CN106475105A - A kind of double-perovskite type O composite metallic oxide catalyst and preparation method and application - Google Patents
A kind of double-perovskite type O composite metallic oxide catalyst and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of double-perovskite type O composite metallic oxide catalyst and preparation method and application, belong to technical field of atmospheric pollution control.The skeleton symbol of this double-perovskite type O composite metallic oxide catalyst is A2B2O6, A position is La, Sr or Ce, and B position is Mn, Fe, Co, Cu or Ni.This catalyst has excellent heat-resisting quantity, water-resistance and resistance against chlorine, can apply to effective degraded of CVOCs under industrial high temperature environment.This catalyst reaction temperature be 500 550 DEG C, reaction velocity be 20000 30000h‑1, oxygen concentration be 10 20% under the conditions of can achieve Typical Industrial CVOCs (1,2 dichloroethanes) complete oxidation.Pass through the load capacity of modulation transition metal oxide simultaneously, can effectively improve the oxidation efficiency of catalyst, increase substantially product CO2Selectivity.Process for synthetic catalyst involved in the present invention is simple, and the prices of raw materials are cheap, have good industrial applications prospect.
Description
Technical field
The invention belongs to technical field of atmospheric pollution control is and in particular to a kind of double-perovskite type metal composite oxide is urged
Agent and preparation method and application.
Background technology
VOC (VOCs), refers to volatile at normal temperatures and pressures, saturated vapour pressure is more than 70Pa or boiling
O'clock between 50~260 DEG C of non-methane organic compound general name.Wherein, chloride volatile organic contaminant (CVOCs) is
In VOCs, a modal class, mainly includes chlorobenzene, dichloromethane, carbon tetrachloride, dichloroethanes, trichloroethane etc..1,2- bis-
Ethyl chloride (DCE), is a kind of colourless liquid having chloroform taste, is slightly soluble in water.It is a kind of important chemical raw material, is raw
Produce vinyl chloride, the intermediate of 1,1,1- trichloroethane, trichloro ethylene and tetrachloroethylene;(metal takes off to be also used as industrial products
Fat agent) solvent;DCE can be also used for removing the lead in gasoline, cleaning yarn fabric and industrial equipment, processing animals fat, kills
Worm agent and medicine etc..It is reported that, the DCE of annual 3000000 tons of the mean consumption of China, wherein more than 90% DCE are used for producing
Vinyl chloride (VC).
The discharge of substantial amounts of CVOCs, not only causes atmosphere quality to decline, and the CVOCs entering human body can destroy
The immune system of human body, produces impact to the function of kidney and respiratory system, increases human body (brain, pancreas, lymph, hemopoietic stomach function regulating
The tissues such as portion and organ) carcinogenic risk.?《Key area prevention and control of air pollution " 12 " is planned》In it is desirable to carry out two
On the basis of sulfur oxide, nitrogen oxides overall control, increasing newly will to the control of smoke-dust and volatile organic contaminant (VOCs)
Ask.2015, Environmental Protection Department was issued《Environmental Protection Department issues environmental conservation synthesis register》, wherein " high pollution, high environment
In risk " product register, contain and 30, plant the product producing a large amount of VOCs more.
The Treatment process of CVOCs can be divided into absorption method and edman degradation Edman.Absorption method is by pressurization, cooling, and adsorbent absorbs,
CVOCs Fraction collection in industrial waste gas is got up by the physics modes such as adsorbent, thus realizing the process recycling, such as condenses
Method, absorption method and absorption process etc..Edman degradation Edman mainly include photocatalytic method, plasma method, biological treatment, catalysis oxidation
The chemistry such as method or biological means.In view of technical costss problem, high concentration CVOCs takes absorption method to process, the employing of low concentration
Edman degradation Edman is processed.High selectivity (desired product CO of catalytic oxidation2、H2O、Cl2And HCl) can greatly reduce the product of CVOCs
Toxicity, reaches the environmental disruption of minimum.The research and development of inexpensive high thermal stability and chlorine resistance material are that industrial CVOCs is high
One of bottleneck problem that effect controls.Chlorine species in CVOCs catabolite are easily distributed with the activearm on most of catalyst
Raw reaction, destroys active phase, reduces catalyst activity.Flue-gas temperature in the commercial production such as metallurgy, chemical industry, building materials is higher than 300
DEG C, (industrial heat accumulating type catalytic combustion method (RCO) operation temperature is often beyond 500 DEG C), Typical precious metal catalyst or transition gold
Genus oxide catalyst runs under this hot environment for a long time and easily leads to sintering of catalyst and inactivation.
