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 PDF

Info

Publication number
CN106475105A
CN106475105A CN201610748894.1A CN201610748894A CN106475105A CN 106475105 A CN106475105 A CN 106475105A CN 201610748894 A CN201610748894 A CN 201610748894A CN 106475105 A CN106475105 A CN 106475105A
Authority
CN
China
Prior art keywords
double
metallic oxide
oxide catalyst
composite metallic
perovskite type
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.)
Granted
Application number
CN201610748894.1A
Other languages
Chinese (zh)
Other versions
CN106475105B (en
Inventor
何炽
徐碧涛
潘华
郑春莉
刘萍萍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Jiaotong University
Original Assignee
Xian Jiaotong University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Xian Jiaotong University filed Critical Xian Jiaotong University
Priority to CN201610748894.1A priority Critical patent/CN106475105B/en
Publication of CN106475105A publication Critical patent/CN106475105A/en
Application granted granted Critical
Publication of CN106475105B publication Critical patent/CN106475105B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8659Removing halogens or halogen compounds
    • B01D53/8662Organic halogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889Manganese, technetium or rhenium
    • B01J23/8892Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/20Halogens or halogen compounds
    • B01D2257/206Organic halogen compounds
    • B01D2257/2064Chlorine
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

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

A kind of double-perovskite type O composite metallic oxide catalyst and preparation method and application
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.
CN201610748894.1A 2016-08-26 2016-08-26 A kind of double-perovskite type O composite metallic oxide catalyst and the preparation method and application thereof Active CN106475105B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610748894.1A CN106475105B (en) 2016-08-26 2016-08-26 A kind of double-perovskite type O composite metallic oxide catalyst and the preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610748894.1A CN106475105B (en) 2016-08-26 2016-08-26 A kind of double-perovskite type O composite metallic oxide catalyst and the preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN106475105A true CN106475105A (en) 2017-03-08
CN106475105B CN106475105B (en) 2019-02-05

Family

ID=58273208

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610748894.1A Active CN106475105B (en) 2016-08-26 2016-08-26 A kind of double-perovskite type O composite metallic oxide catalyst and the preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN106475105B (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106964359A (en) * 2017-03-20 2017-07-21 西安交通大学 A kind of three-dimensional ordered macroporous perovskite type O composite metallic oxide catalyst and its preparation method and application
CN107952441A (en) * 2017-12-11 2018-04-24 大连理工大学 A kind of preparation method and applications of propane catalysis burning composite oxide catalysts
CN108048955A (en) * 2017-12-07 2018-05-18 北京理工大学 The preparation method of strontium iron molybdenum base double-perovskite type metal oxide nanofibres
CN108043419A (en) * 2017-12-12 2018-05-18 安徽大学 The flower-shaped paramagnetism high efficiency photocatalyst Ba of one species2FeMoO6:The preparation method of Dy
CN108404921A (en) * 2018-02-01 2018-08-17 华南理工大学 A kind of B superfluous Ruddlesden-Popper nano catalytic material
CN108889271A (en) * 2018-07-24 2018-11-27 德州智南针知识产权有限公司 Exhaust-gas treatment composite adsorbing material and preparation method thereof and purposes
CN109647420A (en) * 2018-12-27 2019-04-19 中国科学院广州地球化学研究所 Calcium analysis cobalt acid lanthanum perofskite type oxide and its preparation method and application for heat catalytic oxidation toluene
CN109675576A (en) * 2019-01-04 2019-04-26 中国科学院广州地球化学研究所 Sour modified calcium cation doping acid lanthanum perovskite type catalyst and preparation method thereof for heat catalytic oxidation toluene
CN110026185A (en) * 2018-11-23 2019-07-19 江苏中创清源科技有限公司 A kind of modified perovskite type catalyst and preparation method thereof
CN113070066A (en) * 2021-03-16 2021-07-06 西安交通大学 Catalytic material with cobalt-copper bimetallic oxide loaded on foamed nickel, preparation method and application
CN113244926A (en) * 2020-09-14 2021-08-13 昆明理工大学 Perovskite catalyst for synergistically catalyzing and oxidizing nitric oxide and mercury and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107497453B (en) * 2017-08-23 2019-12-03 昆明理工大学 One kind is for CO catalysis reduction SO2Composite catalyst preparation and Recovered sulphur method

