
2the cordierite of coating is impregnated in above-mentioned solution, then takes out, dries up raffinate with hair-dryer, dries 8h for 80 DEG C, and 700 DEG C of calcining 3h, obtain the La that load capacity is 1%
0.8sr
0.2mnO
3cordierite-base catalyst.
Embodiment 5:
(1) heat treatment of cordierite-base ceramic honey comb is in the same manner as in Example 1.
(2) 27.76g is got, 0.064mol cerous nitrate, 5.24g, 0.016mol zirconium iso-propoxide, ultrasonicly respectively be dissolved in 90ml aqueous isopropanol, then by containing zirconium solution under agitation in 80 DEG C of solution be added drop-wise to containing cerium (wherein, total concentration of cerium ion and zirconium ion is 0.4mol/L), drip process lasts 30min, continue to stir 30min and mix rear dropping 5ml, the nitric acid of 1mol/L is 5 ~ 6 to pH, stir 25min ageing again, the pretreated cordierite honeycomb ceramic of heat-obtaining is impregnated in above-mentioned solution, then take out hair-dryer and dry up raffinate, dry 10h for 60 DEG C, repeated impregnations once, 700 DEG C of calcining 6h, obtain the Ce that load capacity is 4.6%
0.8zr
0.2o
2the cordierite of coating.
(3) 16ml is got, the manganese nitrate solution of 0.064mol, 4.656g, 0.016mol cobalt nitrate and 34.64g, 0.08mol lanthanum nitrate are dissolved in (wherein, total concentration of metal ion is 2.6mol/L) in the mixed liquor of 20ml water and 30ml ethanol jointly, ultrasonic disperse 30min, gets containing Ce
0.8zr
0.2o
2the cordierite of coating is impregnated in above-mentioned solution, then takes out, dries up raffinate with hair-dryer, dries 24h for 70 DEG C, and 600 DEG C of calcining 6h, obtain the LaMn that load capacity is 8%
0.8co
0.2o
3cordierite-base catalyst.
Embodiment 6:
(1) heat treatment of cordierite-base ceramic honey comb is in the same manner as in Example 1, wherein heats 60 DEG C, maintains 8h.
(2) 17.36g is got, 0.04mol cerous nitrate, 13.1g, 0.04mol zirconium iso-propoxide, ultrasonicly respectively be dissolved in 90ml normal propyl alcohol solution, then by the solution that is added drop-wise under agitation containing the solution of zirconium containing cerium (wherein, total concentration of cerium ion and zirconium ion is 0.4mol/L), drip process lasts 35min, continue to stir 10min and mix rear dropping 5ml, the nitric acid of 1mol/L is 5 ~ 6 to pH, stir 10min ageing again, the pretreated cordierite honeycomb ceramic of heat-obtaining is impregnated in above-mentioned solution, then take out hair-dryer and dry up raffinate, dry 4h for 80 DEG C, 700 DEG C of calcining 5h, obtain the Ce that load capacity is 4.6%
0.5zr
0.5o
2the cordierite of coating.
(3) 16ml is got, the manganese nitrate solution of 0.064mol, 4.656g, 0.016mol cobalt nitrate, 27.712g, 0.064mol lanthanum nitrate and 3.384g, 0.016mol strontium nitrate to be dissolved in 100ml water (wherein jointly, total concentration of metal ion is 1.38mol/L), ultrasonic disperse 30min, gets containing Ce
0.5zr
0.5o
2the cordierite of coating is impregnated in above-mentioned solution, then takes out, dries up raffinate with hair-dryer, dries 20h for 70 DEG C, and 700 DEG C of calcining 6h, obtain the La that load capacity is 8%
0.8sr
0.2mn
0.8co
0.2o
3cordierite-base catalyst.
Embodiment 7:
(1) heat treatment of cordierite-base ceramic honey comb is in the same manner as in Example 1, wherein heats 80 DEG C, maintains 8h.
(2) 8.68g is got, 0.02mol cerous nitrate is dissolved in 180ml aqueous isopropanol (wherein, the total concentration of metal ion is 0.11mol/L), drips process lasts 35min, continue to stir 10min and mix rear dropping 5ml, the nitric acid of 1mol/L is 5 ~ 6 to pH, then stirs 10min ageing, and the pretreated cordierite honeycomb ceramic of heat-obtaining is impregnated in above-mentioned solution, then take out hair-dryer and dry up raffinate, dry 10h for 80 DEG C, 600 DEG C of calcining 6h, obtain the CeO that load capacity is 1%
2the cordierite of coating.
