CN103934042B - The gas-phase deposition process for preparing of load typed iron catalyst - Google Patents
The gas-phase deposition process for preparing of load typed iron catalyst Download PDFInfo
- Publication number
- CN103934042B CN103934042B CN201410176407.XA CN201410176407A CN103934042B CN 103934042 B CN103934042 B CN 103934042B CN 201410176407 A CN201410176407 A CN 201410176407A CN 103934042 B CN103934042 B CN 103934042B
- Authority
- CN
- China
- Prior art keywords
- gas
- temperature
- catalyst
- preparation
- reaction tube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention belongs to industrial catalyst preparation field, particularly, relate to a kind of gas-phase deposition process for preparing of load typed iron catalyst.The preparation method of load typed iron catalyst, adopt the vapour deposition preparation facilities of load typed iron catalyst, step is as follows: the filling of step 1, catalyst carrier; Step 2, placement ferrocene heap; The deposition of step 3, iron component; Step 4, low-temperature bake; Step 5, high-temperature roasting.The present invention can obtain the load typed iron catalyst with high degree of dispersion iron component; Preparation method is easy and simple to handle, controllability is strong, preparation efficiency is high, strong to different carriers type universality, be convenient to promote; Preparation method does not relate to liquid, therefore need not carry out liquid waste processing; Safe preparation process improves greatly; By the iron catalyst that preparation method of the present invention obtains, fixed bed reactors can be directly used in and carry out Chemical Manufacture.
Description
Technical field
The invention belongs to industrial catalyst preparation field, particularly, relate to a kind of gas-phase deposition process for preparing of load typed iron catalyst, by metal organic chemical compound vapor deposition legal system for load typed iron catalyst.
Background technology
Loading type iron (Fe) is catalyst based is the catalyst of multiple essential industry catalytic production process, and the catalytic oxidation of such as alkane, synthesis gas obtains the processes such as hydrocarbon through Fischer-Tropsch reaction.From microcosmic principle, catalyst is decided by micro Distribution situation and the chemical state of catalyst activity component to a great extent for the catalytic performance of a certain reaction, and how these two factors and catalyst prepare tight association.Therefore the Different Preparation exploring catalyst has great importance for the improvement of catalyst.Two classes can be divided into about in the preparation method of load typed iron catalyst from source of iron at present: one be take infusion process as Main Means, source of iron comes from the method for solution, two is CVD methods that source of iron comes from gas phase.
Publication number is that CN1431048A patent of invention describes a kind of load typed iron catalyst and preparation method thereof, and the presoma of the presoma of Fe component and auxiliary agent is made into the solution that concentration is 0.1 ~ 6mol/L, respectively in proportion by active carbon or γ-Al
2o
3be impregnated in the solution of Fe presoma and auxiliary agent presoma, leave standstill 18 ~ 36 hours after dipping, 110 ~ 120 DEG C of dryings 4 ~ 6 hours, under nitrogen protection in 450 ~ 650 DEG C, roasting 4 ~ 5 hours, enters drier.Catalyst metals source comes from the aqueous solution substantially, therefore the distribution of active metal component on carrier is difficult to control, most of catalyst is in actual oxidation of alkanes process simultaneously, temperature is higher, active component is in constantly oxidation and reduction circulation, cause active component easily to be assembled at catalysis scene, make catalytic activity obviously reduce even inactivation.From application, use the aqueous solution to relate to the process of solution preparation and waste liquid, thus improve process costs.
The report that the CVD method that source of iron comes from gas phase prepares load typed iron catalyst is considerably less, and the people such as Sachtler are once with FeCl
3for source of iron by Fe component deposition on molecular sieve carrier, they once carried out FeCl on H-ZSM molecular sieve
3vapour deposition prepare Fe/ZSM-5 catalyst (bibliography: H.-Y Chen, W. M. H. Sachtler, Catalysis Today 42 (1998) 73-83), preparation process is as follows: (1) is by ZSM-5 molecular sieve and rare NH
4nO
3the aqueous solution carries out three secondary ion exchanges, filters, and dries, in oxygen, 550
oroasting under C; (2) by 5g ZSM-5 molecular sieve, 1g FeCl
3put into a U-shaped pipe and use N
2the glove box of protection, by molecular sieve and FeCl in glove box
3be respectively charged into U-shaped pipe, the two separates with porous plug; (3) U-shaped pipe is taken out, at the FeCl of U-shaped pipe
3one end passes into the Ar gas of 100mL/min, and the temperature simultaneously controlling U-shaped pipe is 320
oc, keeps different time according to target deposition amount; (4) NaOH solution of the airflow passes 1mol/L flowed out; (5) take out a large amount of washed with de-ionized water of molecular sieve after vapour deposition, filter afterwards, dry, at O
2in 600
oClower roasting 2h.