Content of the invention
For the defect overcoming above-mentioned prior art to exist, it is an object of the invention to provide a kind of double-perovskite type is combined
Metal oxide catalyst and preparation method and application, this catalyst has in excellent high temperature resistant, water resistant impact and anti-chlorine
Toxicity energy;This preparation method is simple to operate, and raw material is easy to get, suitable large-scale production;This catalyst can apply to industrial smoke
The efficient oxidation of middle CVOCs removes.
The present invention is to be achieved through the following technical solutions:
A kind of double-perovskite type O composite metallic oxide catalyst, this double-perovskite type O composite metallic oxide catalyst
Skeleton symbol is A2B2O6, A position is La, Sr or Ce, and B position is Mn, Fe, Co, Cu or Ni.
Carry out transition metal oxide on the surface of described double-perovskite type O composite metallic oxide catalyst loaded modified,
The load capacity of transition metal oxide is the oxo transition metal of double-perovskite type O composite metallic oxide catalyst quality and load
The 5~20% of compound quality summation.
Described transition metal oxide is CrOx、MnOxOr CuOx.
The invention also discloses the method preparing above-mentioned double-perovskite type O composite metallic oxide catalyst, including following
Step:
1) press the mol ratio of skeleton symbol, take the nitrate of metallic element or acetate to be dissolved in as under precursor, room temperature
In water, agitating solution is to clear state;
2) press citric acid:Total metal ion number=1~2:1 mol ratio, by citric acid add step 1) be obtained solution
In, agitating solution is to clear state;
3) by step 2) be obtained solution at 70~90 DEG C heating in water bath, magnetic agitation to solution be in gel state;
4) by step 3) after the sample that is obtained dries 12~24h at 80~120 DEG C, at 500~600 DEG C roasting 2~
4h, then in 1100-1200 DEG C of roasting 2~4h, obtains double-perovskite type O composite metallic oxide catalyst.
Also include carrying out loaded modified operation to the double-perovskite type O composite metallic oxide catalyst obtaining, specifically such as
Under:Double-perovskite type O composite metallic oxide catalyst be impregnated in chromic nitrate or the copper nitrate solution of 0.5~1.5mol/L,
After 10-30min is stirred at room temperature, dry 12~24h at 80~120 DEG C, then roasting 4~5h at 500~600 DEG C, obtains
Loaded modified double-perovskite type O composite metallic oxide catalyst.
The invention also discloses above-mentioned double-perovskite type O composite metallic oxide catalyst declines in industrial high temperature environment
Solve the application in chloride VOC CVOCs.
At 500~600 DEG C, reaction velocity is 20000-30000h-1, under the conditions of oxygen concentration is 10-20%, described double
Ca-Ti ore type O composite metallic oxide catalyst catalysis oxidation 1, the efficiency of 2- dichloroethanes reaches 100%.
Under 500~550 DEG C and steam 2%~5% existence condition, this double-perovskite type O composite metallic oxide catalyst
There is stable chlorine resistance, heat-resisting quantity and water-resistance.
Compared with prior art, the present invention has following beneficial technique effect:
Double-perovskite type O composite metallic oxide catalyst disclosed by the invention, skeleton symbol is A2B2O6, wherein A position can be alkali
Soil or rare earth metal (La, Sr, Ce), B position can be transition metal (Mn, Fe, Co, Cu, Ni).This catalyst has excellent
Heat-resisting quantity, water-resistance and resistance against chlorine, successive reaction 700min rear catalyst activity and selectivity is no decreased obviously.Can answer
Effective degraded for CVOCs under industrial high temperature environment.Further, carry out carrying transition metal oxidation in this catalyst surface
Thing (CrOx、MnOx、CuOx) optimize modification, by the load capacity of modulation transition metal oxide, can effectively improve catalyst
Oxidation efficiency, increases substantially product CO2Selectivity.