(3) 10ml is got, the manganese nitrate solution of 0.04mol, 17.32g, 0.04mol lanthanum nitrate is dissolved in (wherein, the volume ratio of water and ethanol is 1:1, and total concentration of metal ion is 1.3mol/L) in the mixed liquor of 50ml water and ethanol jointly, ultrasonic disperse 30min, gets containing CeO
2the cordierite of coating is impregnated in above-mentioned solution, then takes out, dries up raffinate with hair-dryer, dries 10h for 70 DEG C, and 500 DEG C of calcining 6h, obtain the LaMnO that load capacity is 4%
3cordierite-base catalyst.
Embodiment 8:
Except in the gel slurries of the tie coat of configuration in step (2), cerium ion and zirconium ion mol ratio are 0.1:0.9, and total concentration of cerium ion and zirconium ion is 0.5mol/L, are 3 ~ 4 with the nitric acid of 0.5mol/L to pH; The concentration of metal ion total in active component solution in step (3) is 3mol/L, and the volume ratio of water and propyl alcohol is outside 0.2:1, and other steps are all in the same manner as in Example 1, Ce in the catalyst prepared
0.1zr
0.9o
2load capacity be 5%, LaMnO
3load capacity be 8%.
Embodiment 9:
Except the nitric acid of step (2) middle 1.5mol/L is 4 ~ 5 to pH; The concentration of metal ion total in active component solution in step (3) is 0.3mol/L, the volume ratio of water and alcohols solvent (mixture of ethanol and propyl alcohol) is outside 5:1, other steps are all in the same manner as in Example 1, Ce in the catalyst prepared
0.5zr
0.5o
2load capacity be 2.3%, LaMnO
3load capacity be 1%.
Comparative example 1:
With the embodiment 1 in CN 101439290A as a comparison case 1.
Comparative example 2:
Only adopt mode coated tie coat on cordierite-base ceramic honey comb of coagulant liquid dipping, and not coated active ingredient layer, other steps are all in the same manner as in Example 1.
Comparative example 3:
Only coated active ingredient layer on cordierite-base ceramic honey comb, and not coated tie coat, other steps are all in the same manner as in Example 1.
The monoblock type iolite honeycomb ceramic catalyst prepared in above-described embodiment 1-9 and comparative example 1-3 is cut into 16 × 10 × 25mm size and carries out activity rating, catalyst sample is filled in internal diameter 20mm crystal reaction tube, tests and carries out in temperature programming fixed bed reactors.Catalyst activity appreciation condition is as follows: benzene 150ppm, 1000ppm, toluene 150ppm, paraxylene 150ppm, ethyl acetate 1000ppm, and Balance Air is synthesis of air, air speed (GHSV) 4500h
-1.Shimadzu chromatogram, joins two-way fid detector and methane reborner, carries out on-line analysis and detects gas concentration.
Each catalyst sample active testing result is as shown in table 1,2 and Fig. 1: table 1 is catalyst benzene clean-up effect in embodiment 1-9 and comparative example 1-3, table 2 is catalyst benzene in embodiment 3, toluene, paraxylene, ethyl acetate clean-up effect, and Fig. 1 is catalyst sample catalysis benzene heat endurance and influence of moisture result figure in embodiment 3.Wherein, in Fig. 1, abscissa represents 24h in 1 day, and 2 represent 48h, the like; Reaction condition is fixed bed heating-up temperature 400 DEG C, benzene 1000ppm, flow velocity 300mL/min, air speed 4500h
-1.As can be seen from Figure 1, the better heat stability of catalyst prepared by the present invention, the high concentration benzene catalysis test carried out 8 days still can keep the purification efficiency of more than 99%, and 1.5% steam add the only faint transformation efficiency reducing benzene, after removing steam, purification efficiency returns to 99% from 97% again.
Catalyst benzene clean-up effect in table 1: embodiment 1-9 and comparative example 1-3
| Sample | T 10/℃ | T 50/℃ | T 90/℃ |
| Embodiment 1 | 228 | 265 | 330 |
| Embodiment 2 | 232 | 263 | 336 |
| Embodiment 3 | 201 | 242 | 315 |
| Embodiment 4 | 228 | 277 | 347 |
| Embodiment 5 | 214 | 260 | 324 |
| Embodiment 6 | 212 | 254 | 321 |
| Embodiment 7 | 245 | 306 | 427 |
| Embodiment 8 | 220 | 258 | 327 |
| Embodiment 9 | 242 | 297 | 380 |
| Comparative example 1 | 240 | 290 | 310 |
| Comparative example 2 | 342 | 476 | 570 |
| Comparative example 3 | 295 | 330 | 432 |
Note: 1) T
10/ DEG C, T
50/ DEG C and T
90/ represent DEG C respectively the temperature of the beds that conversion ratio is corresponding when being 10%, 50% and 90%.