Although Fe component can be distributed on molecular sieve by above-mentioned technique equably, its shortcoming is also apparent.First, FeCl
3boiling point is higher by (~ 320
oc), cause the energy consumption of this technique higher; FeCl
3the easy moisture absorption, needs before deposition to carry out drying process, and needs to use N
2the glove box of protection; Complex operation.Preparation process relates to following metathesis reaction: FeCl
3+ Zeo-H=Zeo-FeCl
2+ HCl (reaction 1, Zeo-represents the anion position of molecular sieve), preparation facilities needs to consider to absorb HCl tail gas.Zeo-FeCl
2the vapour deposition product of form also needs the processing procedure by solution (water) or steam, has arrived and has removed Cl completely
-object, react and be: Zeo-FeCl
2+ 2H
2o=Zeo-Fe (OH)
2+ 2HCl (reaction 2), finally also needs bakes to burn the article process.Can find out, this preparation process is complicated, and operation requirements is high, and equipment cost is also high, and needs to relate to the aqueous solution; Another one shortcoming is the universality without carrier.Because needs fix Fe component by reaction (1), therefore carrier must have the Br nsted acidic site of higher concentration.
Kazusaka once reported (bibliography: A. Kazusaka, H. Suzuki, I. Toyoshima, J. Chem. Soc., Chem.Commun. (
1983)150.) Fe (CO) is used
5as source of iron at γ-Al
2o
3surface deposition Fe catalyst.Although compared with the preparation method of the people such as Sachtler, technique is relatively simple.But well-known, Fe (CO)
5all have very strong toxicity and explosions, its operating process must bear high safety cost.
In sum, at present in load typed iron catalyst preparation field, also lack a kind of without the need to liquid, raw material without (low) poison, environmental friendliness, handling safety, step simply, cost is compared with the preparation method of iron component particles little (<15 nm) on low, catalyst.
Summary of the invention
For overcoming prior art Problems existing, the invention provides a kind of gas-phase deposition process for preparing of load typed iron catalyst, the method has without the need to liquid, raw material without (low) poison, environmental friendliness, handling safety, step is simple, cost is low feature, and on catalyst, iron component has the feature of particle little (<15 nm) simultaneously.
To achieve these goals, technical scheme of the present invention is:
The vapour deposition preparation facilities of load typed iron catalyst, comprising: reaction tube, and one end of reaction tube is inlet end, the other end is outlet side, and inlet end controls entering of air-flow by stop valve; In reaction tube, place ferrocene heap near the position of inlet end, the center of ferrocene heap is provided with the first thermocouple; Near the position catalyst filling carrier bed of outlet side in reaction tube, the center of catalyst carrier bed is provided with the second thermocouple; First thermocouple is for measuring the temperature of ferrocene heap; Second thermocouple is for measuring the temperature of catalyst carrier bed; Opening stop valve can make the gas of source of the gas enter reaction tube from inlet end, is flowed out form tail gas by outlet side.
The preparation method of load typed iron catalyst, adopt the vapour deposition preparation facilities of above-mentioned load typed iron catalyst, step is as follows:
The filling of step 1, catalyst carrier;
Step 2, placement ferrocene heap;
The deposition of step 3, iron component;
Step 4, low-temperature bake;
Step 5, high-temperature roasting.
Relative to prior art, the following beneficial effect that the present invention has:
(1), the present invention can obtain the load typed iron catalyst with high degree of dispersion iron component (iron component particles size <15nm);
(2), preparation method is easy and simple to handle, controllability is strong, preparation efficiency is high, strong to different carriers type universality, be convenient to promote;
(3), relative to solwution method with FeCl
3for the vapour deposition process of source of iron, preparation method of the present invention does not relate to liquid, therefore need not carry out liquid waste processing;
(4), relative to Fe (CO)
5for the vapour deposition process of source of iron, safe preparation process of the present invention improves greatly;
(5) iron catalyst, by preparation method of the present invention obtained, can be directly used in fixed bed reactors and carry out Chemical Manufacture.