Meanwhile, double-perovskite type O composite metallic oxide catalyst synthetic method disclosed in this invention is simple, raw material
Cheap, there is good industrial applications prospect.
Double-perovskite type O composite metallic oxide catalyst disclosed by the invention can be efficiently applied to industrial high temperature environment
The chloride VOC CVOCs of lower degraded, reaction temperature be 500-550 DEG C, reaction velocity be 20000-30000h-1, oxygen concentration be 10-20%, catalysis oxidation 1, the efficiency of 2- dichloroethanes reaches 100%.And at high temperature (500-550 DEG C)
Under steam (2-5%) existence condition, excellent stability can be kept for a long time.
Brief description
Fig. 1 is the double-perovskite type catalyst La of the present invention2CuNiO6, LaCeFeCoO6, LaSrMnCoO6, 10CuOx/
LaSrMnCoO6And 10CrOx/LaSrMnCoO6Active testing curve;
Fig. 2 is double-perovskite type catalyst 10CrOx/LaSrMnCoO in the present invention6Stability test curve
(700min).
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, described be explanation of the invention and
It is not to limit.
Embodiment 1
First, in molar ratio 2:1:1 weighs Lanthanum (III) nitrate, Schweinfurt green and nickel nitrate for presoma, and room-temperature dissolution goes in 10mL
In ionized water, agitating solution is to clear state;Then, according to citric acid:Total metal ion number (mol ratio)=1.5, by Fructus Citri Limoniae
Acid adds in above-mentioned solution, and agitating solution is to clear state;Afterwards, by resulting solution, water-bath at 70 DEG C, magnetic agitation is extremely molten
Liquid is in gel state;Then, gel is dried at 100 DEG C 24h;Finally by gained solid at 500 DEG C roasting 4h, 1100
DEG C roasting 4h, is down to room temperature, gained catalyst is designated as La2CuNiO6.
Catalytic reaction is carried out in fixed bed, takes the La of 0.5g2CuNiO6, make (DCE) for probe gas with 1,2- dichloroethanes
Body, the concentration of reactant controls in 400ppm, and reaction velocity is 24000h-1, oxygen concentration is 20%, and reaction is in each temperature spot
Keep 40min, product is analyzed through gas chromatogram and on-line mass spectroscopy.Test result indicate that, 200 DEG C, 250 DEG C, 300 DEG C,
At 350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C and 550 DEG C, transformation efficiency is respectively 0%, 8%, 10%, 30%, 32%, 41%,
50% and 56% about.
Embodiment 2
First, in molar ratio 1:1:1:1 weighs Lanthanum (III) nitrate, cerous nitrate, ferric nitrate and cobalt nitrate for presoma, room-temperature dissolution
In 10mL deionized water, agitating solution is to clear state;Then, according to citric acid:Total metal ion number (mol ratio)=
1.5, citric acid is added in above-mentioned solution, agitating solution is to clear state;Afterwards, by resulting solution, water-bath at 70 DEG C, magnetic
It is in gel state that power stirs to solution;Then, gel is dried at 100 DEG C 24h;Finally gained solid is roasted at 500 DEG C
Burn 4h, in 1100 DEG C of roasting 4h, be down to room temperature, gained catalyst is designated as LaCeFeCoO6;
Catalytic reaction is carried out in fixed bed, takes the LaCeFeCoO of 0.5g6, equally using DCE as probe gas, react
Condition is identical with embodiment 1, test result indicate that, 200 DEG C, 250 DEG C, 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C and
At 550 DEG C, the changing effect of catalyst is respectively 0%, 9%, 13%, 32%, 35%, 43%, 53%, 62% about.
