CN108906050A - A kind of carbon nano tube-doped Copper-Aluminum compound metal oxide denitrating catalyst and its preparation method and application - Google Patents
A kind of carbon nano tube-doped Copper-Aluminum compound metal oxide denitrating catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN108906050A CN108906050A CN201810940161.7A CN201810940161A CN108906050A CN 108906050 A CN108906050 A CN 108906050A CN 201810940161 A CN201810940161 A CN 201810940161A CN 108906050 A CN108906050 A CN 108906050A
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- cual
- nano tube
- cnts
- metal oxide
- 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention discloses a kind of carbon nano tube-doped Copper-Aluminum compound metal oxide denitrating catalysts and its preparation method and application, belong to contamination control and technical field.The catalyst is by the way that aluminum nitrate and copper nitrate mixing salt solution, NaOH aqueous slkali to be added dropwise in the dispersion liquid for being mixed with modified carbon nano-tube, pH is in 4.50~5.50 ranges for control synthesis, and carbon nano tube-doped CuAl houghite presoma is made through hydrothermal crystallizing, filtering and washing, drying（CuAl-LDH/CNTs）；It is roasted in a nitrogen atmosphere afterwards and prepares carbon nano tube-doped Copper-Aluminum compound metal oxide denitrating catalyst（CuAl-LDO/CNTs）；Denitration activity test and sulfur resistance evaluation show CuAl-LDO/CNTs catalyst in low-temperature space（180-300℃）With high NH3SCR activity, good N2Selective and strong water resistant sulfur resistance.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof, and in particular to one kind is used for low temperature NH3- SCR reaction
CuAl-LDO/CNTs denitrating catalyst belongs to pollution prevention technique field.
Background technique
Along with the improvement and research of coal-fired flue-gas, coal-fired flue-gas catalytic denitration technology has obtained very fast development.Ammonia choosing
Selecting property catalytic reduction method（NH3-SCR）Before the advantages that since its is high-efficient, selectivity is good, at low cost in business as most developing
The coal-fired flue gas denitration technology of scape.So V mature at this stage2O5-WO3/TiO2Denitrating catalyst operating temperature it is higher (300~
400 DEG C), the denitration technology demand of mediumand smallscale industrial boilers cannot be met very well, therefore, exploitation efficient stable, environmental-friendly
Low-temperature denitration catalyst becomes research hotspot.
Environmentally friendly Cu base oxide catalyst is because its good redox property is in NH3It is shown in-SCR excellent
Low-temperature catalytic activity, receive the extensive concern of scholars, achieve many valuable results of study.In the recent period, China is special
Sharp (CN201610671758.7) report, is compared to support type CuO/ γ-Al2O3, roast and make through CuAl houghite presoma
The Cu obtainedxAlOyWith better low temperature NH3- SCR catalytic activity, but the problems such as active window is narrow, water resistant sulfur resistance is not prominent
It still needs to advanced optimize solution.
Summary of the invention
In order to make up the deficiency through CuAl houghite precursor preparation metal composite oxide denitrating catalyst, it is surrounded with
It imitates dispersed catalyst activated centre, promote catalyst sulfur resistance, the present invention provides a kind of CuAl-LDO/CNTs denitrations to urge
Agent and its preparation method and application.
The carbon nanotube that the present invention chooses（CNTs）With specific one-dimensional tubular structure, because of its bigger serface and good electricity
Sub- transfer performance and be commonly used for catalyst doping vario-property.Based on the anti-SO of carbon nanotube2The excellent properties for aspect of being poisoned, the present invention
Carbon nanotube and CuAl houghite are effectively assembled, surface is had into positive electricity with electronegative modified carbon nano-tube and laminate
Property houghite by electrostatic attraction act on it is interlaced together, play both synergistic effect, successfully prepare catalytic performance
Excellent low temperature NH3SCR denitration.