Accompanying drawing explanation
Fig. 1 is the vapour deposition preparation facilities schematic diagram of load typed iron catalyst;
In figure: 1, reaction tube; 2, catalyst carrier bed; 3, ferrocene heap; 4, the first thermocouple; 5, the second thermocouple; 6, source of the gas; 7, stop valve; 8, tail gas.The direction of arrow of thick line represents the flow direction of gas.
Detailed description of the invention
As shown in Figure 1, the vapour deposition preparation facilities of load typed iron catalyst, comprising: reaction tube 1, and one end of reaction tube is inlet end, the other end is outlet side, and inlet end controls entering of air-flow by stop valve 7; In reaction tube, place ferrocene heap 3 near the position of inlet end, the center of ferrocene heap 3 is provided with the first thermocouple 4; Near the position catalyst filling carrier bed 2 of outlet side in reaction tube, the center of catalyst carrier bed 2 is provided with the second thermocouple 5; First thermocouple 4 is for measuring the temperature of ferrocene heap 3; Second thermocouple 5 is for measuring the temperature of catalyst carrier bed 2; Opening stop valve 7 can make the gas of source of the gas 6 enter reaction tube from inlet end, is flowed out form tail gas 8 by outlet side.
The preparation method of load typed iron catalyst, step is as follows.
The filling of step 1, catalyst carrier; Concrete grammar is as follows:
Catalyst carrier adopts Al
2o
3, SiO
2, alumino-silicate, zeolite molecular sieve, MgO or ZrO
2in the mixture of one or more; Catalyst carrier is graininess, and granular size is within the scope of 10 ~ 100 objects; Catalyst carrier loaded in reaction tube, catalyst carrier is full of the cross section of reaction tube, forms catalyst carrier bed 3; Catalyst carrier bed 3 adopts wire netting, mineral wool or silica wool to fix.
Step 2, placement ferrocene heap; Concrete grammar is as follows:
Ferrocene heap is placed near the position of inlet end in reaction tube; The mass ratio of ferrocene and catalyst carrier is 1:30 ~ 20:1; The centre distance of ferrocene heap and catalyst carrier bed 3 is 0 ~ 50cm;
The deposition of step 3, iron component; Concrete grammar is as follows:
Open stop valve 7, make the gas in source of the gas 6 pass into reaction tube 1; The flow velocity controlling gas is 2 ~ 200 ml/min; Heating the temperature that the first thermocouple is recorded and reach certain value between 80 ~ 200 DEG C, the temperature that the temperature that the second thermocouple records records with the first thermocouple, deviation is no more than ± and 5
oc; Start timing when said temperature and air-flow velocity reach setting value, keep air temperature and current flow velocity constant, the retention time is 20min ~ 4h.
The source of the gas of this step adopts N
2the gaseous mixture of gas, He gas, Ar gas or above-mentioned gas.
Step 4, low-temperature bake: concrete grammar is as follows:
Change the gas in source of the gas 6 into compressed air, or any O
2content is greater than the gas of >3%.Flow control certain value within the scope of 1 ~ 200 ml/min of gas; Control temperature that the second thermocouple records and reach certain value between 160 ~ 240 DEG C; When said temperature and air-flow velocity reach setting value, start timing; Keep said temperature and air-flow velocity constant, the retention time is 20min ~ 4h.
Step 5, high-temperature roasting: concrete grammar is as follows:
The flow velocity of gas in step 4 is tuned up, makes it certain value be in the scope of 20 ~ 400 ml/min; Raise the temperature in reaction tube 1, the temperature recorded when the second thermocouple reaches certain value between 300 ~ 700 DEG C, starts timing; Keep said temperature and air-flow velocity constant, the retention time is 30 min ~ 6h; Catalyst carrier becomes final load typed iron catalyst.