Embodiment 3
First, in molar ratio 1:1:1:1 weighs Lanthanum (III) nitrate, strontium nitrate, manganese acetate and cobalt nitrate for presoma, room-temperature dissolution
In 10mL deionized water, agitating solution is to clear state;Then, according to citric acid:Total metal ion number (mol ratio)=
1.5, citric acid is added in above-mentioned solution, agitating solution is to clear state;Afterwards, by resulting solution, water-bath at 70 DEG C, magnetic
It is in gel state that power stirs to solution;Then, gel is dried at 100 DEG C 24h;Finally gained solid is roasted at 550 DEG C
Burn 4h, in 1100 DEG C of roasting 4h, be down to room temperature, gained catalyst is designated as LaSrMnCoO6;
Catalytic reaction is carried out in fixed bed, takes the LaSrMnCoO of 0.5g6, equally using DCE as probe gas, react
Condition is identical with embodiment 1, test result indicate that, 200 DEG C, 250 DEG C, 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C and
At 550 DEG C, the changing effect of catalyst is respectively 0%, 10%, 13%, 35%, 38%, 46%, 55% and 68% about,
CO at 550 DEG C2Selectivity can reach more than 40%, HCl selectivity be 23% about.
Embodiment 4
Take the copper nitrate solution of 5mL0.8mol/L first, add the LaSrMnCoO of preparation in 2g embodiment 36, room temperature stirs
Mix 30min;Then, gained sample is dried 12h at 80 DEG C;Finally, by the solid of gained in Muffle furnace 500 DEG C of roasting 4h,
It is down to room temperature, gained catalyst is designated as 10CuOx/LaSrMnCoO6.
Using DCE as probe gas, take 0.5g10CuOx/LaSrMnCoO6, other conditions are identical with embodiment 1, are lived
Property test, temperature be 200 DEG C, 250 DEG C, 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C, under the conditions of 550 DEG C, conversion ratio is
8%, 12%, 38%, 50%, 86%, 92%, 96% and 100%, CO under the conditions of 550 DEG C2Selectivity to reach 68% left
The right side, the selectivity 50% about of HCl is it will be apparent that improve CO2Selectivity with HCl.
Embodiment 5
Take the chromium nitrate solution of 5mL 0.8mol/L first, add the LaSrMnCoO of preparation in 2g embodiment 36, room temperature stirs
Mix 30min;Then, gained sample is dried 12h at 80 DEG C;Finally, by the solid of gained in Muffle furnace 500 DEG C of roasting 4h,
It is down to room temperature, gained catalyst is designated as 10CrOx/LaSrMnCoO6.
Using DCE as probe gas, take the 10CrOx/LaSrMnCoO of 0.5g6, other conditions are identical with embodiment 1, enter
Row active testing, temperature be 200 DEG C, 250 DEG C, 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C, under the conditions of 500 DEG C, conversion ratio is
9%, 18%, 40%, 70%, 90%, 98% and 100% about, CO under the conditions of 550 DEG C2Selectivity reach 70% about,
The selectivity of HCl is 56% about it will be apparent that improve CO2Selectivity with HCl.
The double-perovskite type catalyst La that each embodiment above is obtained2CuNiO6, LaCeFeCoO6, LaSrMnCoO6,
10CuOx/LaSrMnCoO6And 10CrOx/LaSrMnCoO6Active testing curve is referring to Fig. 1.
Embodiment 6
The stability test of catalyst maintains and carries out at 550 DEG C, the other conditions of selective response keep constant (with enforcement
Example 1 is identical), 10CrOx/LaSrMnCoO6Show excellent stability.Referring to Fig. 2, reaction, after 250min, is catalyzed
Agent activity still can keep 97% about, and afterwards, reaction proceeds to 700min, and catalyst activity remains to 80% about, table
Reveal excellent high temperature resistant and anti-chlorine stability.
Embodiment 7
The water resistance test of catalyst is carried out in fixed bed, and catalyst choice is 10CrOx/LaSrMnCoO6Reaction temperature
Degree is maintained at 550 DEG C, and other test conditions are same as Example 1, and steam blows into reactor by constant temperature Bubbling method, by quality
Effusion meter controls the content of steam, and the content of steam is 2-5%, and through 120min, catalyst activity is decreased obviously, keep
95% about;Close steam activation recovering to 98% about, afterwards, increase the content of steam, reactivity drops to 90%
Left and right;Close steam, the activation recovering of catalyst to 93% about.