Table 2: catalyst benzene, toluene, paraxylene, ethyl acetate clean-up effect in embodiment 3
| VOCs | Concentration ppm | T 10/℃ | T 50/℃ | T 90/℃ |
| Benzene | 150 | 209 | 236 | 311 |
| Toluene | 150 | 195 | 225 | 267 |
| Paraxylene | 150 | 189 | 208 | 281 |
| Ethyl acetate | 1000 | 182 | 226 | 255 |
Note: reaction condition: flow velocity 300mL/min, air speed 4500h
-1.
Comprehensive the above results can be found out, the present invention adopts the Ce of coagulant liquid preparation catalyst
xzr
1-xo
2tie coat, avoids previously prepared Ce
xzr
1-xo
2composite oxide power stirs again or high speed shear causes dispersion is uneven, thus the problem such as the coating caused is uneven and easily come off; And Ce has and stores the activity that oxygen function can strengthen catalyst.Floating coat of the present invention has high-specific surface area, with basal body binding force jail, the load capacity of active component can be increased, the high-temperature hot between active component and substrate can be avoided again to interact, and synergy promotes catalytic effect between coating and active component, the catalyst prepared conversion ratio in catalysis benzene purification process is that the temperature of beds corresponding when 10%, 50% and 90% is respectively lower than 250 DEG C, 310 DEG C and 427 DEG C, after purification, the concentration of benzene, toluene and paraxylene is all low to moderate 80ppm, obtains good clean-up effect.
Applicant states, the present invention illustrates process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned processing step, does not namely mean that the present invention must rely on above-mentioned processing step and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of raw material selected by the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a cordierite monolithic catalyst, is characterized in that, described catalyst with cordierite-base ceramic honey comb for carrier, coated tie coat and active component successively on carrier;
Tie coat comprises conductive black and has the oxide of following structure: Ce
mzr
1-mo
2, and 0 < m≤1;
Active component is La
1-xsr
xco
ymn
1-yo
3, 0≤x≤0.2,0≤y≤0.2;
The mass ratio of carrier, tie coat and active component is 1:(0.01 ~ 0.05): (0.01 ~ 0.08).
2. cordierite monolithic catalyst according to claim 1, is characterized in that, described tie coat comprises following component by mass percentage:
Ce
mZr
1-mO
295～100％
Conductive black 0 ~ 5%
Described Ce
mzr
1-mo
2be 100% with the mass percent sum of conductive black;
Preferably, described Ce
mzr
1-mo
2in 0.2≤m≤0.7, more preferably m=0.5.
3. cordierite monolithic catalyst according to claim 1 and 2, is characterized in that, described active component La
1-xsr
xco
ymn
1-yo
3in 0.05≤x≤0.1,0.02≤y≤0.08;
Preferably, the mass ratio of described carrier, tie coat and active component is 1:(0.02 ~ 0.04): (0.02 ~ 0.05), more preferably 1:0.02:0.04;
Preferably, described cordierite-base ceramic honey comb is square and/or circular;
Preferably, the perforate on described cordierite-base ceramic honey comb be hexagon, circle or square in any one;
Preferably, described cordierite-base ceramic honey comb is square duration is 5 ~ 15cm, more preferably 10cm;
Preferably, wide when described cordierite-base ceramic honey comb is square is 5 ~ 15cm, more preferably 10cm;
Preferably, high when described cordierite-base ceramic honey comb is square is 5 ~ 10cm, more preferably 5cm;
Preferably, the hole count of described cordierite-base ceramic honey comb is 5 ~ 14 holes/cm
2;
Preferably, described tie coat adopts the mode of coagulant liquid dipping to be coated on carrier.
4. the preparation method of the cordierite monolithic catalyst according to any one of claim 1-3, is characterized in that, said method comprising the steps of:
(1) be immersed in through heat treated cordierite-base ceramic honey comb in the gel slurries of tie coat, take out, dry up, dry and roasting, obtain the cordierite-base ceramic honey comb being coated with tie coat;
(2) be immersed in the maceration extract containing active component by the cordierite-base ceramic honey comb being coated with tie coat, then taking-up, dry and roasting, obtain cordierite monolithic catalyst.