Take out load typed iron catalyst and carry out catalyst characterization; By the loaded catalyst that technique scheme prepares, its active metal component is elemental iron, and iron content is between 0.5 ~ 20 wt%; The microcosmic of iron component on carrier gathers level size within the scope of 1 ~ 15nm.
embodiment one,
As shown in Figure 1, reaction tube material is quartz to the preparation facilities of load typed iron catalyst; First thermocouple, the second thermocouple adopt K type thermocouple; Stop valve and gas line adopt stainless steel material; Source of the gas is high-purity N
2and compressed air; The flow velocity flowmeter of source gas controls and shows.
The preparation method of load typed iron catalyst, preparation process is as follows:
Step (1), take 1.0 g γ-Al
2o
3carrier, granular size is 20 ~ 50 orders, is placed in crystal reaction tube by Fig. 1, is fixed with wire netting.
Step (2), take 0.8 g ferrocene solid, put into reaction tube by the mode of Fig. 1, the centre distance of ferrocene heap and carrier layer is 10 cm.
Step (3), with N
2for source of the gas, open stop valve, make N
2flow into reaction tube inlet end, N
2flow velocity be 25 mL/min; The temperature that heating reaction tube makes two thermocouples record is all 140 DEG C; Keep above-mentioned heating-up temperature and gas flow rate 1 h.
Step (4), the gas of source of the gas is switched to compressed air; By compressed-air actuated flow control at 8 mL/min; The temperature raised in reaction tube makes the second thermocouple displays temperature reach 185
oc; Keep said temperature and air-flow velocity constant, the retention time is 1h.
Step (5), the temperature raised in reaction tube make the second thermocouple displays temperature reach 500
oc; By compressed-air actuated flow control at 50 mL/min; Keep said temperature and air-flow velocity constant, the retention time is 4h; Catalyst carrier becomes Al
2o
3load typed iron catalyst.
Prepare complete, in analysis of catalyst, the content of iron is 6.8wt%, is of a size of 3 ~ 9nm with transmission electron microscope analysis Nanoscale Iron.
embodiment two,be with the difference of embodiment one: step (1) uses γ-Al
2o
3the granular size of carrier is 40 ~ 80 orders.Step (3) two temperature that thermocouple records are all 130 DEG C; N
2flow velocity is 40 mL/min.Step (5) second thermocouple displays temperature reaches 400
oc; Time is 6h.
Prepare complete, in analysis of catalyst, the content of iron is 5.5 wt%, is of a size of 2 ~ 7nm with transmission electron microscope analysis Nanoscale Iron.
embodiment three,be with the difference of embodiment one: step (1) uses SiO
2carrier; Granular size is 40 ~ 80 orders.Step (3) two temperature that thermocouple records are all 110 DEG C, N
2flow velocity is 30 mL/min.
Prepare complete, in analysis of catalyst, the content of iron is 4.3 wt%, is of a size of 3 ~ 10 nm with transmission electron microscope analysis Nanoscale Iron.
embodiment four,be with the difference of embodiment one: step (1) uses shaping SBA-15 molecular sieve carrier; Granular size is 50 ~ 80 orders.
Prepare complete, in analysis of catalyst, the content of iron is 6.5 wt%, is of a size of 2 ~ 4 nm with transmission electron microscope analysis Nanoscale Iron.
embodiment five,be with the difference of embodiment one: step (3) is by N
2flow velocity changes 80 mL/min into.
Prepare complete, in analysis of catalyst, the content of iron is 3.1 wt%, is of a size of 2 ~ 6 nm with transmission electron microscope analysis Nanoscale Iron.
embodiment six,be with the difference of embodiment one: step (2) changes the consumption of ferrocene into 1.4 g.
Prepare complete, in analysis of catalyst, the content of iron is 7.7 wt%, is of a size of 3 ~ 14 nm with transmission electron microscope analysis Nanoscale Iron.
embodiment seven,be with the difference of embodiment one: step (2) changes the consumption of ferrocene into 1.4 g.Step (4) second thermocouple displays temperature changes 215 into
oc.
Prepare complete, in analysis of catalyst, the content of iron is 4.8 wt%, is of a size of 2 ~ 9 nm with transmission electron microscope analysis Nanoscale Iron.
embodiment eight,be with the difference of embodiment one: the distance adjustment at the central temperature that ferrocene is piled by step (2) and beds center is to 25 cm.
After preparation, the characteristic feature of catalyst is substantially identical with embodiment one result.