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1885445A (en) * 2006-06-16 2006-12-27 中国科学院长春应用化学研究所 Method for preparing double perovskite magnetic material Sr2MWO6(M=Fe or Mn)
CN102441397A (en) * 2010-10-12 2012-05-09 中国石油化工股份有限公司 Chemical looping combustion double perovskite type oxide oxygen carrier and preparation method and application thereof
CN104607234A (en) * 2015-01-11 2015-05-13 北京化工大学 Molecular sieve-based catalyst used for dechloridation of methane chloride
CN105056962A (en) * 2015-08-05 2015-11-18 内蒙古大学 Preparation method of load-type rare earth double perovskite composite oxide photocatalyst and preparation method thereof
CN105107520A (en) * 2015-07-21 2015-12-02 新奥科技发展有限公司 Double perovskite type metal oxide catalyst and preparation method thereof
CN105289639A (en) * 2015-10-16 2016-02-03 上海纳米技术及应用国家工程研究中心有限公司 Cobalt-loaded lanthanum, manganese, calcium and titanium ore type nitric oxide oxidation catalyst and preparation method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1885445A (en) * 2006-06-16 2006-12-27 中国科学院长春应用化学研究所 Method for preparing double perovskite magnetic material Sr2MWO6(M=Fe or Mn)
CN102441397A (en) * 2010-10-12 2012-05-09 中国石油化工股份有限公司 Chemical looping combustion double perovskite type oxide oxygen carrier and preparation method and application thereof
CN104607234A (en) * 2015-01-11 2015-05-13 北京化工大学 Molecular sieve-based catalyst used for dechloridation of methane chloride
CN105107520A (en) * 2015-07-21 2015-12-02 新奥科技发展有限公司 Double perovskite type metal oxide catalyst and preparation method thereof
CN105056962A (en) * 2015-08-05 2015-11-18 内蒙古大学 Preparation method of load-type rare earth double perovskite composite oxide photocatalyst and preparation method thereof
CN105289639A (en) * 2015-10-16 2016-02-03 上海纳米技术及应用国家工程研究中心有限公司 Cobalt-loaded lanthanum, manganese, calcium and titanium ore type nitric oxide oxidation catalyst and preparation method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
SHU-XIA CHEN等: ""Enhanced activity for catalytic oxidation of 1,2-dichloroethane over Al-substituted LaMnO3 perovskite catalysts"", 《APPLIED SURFACE SCIENCE》 *
琚伟伟,李同伟著: "《复杂磁性材料电子性质及旋轨耦合效应》", 28 February 2015 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106964359A (en) * 2017-03-20 2017-07-21 西安交通大学 A kind of three-dimensional ordered macroporous perovskite type O composite metallic oxide catalyst and its preparation method and application
CN108048955B (en) * 2017-12-07 2020-03-10 北京理工大学 Preparation method of strontium iron molybdenum based double perovskite type metal oxide nano fiber
CN108048955A (en) * 2017-12-07 2018-05-18 北京理工大学 The preparation method of strontium iron molybdenum base double-perovskite type metal oxide nanofibres
CN107952441A (en) * 2017-12-11 2018-04-24 大连理工大学 A kind of preparation method and applications of propane catalysis burning composite oxide catalysts
CN108043419A (en) * 2017-12-12 2018-05-18 安徽大学 The flower-shaped paramagnetism high efficiency photocatalyst Ba of one species2FeMoO6:The preparation method of Dy
CN108043419B (en) * 2017-12-12 2020-08-25 安徽大学 Flower-like paramagnetic high-efficiency photocatalyst Ba2FeMoO6: preparation method of Dy
CN108404921A (en) * 2018-02-01 2018-08-17 华南理工大学 A kind of B superfluous Ruddlesden-Popper nano catalytic material
CN108889271A (en) * 2018-07-24 2018-11-27 德州智南针知识产权有限公司 Exhaust-gas treatment composite adsorbing material and preparation method thereof and purposes
CN110026185A (en) * 2018-11-23 2019-07-19 江苏中创清源科技有限公司 A kind of modified perovskite type catalyst and preparation method thereof
CN109647420A (en) * 2018-12-27 2019-04-19 中国科学院广州地球化学研究所 Calcium analysis cobalt acid lanthanum perofskite type oxide and its preparation method and application for heat catalytic oxidation toluene
CN109675576A (en) * 2019-01-04 2019-04-26 中国科学院广州地球化学研究所 Sour modified calcium cation doping acid lanthanum perovskite type catalyst and preparation method thereof for heat catalytic oxidation toluene
CN109675576B (en) * 2019-01-04 2021-07-20 中国科学院广州地球化学研究所 Acid modified calcium-doped lanthanum calcium cobaltite perovskite type catalyst for thermal catalytic oxidation of toluene and preparation method thereof
CN113244926A (en) * 2020-09-14 2021-08-13 昆明理工大学 Perovskite catalyst for synergistically catalyzing and oxidizing nitric oxide and mercury and preparation method thereof
CN113070066A (en) * 2021-03-16 2021-07-06 西安交通大学 Catalytic material with cobalt-copper bimetallic oxide loaded on foamed nickel, preparation method and application