In sum, catalyst disclosed by the invention has excellent heat-resisting quantity, water-resistance and resistance against chlorine, Ke Yiying
Effective degraded for CVOCs under industrial high temperature environment.This catalyst reaction temperature be 500-550 DEG C, reaction velocity be
20000-30000h-1, oxygen concentration be 10-20% under the conditions of can achieve Typical Industrial CVOCs (1,2- dichloroethanes) complete
Oxidation.Pass through the load capacity of modulation transition metal oxide simultaneously, can effectively improve the oxidation efficiency of catalyst, significantly carry
High product CO2Selectivity.This catalysis material has good heat stability and water resistant impact capacity, successive reaction
700min rear catalyst activity and selectivity is no decreased obviously.Meanwhile, process for synthetic catalyst involved in the present invention is simple, former material
Material is cheap, has good industrial applications prospect.
Claims (8)
1. a kind of double-perovskite type O composite metallic oxide catalyst is it is characterised in that this double-perovskite type composition metal aoxidizes
The skeleton symbol of thing catalyst is A2B2O6, A position is La, Sr or Ce, and B position is Mn, Fe, Co, Cu or Ni.
2. double-perovskite type O composite metallic oxide catalyst according to claim 1 is it is characterised in that in described pair of calcium
The surface of titanium ore type O composite metallic oxide catalyst carries out that transition metal oxide is loaded modified, transition metal oxide negative
Carrying capacity be double-perovskite type O composite metallic oxide catalyst quality with load transition metal oxide quality summation 5~
20%.
3. double-perovskite type O composite metallic oxide catalyst according to claim 2 is it is characterised in that described transition is golden
Genus oxide is CrOx、MnOxOr CuOx.
4. the method for the double-perovskite type O composite metallic oxide catalyst described in preparation claim 1 is it is characterised in that include
Following steps:
1) press the mol ratio of skeleton symbol, take the nitrate of metallic element or acetate to be dissolved in the water as under precursor, room temperature,
Agitating solution is to clear state;
2) press citric acid:Total metal ion number=1~2:1 mol ratio, by citric acid add step 1) be obtained solution in, stir
Mix solution to clear state;
3) by step 2) be obtained solution at 70~90 DEG C heating in water bath, magnetic agitation to solution be in gel state;
4) by step 3) be obtained sample dry 12~24h at 80~120 DEG C after, roasting 2~4h at 500~600 DEG C, so
Afterwards in 1100-1200 DEG C of roasting 2~4h, obtain double-perovskite type O composite metallic oxide catalyst.
5. the method for double-perovskite type O composite metallic oxide catalyst according to claim 4 is it is characterised in that also wrap
Include and loaded modified operation is carried out to the double-perovskite type O composite metallic oxide catalyst obtaining, specific as follows:By double calcium titaniums
Ore deposit type O composite metallic oxide catalyst impregnated in chromic nitrate or the copper nitrate solution of 0.5~1.5mol/L, and 10- is stirred at room temperature
After 30min, at 80~120 DEG C, dry 12~24h, then roasting 4~5h at 500~600 DEG C, obtain loaded modified double
Ca-Ti ore type O composite metallic oxide catalyst.
6. in claims 1 to 3 the double-perovskite type O composite metallic oxide catalyst described in any one in industrial high temperature ring
The application degraded under border in chloride VOC CVOCs.
7. application as claimed in claim 6 is it is characterised in that at 500~600 DEG C, reaction velocity is 20000-30000h-1, oxygen concentration be 10-20% under the conditions of, described double-perovskite type O composite metallic oxide catalyst catalysis oxidation 1,2- dichloro
The efficiency of ethane reaches 100%.
8. application as claimed in claim 6 is it is characterised in that under 500~550 DEG C and steam 2%~5% existence condition,
This double-perovskite type O composite metallic oxide catalyst has stable chlorine resistance, heat-resisting quantity and water-resistance.
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