Claims (2)
1. the preparation method of a load typed iron catalyst, adopt the vapour deposition preparation facilities of load typed iron catalyst, the vapour deposition preparation facilities of load typed iron catalyst comprises: reaction tube, one end of reaction tube is inlet end, the other end is outlet side, and inlet end controls entering of air-flow by stop valve; In reaction tube, place ferrocene heap near the position of inlet end, the center of ferrocene heap is provided with the first thermocouple; Near the position catalyst filling carrier bed of outlet side in reaction tube, the center of catalyst carrier bed is provided with the second thermocouple; First thermocouple is for measuring the temperature of ferrocene heap; Second thermocouple is for measuring the temperature of catalyst carrier bed; Opening stop valve can make the gas of source of the gas enter reaction tube from inlet end, is flowed out form tail gas by outlet side; Catalyst carrier bed adopts wire netting, mineral wool or silica wool to fix; It is characterized in that, step is as follows:
The filling of step 1, catalyst carrier;
Step 2, placement ferrocene heap;
The deposition of step 3, iron component;
Step 4, low-temperature bake;
Step 5, high-temperature roasting;
The concrete grammar of step 1 is as follows: catalyst carrier adopts Al
2o
3, SiO
2, alumino-silicate, zeolite molecular sieve, MgO or ZrO
2in the mixture of one or more; Catalyst carrier is graininess, and granular size is within the scope of 10 ~ 100 objects; Catalyst carrier loaded in reaction tube, catalyst carrier is full of the cross section of reaction tube, forms catalyst carrier bed;
The concrete grammar of step 2 is as follows: in reaction tube, place ferrocene heap near the position of inlet end; The mass ratio of ferrocene and catalyst carrier is 1:30 ~ 20:1; The centre distance of ferrocene heap and catalyst carrier bed is 0 ~ 50cm;
The concrete grammar of step 3 is as follows: open stop valve, makes the gas in source of the gas pass into reaction tube; The flow velocity controlling gas is 2 ~ 200 ml/min; Heating the temperature that the first thermocouple is recorded and reach certain value between 80 ~ 200 DEG C, the temperature that the temperature that the second thermocouple records records with the first thermocouple, deviation is no more than ± and 5
oc; Start timing when said temperature and air-flow velocity reach setting value, keep air temperature and current flow velocity constant, the retention time is 20min ~ 4h;
The concrete grammar of step 4 is as follows: change the gas in source of the gas into compressed air, or any O
2content is greater than the gas of >3%; Flow control certain value within the scope of 1 ~ 200 ml/min of gas; Control temperature that the second thermocouple records and reach certain value between 160 ~ 240 DEG C; When said temperature and air-flow velocity reach setting value, start timing; Keep said temperature and air-flow velocity constant, the retention time is 20min ~ 4h;
The concrete grammar of step 5 is as follows: tuned up by the flow velocity of gas in step 4, makes it certain value be in the scope of 20 ~ 400 ml/min; Raise the temperature in reaction tube, the temperature recorded when the second thermocouple reaches certain value between 300 ~ 700 DEG C, starts timing; Keep said temperature and air-flow velocity constant, the retention time is 30 min ~ 6h; Catalyst carrier becomes final load typed iron catalyst.
2. the preparation method of load typed iron catalyst according to claim 1, is characterized in that, the source of the gas of step 3 adopts N
2the gaseous mixture of gas, He gas, Ar gas or above-mentioned gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410176407.XA CN103934042B (en) | 2014-04-29 | 2014-04-29 | The gas-phase deposition process for preparing of load typed iron catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410176407.XA CN103934042B (en) | 2014-04-29 | 2014-04-29 | The gas-phase deposition process for preparing of load typed iron catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103934042A CN103934042A (en) | 2014-07-23 |
| CN103934042B true CN103934042B (en) | 2015-07-29 |
Family
ID=51182071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410176407.XA Expired - Fee Related CN103934042B (en) | 2014-04-29 | 2014-04-29 | The gas-phase deposition process for preparing of load typed iron catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103934042B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106693973A (en) * | 2017-01-20 | 2017-05-24 | 平潭自贸区金瑜环保材料有限公司 | Preparation method of integral type iron catalyst |
| CN106824194A (en) * | 2017-01-20 | 2017-06-13 | 平潭自贸区金瑜环保材料有限公司 | A kind of integral alumina supported ferric catalyst based on vapour deposition process |
| CN108607601A (en) * | 2018-05-15 | 2018-10-02 | 中国石油大学(华东) | Iron catalyst for Catalytic Decomposition of Hydrogen Peroxide prepares and reaction process |
| CN108816272A (en) * | 2018-05-15 | 2018-11-16 | 中国石油大学(华东) | A kind of novel ferrimanganic two-component catalyst and catalytic degradation acetone method |
| CN108554442A (en) * | 2018-05-15 | 2018-09-21 | 中国石油大学(华东) | Novel ferrimanganic two-component catalyst and its Catalytic processes decomposed for hydrogen peroxide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288072A (en) * | 2013-05-24 | 2013-09-11 | 大连理工大学 | Preparation method of iron filled carbon nano tube and reaction device |
-
2014
- 2014-04-29 CN CN201410176407.XA patent/CN103934042B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288072A (en) * | 2013-05-24 | 2013-09-11 | 大连理工大学 | Preparation method of iron filled carbon nano tube and reaction device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103934042A (en) | 2014-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103934042B (en) | The gas-phase deposition process for preparing of load typed iron catalyst | |
| Cui et al. | Holey Co-Ce oxide nanosheets as a highly efficient catalyst for diesel soot combustion | |
| Yu et al. | Sulfur poisoning resistant mesoporous Mn-base catalyst for low-temperature SCR of NO with NH3 | |
| Wagloehner et al. | Structure–activity relation of iron oxide catalysts in soot oxidation | |
| Zhang et al. | MIL-100 (Fe) supported Mn-based catalyst and its behavior in Hg0 removal from flue gas | |
| JP5688096B2 (en) | Iron zeolite, method for producing iron zeolite, and method for catalytic reduction of nitrous oxide | |
| JP5625622B2 (en) | High heat resistant water SCR catalyst and method for producing the same | |
| CN103381371B (en) | Preparation method of carbon nitride/microporous molecular sieve composite material | |
| Qin et al. | Catalytic oxidation of ethyl acetate over silver catalysts supported on CeO2 with different morphologies | |
| CN102133547B (en) | Ozone treatment regeneration method and device for vanadium titanium-based flue gas denitration catalyst | |
| Huang et al. | Study on the NO reduction by NH3 on a SO42−/AC catalyst at low temperature | |
| CN104923213B (en) | A kind of nontoxic rare-earth type denitrating catalyst and its preparation method and application | |
| CN106076318A (en) | A kind of preparation method of integral catalyzer | |
| CN110038579A (en) | A kind of SCR catalyst and preparation method thereof promoting the dissociation of ammonium hydrogen sulfate low temperature | |
| Liu et al. | Study on catalytic performance and kinetics of high efficiency CeO2 catalyst prepared by freeze drying for the synthesis of dimethyl carbonate from CO2 and methanol | |
| CN105233860B (en) | A kind of preparation method of catalytic cracking flue gas denitration auxiliary agent | |
| Bo et al. | Promotional effects of copper doping on Ti-Ce-Ox for selective catalytic reduction of NO by NH3 at low temperature | |
| CN106362727B (en) | A kind of method and application improving ceria-based denitration catalyst catalytic performance | |
| CN110694640A (en) | Water-resistant sulfur-resistant denitration catalyst and preparation method thereof | |
| Han et al. | Synergistic Reduction Mechanism of NO x by NH3 and CO Catalyzed by Mn–Co Oxides and the Oxidation Process of CO: In Situ DRIFTS and DFT Study | |
| CN104815675B (en) | Denitrifying catalyst with selective catalytic reduction and its regeneration method and application | |
| Gao et al. | Nickel foam supported CuCe mixed metal oxide as monolith catalyst for NO removal | |
| Zhang et al. | Promotional effects of phosphotungstic acid on CePO4 catalyst for the selective catalytic reduction of NOx with NH3 | |
| CN103374431A (en) | Oxygen carrier, preparation method therefor, and applications thereof | |
| CN112473688A (en) | Preparation method of rare earth chelated vanadium low-cost wide-temperature-window denitration catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150729 Termination date: 20160429 |