5. preparation method according to claim 4, is characterized in that, in step (1), the heat treatment of cordierite-base ceramic honey comb is:
Cordierite-base ceramic honey comb is placed in drying box, dry 1 ~ 8h at 60 ~ 80 DEG C.
6. the preparation method according to claim 4 or 5, is characterized in that, in step (1), the preparation method of the gel slurries of tie coat is:
Cerium salt is dissolved in solvent and forms solution A, the alkoxide of zirconium is dissolved in solvent and forms solution B, solution B is dripped in solution A, at 25 ~ 80 DEG C, stir 0.5 ~ 3h, then add conductive black under agitation, obtain the gel slurries of tie coat;
Preferably, described cerium salt is the combination of any one or at least two kinds in cerous nitrate, cerous acetate, cerous sulfate or cerium chloride;
Preferably, the alkoxide of described zirconium is zirconium-n-propylate and/or zirconium iso-propoxide;
Preferably, described solvent is normal propyl alcohol and/or isopropyl alcohol;
Preferably, the pH regulating solution while stirring 0.5 ~ 3h at 25 ~ 80 DEG C is 3 ~ 6;
Preferably, the pH of nitre acid-conditioning solution is dripped while stirring 0.5 ~ 3h at 25 ~ 80 DEG C;
Preferably, the concentration of the nitric acid of dropping is 0.5 ~ 1.5mol/L, is preferably 1mol/L;
Preferably, the particle diameter of the conductive black added is 10 ~ 100nm;
Preferably, in the gel slurries of tie coat, total concentration of cerium ion and zirconium ion is 0.1 ~ 0.5mol/L.
7. the preparation method according to any one of claim 4-6, is characterized in that, 5 ~ 10min in the gel slurries being immersed in tie coat through heat treated cordierite-base ceramic honey comb takes out by step (1) again;
Preferably, the baking temperature in step (1) is 60 ~ 80 DEG C;
Preferably, the drying time in step (1) is 8 ~ 24h;
Preferably, the sintering temperature in step (1) is 500 ~ 700 DEG C;
Preferably, the roasting time in step (1) is 3 ~ 6h;
Preferably, what obtain in step (1) is coated with Ce in the cordierite-base ceramic honey comb of tie coat
mzr
1-mo
2quality be 1 ~ 5% of cordierite-base ceramic honey comb quality;
Preferably, the quality being coated with conductive black in the cordierite-base ceramic honey comb of tie coat obtained in step (1) is Ce
mzr
1-mo
20 ~ 5%.
8. the preparation method according to any one of claim 4-7, is characterized in that, the preparation method of the maceration extract containing active component in step (2) is:
By La salt, Sr salt, Mn salt and Co salt ultrasonic disperse in the mixed solvent of water and alcohols solvent, obtain the maceration extract containing active component;
Preferably, described La salt is the combination of any one or at least two kinds in the nitrate of La, sulfate or chlorate;
Preferably, described Sr salt is the combination of any one or at least two kinds in the nitrate of Sr, sulfate or chlorate;
Preferably, described Mn salt is the combination of any one or at least two kinds in the nitrate of Mn, sulfate or chlorate;
Preferably, described Co salt is the combination of any one or at least two kinds in the nitrate of Co, sulfate or chlorate;
Preferably, the ion mol ratio controlling (La+Sr) and (Mn+Co) in the maceration extract containing active component is 1:1;
Preferably, the ion mol ratio controlling Sr and (La+Sr) in the maceration extract containing active component is (0 ~ 0.2): 1;
Preferably, the ion mol ratio controlling Co and (Mn+Co) in the maceration extract containing active component is (0 ~ 0.2): 1;
Preferably, in the mixed solvent of described water and alcohols solvent, the volume ratio of water and alcohols solvent is (0.2 ~ 5): 1;
Preferably, described alcohols solvent is ethanol and/or propyl alcohol;
Preferably, described water is deionized water;
Preferably, described is 0.3 ~ 3mol/L containing total concentration of La, Sr, Mn and Co ion in the maceration extract of active component.
9. the preparation method according to any one of claim 4-8, is characterized in that, temperature dry in step (2) is 60 ~ 80 DEG C;
Preferably, dry in step (2) time is 8 ~ 24h;
Preferably, in step (2), the temperature of roasting is 500 ~ 700 DEG C;
Preferably, in step (2), the time of roasting is 3 ~ 6h.
10. the purposes of the cordierite monolithic catalyst according to any one of claim 1-3, it to be applied in benzene,toluene,xylene in industrial organic exhaust gas, ethyl acetate or n-hexane the purification of any one or at least two kinds.
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Application publication date: 20151028 |
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