The present invention provides a kind of carbon nano tube-doped Copper-Aluminum compound metal oxide denitrating catalysts, which is logical
It crosses and aluminum nitrate and copper nitrate mixing salt solution, NaOH aqueous slkali is added dropwise in the dispersion liquid for being mixed with oxide/carbon nanometer tube, control
PH is in 4.50~5.50 ranges for system synthesis, and carbon nano tube-doped CuAl class neatly is made through hydrothermal crystallizing, filtering and washing, drying
Stone presoma（CuAl-LDH/CNTs）；It is roasted to preparation in a nitrogen atmosphere afterwards has the carbon nano tube-doped of high degree of dispersion
Copper-Aluminum compound metal oxide（CuAl-LDO/CNTs）Denitrating catalyst；Denitration activity test and sulfur resistance evaluation discovery
CuAl-LDO/CNTs catalyst is in low-temperature space（180-300 ℃）With high NH3SCR activity, good N2Selective and strong
Water resistant sulfur resistance.
The present invention provides the preparation method of above-mentioned carbon nano tube-doped Copper-Aluminum compound metal oxide denitrating catalyst, packets
Include following steps：
（1）Prepare modified multiwalled carbon nanotube
1.0~5.0g multi-walled carbon nanotube (MWCNTs) is added in the round-bottomed flask containing 100ml~500ml concentrated nitric acid,
6~12 h are condensed back at 120~160 DEG C；The purifying carbon nano-tube is placed in 2 mol L-1NaOH aqueous solution in, 80 DEG C
Lower 6 h of stir process filters sediment, washing is until neutrality, 60~120 DEG C of 12~24 h of drying obtain modified multi wall carbon
Nanotube (CNTs-COO-)；
（2）Prepare mixing salt solution
Prepare 1.0 mol L respectively using volumetric flask-1Gerhardite aqueous solution and 0.5 mol L-1Nine nitric hydrates
Aluminum water solution；It weighs two kinds of prepared salting liquids respectively to mix into beaker, 5~15 min of stirring form clear solution, will
It is moved in dropping funel one for use, wherein Cu2+With Al3+The ratio between substance withdrawl syndrome is 2~4：1；
（3）Prepare sodium hydroxide solution
NaOH is taken to be dissolved in deionized water, being configured to concentration is 1.0 mol L-1NaOH aqueous solution, be transferred to dropping liquid leakage
It is stand-by in bucket two；
（4）Prepare carbon nano tube dispersion liquid
Take step（1）The modified carbon nano-tube of preparation is scattered in deionized water, is ultrasonically treated 30~60 min, and obtained concentration is
30 g▪L-1Carbon nano tube dispersion liquid.
（5）Prepare carbon nano tube-doped CuAl houghite presoma
Take step（4）The carbon nano tube dispersion liquid of preparation, it is under magnetic stirring that solution in dropping funel one and two is slow simultaneously
Above-mentioned dispersion liquid is instilled, the rate of addition for controlling mixing salt solution is 1.5~2.5 ml min-1, molten by adjusting sodium hydroxide
The rate of addition of liquid makes the pH value of solution maintain 4.50~5.50；Precipitating and mother liquor are placed in reaction under high pressure after titration
In kettle, 100~150 DEG C of 4~48 h of crystallization；It is filtered, is washed, before obtaining carbon nano tube-doped CuAl houghite after dry
Drive body（CuAl-LDH/CNTs）.
（6）Prepare CuAl-LDO/CNTs denitrating catalyst
By step（5）The presoma of acquisition roasts 3~6 h in a nitrogen atmosphere, obtains CuAl-LDO/CNTs denitrating catalyst.
The above method, the step（1）In, the mass concentration of concentrated nitric acid used is 65%~68%.
The above method, the step（5）In, the volume ratio of the oxide/carbon nanometer tube dispersion liquid and mixing salt solution that are added
It is 0.2~1：1.
The above method, the step（6）In, the flow control of nitrogen is passed through in 60ml min-1~120ml min-1.Journey
Sequence heating rate is 5~10 DEG C of min-1.The maturing temperature set is 400~600 DEG C.
The present invention is by x-ray diffractometer（XRD）Phenetic analysis has been carried out to the crystal structure for preparing product.
The present invention provides above-mentioned CuAl-LDO/CNTs denitrating catalysts in NH3Application in-SCR.
Concrete application process is：Catalysis reaction test continuously flows in quartz reactor in fixed bed to carry out.Catalyst pellets
Degree is 40-60 mesh, dosage 400mg.Reaction gas group becomes：600 ppm NO, 600 ppm NH3, 100 ppm SO2 It is (anti-
Sulphur), 10% H2O (water resistant), 5% O2, N2Make Balance Air, reaction gas air speed is 45000 h-1.Catalysis reaction is in 150-330
DEG C carry out, activity data reaction reach balance after acquire.Product is tested and analyzed by Thermofisher IS10 FTIR.
Beneficial effects of the present invention：
（1）By the structure-activity relationship between carbon nanotube and CuAl-LDO, active component problem easy to reunite has been effectively relieved.
（2）It is adjusted by structure and crystal phase of the synergistic effect between carbon nanotube and CuAl-LDO to activated centre
Control, improves NH3SCR activity.
（3）The addition of carbon nanotube can significantly increase the water resistant sulfur resistance of CuAl-LDO catalyst, slow down SO2And H2O
Effect is poisoned to catalyst, ensure that the application under physical condition.
Detailed description of the invention
Fig. 1 is the X ray diffracting spectrum of gained presoma and final products in embodiment 1 ~ 3（XRD）：（A）Before roasting
Presoma CuAl-LDH/CNTs；（B）For the CuAl-LDO/CNTs obtained after roasting.
Fig. 2 is the scanning electron microscope of CuAl-LDH/CNTs-1 in embodiment 1（SEM）Figure.
Fig. 3 is the NH of CuAl-LDO/CNTs catalyst in embodiment 43SCR activity test result：A: N2Selectivity；B:
NO conversion ratio.
Fig. 4 is sulfur resistive, the water repelling property test result of CuAl-LDO/CNTs catalyst in embodiment 5.
Specific embodiment
The present invention is further illustrated below by embodiment, but is not limited to following embodiment.
Embodiment 1：
（1）Taking 20ml concentration respectively is 0.5 mol L-1ANN aluminium nitrate nonahydrate aqueous solution and 20ml concentration be 1.0 mol L-1
Gerhardite aqueous solution be allowed to uniformly mix into beaker, and with magnetic stirrer 10min, by prepared salt
Solution is transferred in dropping funel 1 for use；
（2）Taking 200ml concentration is 1.00 mol L-1Sodium hydrate aqueous solution, transfer them in dropping funel 2 stand-by；
（3）Taking 8ml concentration is 30 g L-1Oxide/carbon nanometer tube dispersion liquid in beaker, under magnetic stirring by sodium hydroxide
Aqueous solution and mixing salt solution are instilled simultaneously in above-mentioned dispersion liquid, and use the pH value in acidometer real-time monitoring titration process, are controlled
Rate of titration processed is maintained at system pH in entire reaction process between 4.50~5.50；Continue stirring 30 after dripping
Obtained precipitating and mother liquor sealing are then placed in the stainless steel cauldron of polytetrafluoroethyllining lining, 110 DEG C of crystallization 12 by min
h；
（4）After reaction kettle natural cooling, the product after reaction is filtered and is washed with deionized to neutrality, sets 80
DEG C 12 h of oven drying.Carbon nano tube-doped CuAl houghite presoma is obtained by being fully ground（CuAl-LDH/
CNTs-1）.X-ray diffraction and scanning electron microscope analysis are carried out to product, such as attached drawing 1（A）With shown in attached drawing 2.
（5）Obtained CuAl-LDH/CNTs is put into tube furnace, leads to nitrogen protection from room temperature temperature programming to 500 DEG C
Roast 5h（Nitrogen flow rate is 80 ml min-1, programmed rate is 10 DEG C of min-1）, finally obtain carbon nano tube-doped
CuAl metal composite oxide denitrating catalyst（CuAl-LDO/CNTs-1）.X-ray diffraction analysis, diffraction are carried out to product
Spectrogram such as attached drawing 1（B）It is shown.
Embodiment 2：
（1）Taking 20ml concentration respectively is 0.5 mol L-1ANN aluminium nitrate nonahydrate aqueous solution and 30ml concentration be 1.0 mol L-1
Gerhardite aqueous solution be allowed to uniformly mix into beaker, and with 10 min of magnetic stirrer, will be prepared
Salting liquid is transferred in dropping funel 1 for use；
（2）Taking 200ml concentration is 1.00 mol L-1Sodium hydrate aqueous solution, transfer them in dropping funel 2 stand-by；
（3）Taking 25ml concentration is 30 g L-1Oxide/carbon nanometer tube dispersion liquid is in beaker, under magnetic stirring by sodium hydroxide
Aqueous solution and mixing salt solution are instilled simultaneously in above-mentioned dispersion liquid, and use the pH value in acidometer real-time monitoring titration process, are controlled
Rate of titration processed is maintained at system pH in entire reaction process between 4.50~5.50；Continue stirring 30 after dripping
Obtained precipitating and mother liquor sealing are then placed in the stainless steel cauldron of polytetrafluoroethyllining lining, in 120 DEG C of baking ovens by min
Interior 18 h of crystallization；
（4）After reaction kettle natural cooling, the product after reaction is filtered and is washed with deionized to neutrality, sets 80
DEG C 12 h of oven drying.Carbon nano tube-doped CuAl houghite presoma is obtained by being fully ground（CuAl-LDH/
CNTs-2）.X-ray diffraction analysis, diffraction spectrogram such as attached drawing 1 are carried out to product（A）It is shown.
（5）Obtained CuAl-LDH/CNTs-2 is placed in tube furnace, leads to nitrogen protection from room temperature temperature programming to 400
DEG C roasting 6h（Nitrogen flow rate is 80 ml min-1, programmed rate is 8 DEG C of min-1）, finally obtain carbon nano tube-doped
CuAl metal composite oxide（CuAl-LDO/CNTs-2）Denitrating catalyst.X-ray diffraction analysis, diffraction are carried out to product
Spectrogram such as attached drawing 1（B）It is shown.
Embodiment 3：
（1）Weighing 20ml concentration respectively is 0.5 mol L-1ANN aluminium nitrate nonahydrate aqueous solution and 40ml concentration be 1 mol L-1
Gerhardite mix into beaker, and be allowed to uniformly mix with 10 min of magnetic stirrer, by prepared salt
Solution is transferred in dropping funel for use
（2）Taking 200ml concentration is 1.00 mol L-1Sodium hydrate aqueous solution, transfer them in dropping funel stand-by；
（3）Taking 60ml concentration is 30 g L-1Oxide/carbon nanometer tube dispersion liquid in beaker, under magnetic stirring by hydroxide
Sodium water solution and mixing salt solution are instilled simultaneously in above-mentioned dispersion liquid, and with the pH value in acidometer real-time monitoring titration process,
Control rate of titration is maintained at system pH in entire reaction process between 4.50~5.50；Continue stirring 30 after dripping
Obtained precipitating and mother liquor sealing are then placed in the stainless steel cauldron of polytetrafluoroethyllining lining, in 150 DEG C of baking ovens by min
48 h of interior heating；
（4）After reaction kettle natural cooling, the product after reaction is filtered and is washed with deionized to neutrality, sets 80
DEG C 12 h of oven drying.Carbon nano tube-doped CuAl houghite presoma is obtained by being fully ground（CuAl-LDH/
CNTs-3）.X-ray diffraction analysis, diffraction spectrogram such as attached drawing 1 are carried out to product（A）It is shown.
（5）Obtained CuAl-LDH/CNTs-3 is put into tube furnace, leads to nitrogen protection from room temperature temperature programming to 600
DEG C roasting 5h（Nitrogen flow rate is 80 ml min-1, programmed rate is 5 DEG C of min-1）, finally obtain carbon nano tube-doped
CuAl metal composite oxide（CuAl-LDO/CNTs-3）Denitrating catalyst.X-ray diffraction analysis, diffraction are carried out to product
Spectrogram such as attached drawing 1（B）It is shown.
Embodiment 4：The NH of catalyst3- SCR performance evaluation
The CuAl-LDO/CNTs-2 catalyst prepared in embodiment 2 is applied to NH3- SCR reaction, the result is shown in attached drawings 3.It should
Catalyst shows good low-temperature catalyzed performance, and NO conversion ratio is at 180-300 DEG C up to 80% or more, N2Selectivity is in institute
90% or more can be maintained in Range of measuring temp.
Specific reaction condition is as follows：Catalysis reaction test continuously flows in quartz reactor in fixed bed to carry out.Catalyst
Granularity is 40-60 mesh, dosage 400mg.Reaction gas group becomes：600 ppm NO, 600 ppm NH3, 5% O2, N2It puts down
Weigh gas, and reaction gas air speed is 45000 h-1.Catalysis reaction is carried out at 150-330 DEG C, and activity data is after reaction reaches balance
Acquisition.Product is tested and analyzed by Thermofisher IS10 FTIR, NO conversion ratio and N2Selectivity is calculated by the following formula：
In above formula, [NO]in、[NO2]in、[NH3]inRespectively refer to NO, NO at reactor inlet2 And NH3The concentration of gas；
[NO]out、[NO2]out、[N2O]outRespectively refer to reactor outlet NO, NO2And N2The concentration of O.
Embodiment 5：The anti-SO of catalyst2With anti-H2O performance evaluation
The CuAl-LDO/CNTs-3 catalyst prepared to embodiment 3 carries out anti-SO2With anti-H2O performance evaluation, the result is shown in attached drawings
4.There is the catalyst excellent water resistant sulfur resistive to show, and work as H2O and SO2Simultaneously when being added NO conversion ratio can still maintain 85% with
On, and stop that H is added2O and SO2Afterwards, catalytic activity is restored.
Specific reaction condition：Test device and catalyst amount and to apply example 4 identical.Reaction gas group becomes 600 ppm
NO, 600 ppm NH3, 5% O2, 100 ppm SO2, 10% H2O, N2 Make Balance Air, reaction gas air speed is 45000 h-1, instead
Answering temperature is 240 DEG C.
Claims (7)
1. a kind of carbon nano tube-doped Copper-Aluminum compound metal oxide denitrating catalyst, it is characterised in that：The catalyst is to pass through
Aluminum nitrate and copper nitrate mixing salt solution, NaOH aqueous slkali are added dropwise in the dispersion liquid for being mixed with modified carbon nano-tube, controlled
PH is synthesized in acid range, carbon nano tube-doped CuAl houghite forerunner is made through hydrothermal crystallizing, filtering and washing, drying
Body；It is roasted to the carbon nano tube-doped Copper-Aluminum compound metal oxide that preparation has high degree of dispersion in a nitrogen atmosphere afterwards
CuAl-LDO/CNTs denitrating catalyst；Wherein the mass fraction of CNTs is 9~45%.
2. a kind of preparation method of carbon nano tube-doped Copper-Aluminum compound metal oxide denitrating catalyst described in claim 1,
Characterized by the following steps：
（1）Prepare modified multiwalled carbon nanotube
1.0~5.0g multi-walled carbon nanotube MWCNTs is added in the round-bottomed flask containing 100ml~500ml concentrated nitric acid, 120
6~12 h are condensed back at~160 DEG C；The purifying carbon nano-tube is placed in 2 mol L-1NaOH aqueous solution in, at 80 DEG C
6 h of stir process filters sediment, washing is until neutrality, 60~120 DEG C of 12~24 h of drying obtain modified multi wall carbon and receive
Mitron CNTs-COO-；
（2）Prepare mixing salt solution
Prepare 1.0 mol L respectively using volumetric flask-1Gerhardite aqueous solution and 0.5 mol L-1Nine nitric hydrates
Aluminum water solution；
It weighs two kinds of prepared salting liquids respectively to mix into beaker, 5~15 min of stirring form clear solution, move it to
It is stand-by in dropping funel one, wherein Cu2+With Al3+The ratio between substance withdrawl syndrome is 2~4：1；
（3）Prepare sodium hydroxide solution
NaOH is taken to be dissolved in deionized water, being configured to concentration is 1.0 mol L-1NaOH aqueous solution, be transferred to dropping liquid leakage
It is stand-by in bucket two；
（4）Prepare carbon nano tube dispersion liquid
Take step（1）The modified carbon nano-tube of preparation is scattered in deionized water, is ultrasonically treated 30~60 min, and obtained concentration is
30g▪L-1Carbon nano tube dispersion liquid；
（5）Prepare carbon nano tube-doped CuAl houghite presoma
Take step（4）The carbon nano tube dispersion liquid of preparation, under magnetic stirring by solution in dropping funel one and dropping funel two
It is slowly dropped into above-mentioned dispersion liquid, the rate of addition for controlling mixing salt solution is 1.5~2.5ml min-1, by adjusting sodium hydroxide
The rate of addition of solution makes the pH value of solution maintain 4.50~5.50；After titration will precipitating and mother liquor to be placed in high pressure anti-
It answers in kettle, 100~150 DEG C of 4~48 h of crystallization；It is filtered, is washed, obtain carbon nano tube-doped CuAl houghite after dry
Presoma CuAl-LDH/CNTs；
（6）Prepare CuAl-LDO/CNTs denitrating catalyst
By step（5）The presoma of acquisition roasts 3~6 h in a nitrogen atmosphere, obtains CuAl-LDO/CNTs denitrating catalyst.
3. the preparation method of carbon nano tube-doped Copper-Aluminum compound metal oxide denitrating catalyst according to claim 2,
It is characterized in that：The step（1）In, the mass concentration of concentrated nitric acid used is 65%~68%.
4. the preparation method of carbon nano tube-doped Copper-Aluminum compound metal oxide denitrating catalyst according to claim 2,
It is characterized in that：The step（5）In, the volume ratio of the modified carbon nano-tube dispersion liquid and mixing salt solution that are added is 0.2
~1, the pH value of solution is controlled in titration process 4.50~5.50.
5. the preparation method of carbon nano tube-doped Copper-Aluminum compound metal oxide denitrating catalyst according to claim 2,
It is characterized in that：The step（6）In, the flow control of nitrogen is passed through in 60 ml min-1~120 ml min-1；Program liter
Warm rate is 5~10 DEG C of min-1；The maturing temperature set is 400~600 DEG C.
6. a kind of carbon nano tube-doped Copper-Aluminum compound metal oxide denitrating catalyst described in claim 1 is in NH3In-SCR
Using.
7. application according to claim 6, it is characterised in that：Concrete application process is：Catalytic activity is tested in fixed bed
It is carried out in continuous flowing quartz reactor；Catalyst grain size is 40-60 mesh, dosage 400mg；Reaction gas group becomes：600
Ppm NO, 600 ppm NH3, 100 ppm SO2, 10% H2O, 5% O2, N2Make Balance Air, reaction gas air speed is 45000 h-1；Catalysis reaction is carried out at 150-330 DEG C, and activity data acquires after reaction reaches balance；
Denitration activity test and sulfur resistance evaluation show that CuAl-LDO/CNTs catalyst has high NH at 180-300 DEG C3-
SCR activity, good N2Selective and strong water resistant sulfur resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810940161.7A CN108906050B (en) | 2018-08-17 | 2018-08-17 | Carbon nanotube doped copper-aluminum composite metal oxide denitration catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810940161.7A CN108906050B (en) | 2018-08-17 | 2018-08-17 | Carbon nanotube doped copper-aluminum composite metal oxide denitration catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108906050A true CN108906050A (en) | 2018-11-30 |
| CN108906050B CN108906050B (en) | 2021-02-09 |
Family
ID=64404819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810940161.7A Active CN108906050B (en) | 2018-08-17 | 2018-08-17 | Carbon nanotube doped copper-aluminum composite metal oxide denitration catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108906050B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112076771A (en) * | 2020-10-21 | 2020-12-15 | 浙江工业大学 | Bimetal hydroxide @ carbon nanotube composite catalyst and preparation method and application thereof |
| CN114534731A (en) * | 2022-01-25 | 2022-05-27 | 晋中学院 | Preparation method and application of hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide catalyst |
| CN115155600A (en) * | 2022-06-24 | 2022-10-11 | 盐城工学院 | Catalyst for synthesizing methanol and preparation method and application thereof |
| CN115448723A (en) * | 2022-07-11 | 2022-12-09 | 中晶城康资源再生利用技术有限公司 | Preparation method and application of boron carbide-based ceramic modified by magnesium-aluminum hydrotalcite |
| CN115920900A (en) * | 2022-11-24 | 2023-04-07 | 大唐南京环保科技有限责任公司 | Supermolecule low-temperature honeycomb denitration catalyst with ball-like structure and preparation method thereof |
| CN116161768A (en) * | 2023-04-26 | 2023-05-26 | 四川省生态环境科学研究院 | Sewage treatment method, adopted sewage treatment agent and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010025948A1 (en) * | 2008-09-08 | 2010-03-11 | Amminex A/S | Additives for highly compacted ammonia storage materials |
| CN101869837A (en) * | 2010-06-04 | 2010-10-27 | 北京化工大学 | CoAl-metallic oxide/carbon nano tube composite as well as preparation method and application thereof as ammonium porchlorate catalyst |
| CN102000572A (en) * | 2010-10-15 | 2011-04-06 | 大连理工大学 | Method for preparing denitration catalyst by performing selective catalytic reduction on CuMgAl composite oxide |
| CN102335604A (en) * | 2011-07-21 | 2012-02-01 | 上海大学 | SCR (selective catalyctic reduction) low-temperature denitrification catalyst with nano core-shell structure and preparation method thereof |
| CN102861579A (en) * | 2012-09-22 | 2013-01-09 | 台州学院 | Copper-based nano denitration catalyst and preparation method thereof |
| CN106334558A (en) * | 2016-08-15 | 2017-01-18 | 北京林业大学 | Low-temperature selective catalytic reduction catalyst and preparation and regeneration methods thereof |
-
2018
- 2018-08-17 CN CN201810940161.7A patent/CN108906050B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010025948A1 (en) * | 2008-09-08 | 2010-03-11 | Amminex A/S | Additives for highly compacted ammonia storage materials |
| CN101869837A (en) * | 2010-06-04 | 2010-10-27 | 北京化工大学 | CoAl-metallic oxide/carbon nano tube composite as well as preparation method and application thereof as ammonium porchlorate catalyst |
| CN102000572A (en) * | 2010-10-15 | 2011-04-06 | 大连理工大学 | Method for preparing denitration catalyst by performing selective catalytic reduction on CuMgAl composite oxide |
| CN102335604A (en) * | 2011-07-21 | 2012-02-01 | 上海大学 | SCR (selective catalyctic reduction) low-temperature denitrification catalyst with nano core-shell structure and preparation method thereof |
| CN102861579A (en) * | 2012-09-22 | 2013-01-09 | 台州学院 | Copper-based nano denitration catalyst and preparation method thereof |
| CN106334558A (en) * | 2016-08-15 | 2017-01-18 | 北京林业大学 | Low-temperature selective catalytic reduction catalyst and preparation and regeneration methods thereof |
Non-Patent Citations (1)
| Title |
|---|
| 小野嘉夫等: "《固体碱催化》", 31 May 2013, 复旦大学出版社 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112076771A (en) * | 2020-10-21 | 2020-12-15 | 浙江工业大学 | Bimetal hydroxide @ carbon nanotube composite catalyst and preparation method and application thereof |
| CN112076771B (en) * | 2020-10-21 | 2023-05-30 | 浙江工业大学 | Double metal hydroxide@carbon nano tube composite catalyst and preparation method and application thereof |
| CN114534731A (en) * | 2022-01-25 | 2022-05-27 | 晋中学院 | Preparation method and application of hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide catalyst |
| CN114534731B (en) * | 2022-01-25 | 2023-10-31 | 晋中学院 | Preparation method and application of hydrotalcite-based carbon doped copper-magnesium-aluminum composite oxide catalyst |
| CN115155600A (en) * | 2022-06-24 | 2022-10-11 | 盐城工学院 | Catalyst for synthesizing methanol and preparation method and application thereof |
| CN115155600B (en) * | 2022-06-24 | 2023-11-21 | 盐城工学院 | Catalyst for synthesizing methanol and preparation method and application thereof |
| CN115448723A (en) * | 2022-07-11 | 2022-12-09 | 中晶城康资源再生利用技术有限公司 | Preparation method and application of boron carbide-based ceramic modified by magnesium-aluminum hydrotalcite |
| CN115920900A (en) * | 2022-11-24 | 2023-04-07 | 大唐南京环保科技有限责任公司 | Supermolecule low-temperature honeycomb denitration catalyst with ball-like structure and preparation method thereof |
| CN116161768A (en) * | 2023-04-26 | 2023-05-26 | 四川省生态环境科学研究院 | Sewage treatment method, adopted sewage treatment agent and preparation method thereof |
| CN116161768B (en) * | 2023-04-26 | 2023-08-04 | 四川省生态环境科学研究院 | Sewage treatment method, adopted sewage treatment agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108906050B (en) | 2021-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108906050A (en) | A kind of carbon nano tube-doped Copper-Aluminum compound metal oxide denitrating catalyst and its preparation method and application | |
| CN107285334B (en) | A kind of method and catalyst of synthesis in solid state AEI type molecular sieve | |
| CN105944753A (en) | Cu-SSZ-13 molecular sieve based catalyst adopting core-shell structure as well as preparation and application of catalyst | |
| CN107115888A (en) | A kind of preparation method and its usage of the catalyst of Cu SSZ 13 | |
| CN105833901B (en) | A kind of PrOx-MnOx/ SAPO-34 low-temperature SCR catalyst for denitrating flue gas and the preparation method and application thereof | |
| CN106824247B (en) | A kind of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst and its preparation method and application | |
| CN105597737B (en) | One kind is used for NH3Composite oxide catalysts of SCR denitration and preparation method thereof | |
| CN108927169B (en) | Preparation method and application of hydrotalcite-based CoMnFe composite metal oxide denitration catalyst | |
| CN109701657B (en) | Synthesis method and application of MOF-74-NiCo material | |
| CN104069861B (en) | A kind of mesoporous iron-based composite oxide catalysts, preparation method and the application in ammonia selective catalysis nitrogen oxides reduction thereof | |
| CN109982969A (en) | The new synthesis of the zeolite catalyst of metal promoted | |
| CN106268787A (en) | A kind of samarium doping MnOxlow-temperature SCR catalyst and its preparation method and application | |
| CN102000572B (en) | Method for preparing denitration catalyst by performing selective catalytic reduction on CuMgAl composite oxide | |
| CN103752323A (en) | Preparation method for denitrified catalyst with nanometer multi-wall spherical spinel structure | |
| CN106276963B (en) | A kind of synthetic method of metal-ZSM molecular sieve | |
| CN105312080B (en) | A kind of method that molecular sieve catalyst for nitrous oxide catalytic decomposition is modified | |
| CN109589962A (en) | A kind of high resistance to SO_2 cerium based low-temperature denitration catalyst and preparation method thereof | |
| CN105797714A (en) | Holmium modified manganese-titanium complex oxide low-temperature denitrification catalyst and preparation method thereof | |
| CN108404930A (en) | A kind of low-temperature denitration catalyst and preparation method thereof with nucleocapsid | |
| CN104437501B (en) | A kind of cobalt-base catalyst and the preparation method and application thereof | |
| CN107185555B (en) | Preparation method of copper-doped cerium sulfide-based nanocrystalline denitration catalyst | |
| CN107469811A (en) | A kind of wide temperature window denitrating catalyst and its preparation method and application | |
| CN108514881A (en) | One kind being used for NH3Cu-Ce catalyst, preparation method and the application of the nano bar-shape structure of catalysis oxidation | |
| CN106466607B (en) | A kind of environmental-friendly sections antimony composite oxides denitrating catalyst and preparation method thereof | |
| CN111514929B (en) | Cu-SSZ-13 catalyst with double aluminum centers, H-SSZ-13 molecular sieve, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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 |