Also Published As

Publication number Publication date
CN106475105B (en) 2019-02-05

Similar Documents

Publication Publication Date Title
CN106475105B (en) A kind of double-perovskite type O composite metallic oxide catalyst and the preparation method and application thereof
Tang et al. Low temperature selective catalytic reduction of NOx with NH3 over amorphous MnOx catalysts prepared by three methods
CN106925265B (en) A kind of transition metal composite oxide catalytic agent
CN106345523B (en) A kind of low-temperature denitration catalyst and preparation method thereof based on carbonization MOFs
CN106944092B (en) A kind of preparation method of the Fe-MnO2 catalyst with efficient photo-thermal concerted catalysis purifying VOCs
CN106391037B (en) One kind decomposing N for high-temperature catalytic2The preparation process of the catalyst of O
CN105833901B (en) A kind of PrOx-MnOx/ SAPO-34 low-temperature SCR catalyst for denitrating flue gas and the preparation method and application thereof
CN109364924B (en) Magnetic nano ozone catalyst CoFe2O4And preparation method and application thereof
CN107986382A (en) A kind of method of microwave irradiation high concentrated organic wastewater
CN104759277A (en) CeOx-MnOx/graphene low-temperature SCR flue gas denitration catalyst and preparation method thereof
WO2009142520A1 (en) Catalyst for low-temperature decomposition of dinitrogen oxide and a process for the preparation thereof
CN108927169A (en) A kind of preparation method and application of hydrotalcite CoMnFe metal composite oxide denitrating catalyst
Pu et al. Low-cost Mn–Fe/SAPO-34 catalyst from natural ferromanganese ore and lithium-silicon-powder waste for efficient low-temperature NH3-SCR removal of NOx
CN110026206A (en) A kind of NH of the anti-ABS poisoning of new type low temperature3The preparation method and application of SCR catalyst
CN109603807A (en) A kind of modified activated carbon Ce-Nb/TiO2@AC efficient cryogenic desulphurization denitration catalyst and preparation method thereof
CN107649121A (en) The method of modifying and modified manganese based denitration catalyst and preparation method of a kind of manganese based denitration catalyst
CN105312080B (en) A kind of method that molecular sieve catalyst for nitrous oxide catalytic decomposition is modified
Jia et al. Enhanced low-temperature NO oxidation by iron-modified MnO2 catalysts
CN112337460A (en) Method for preparing Mn-based spinel low-temperature denitration catalyst by using complex acid solution
CN111495371A (en) Rapid preparation method of cobalt spinel catalyst
CN105727965B (en) A kind of copper zirconium cerium and titanium compound oxide catalyst and its preparation method for denitrating flue gas
Li et al. High-yield synthesis of Ce modified Fe–Mn composite oxides benefitting from catalytic destruction of chlorobenzene
CN106582646B (en) Carbon-based acid anhydrides collaboration transition metal denitrating catalyst and preparation method thereof
CN107649144A (en) A kind of preparation method of novel denitration catalyst
CN106542584A (en) A kind of preparation method of rich defect cobalt oxide photocatalyst

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant