CN106563464A - Cerium-based catalyst for benzene low-temperature catalytic removal, and preparation and application thereof - Google Patents
Cerium-based catalyst for benzene low-temperature catalytic removal, and preparation and application thereof Download PDFInfo
- Publication number
- CN106563464A CN106563464A CN201610953189.5A CN201610953189A CN106563464A CN 106563464 A CN106563464 A CN 106563464A CN 201610953189 A CN201610953189 A CN 201610953189A CN 106563464 A CN106563464 A CN 106563464A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- cerium
- cobalt
- low
- solution
- 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.)
- Pending
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
- B01J23/76—Catalysts 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
- B01J23/84—Catalysts 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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- 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
-
- 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
- B01J2523/00—Constitutive 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 cerium-based catalyst for benzene low-temperature catalytic removal, and preparation and application thereof. The catalyst is characterized in that cobalt doping cerium oxide is used as active ingredients, wherein the mol ratio of cobalt to cerium is (1:9) to (3:7); the catalyst is prepared by a citric acid sodium hydroxide method; the preparation method is simple; and the particles of the catalyst are uniform. Composite oxides formed by non-noble metal cobalt and cerium are used as active ingredients of the catalyst, so that the cost of the catalyst is greatly reduced; in addition, the catalyst provided by the invention has good catalytic oxidation activity at high air speed and low reaction temperature. The cobalt doping is used for modifying the cerium-based catalyst, so that the high-temperature catalytic oxidation activity on benzene series compounds is greatly improved; and the foundation is laid for the development of the cerium-based catalyst.
Description
Technical field
The present invention relates to a kind of cerium manganese load cobalt oxide low-temperature denitration catalyst and preparation method thereof, it is adaptable to environmental pollution
The SCR of thing NO, has application prospect in depollution of environment field.
Background technology
NOx is major pollutants common in air, as primary pollution, any animals and plants can be caused with various direct
Harm, and NO can also be converted into NO by photochemical oxidation effect2, nitric acid and nitrous acid are formed then, it is the main of acid rain
Contributor.China's NOx emission is concentrated mainly on the industries such as thermoelectricity and cement and automotive emission.
At present widely used gas denitrifying technology is mainly SNCR technology（SNCR）And select
Property catalytic reduction technique（SCR）, the reaction temperature of SNCR technologies is higher, and about 800-1100 DEG C, whole catalysis system is more simple
It is single, but denitration efficiency is not satisfactory.SCR technology is most widely used, the most ripe and maximally effective cigarette in the world
Gas denitration technology.In NH3The use of most ripe catalyst is MoO in-SCR technology3Or WO3The V of auxiliary2O5/TiO2Catalyst,
It is mainly characterized by with high activity and can bear certain SO2Toxic action, active window is generally 300-420 DEG C.But
It is V2O5Catalyst has significantly biological toxic effect processed, and ecological environmental toxic evil is acted on, and reaction temperature is higher, uncomfortable
For the relatively low boiler of furnace temperature.Based on above reason, people are by NH3The research emphasis of-SCR technology are placed on exploitation and have high living
Property, the non-V of hypotoxicity, low temperature2O5Catalyst, so as to can be by NH3- SCR reactors be directly configured at dedusting and desulfurizer it
Afterwards, the harm of dust and sulfur to catalyst is reduced.
The content of the invention
The invention aims to overcome above-mentioned existing nitrogen oxides to administer the defect that catalyst is present, such as catalyst has
Toxicity, reaction temperature is higher etc., there is provided a kind of cerium manganese for reducing reaction temperature loads the preparation of cobalt oxide denitrating catalyst
Method, the catalyst preparation process is easy, and cost is relatively low.
The purpose of the present invention can be achieved through the following technical solutions, and the oxidation of cerium manganese is prepared with ammonium carbonate coprecipitation method
Thing, then loads cobalt oxide, comprises the following steps that：
A kind of cerium manganese loads the preparation method of cobalt oxide low-temperature denitration catalyst, it is characterised in that comprise the steps：
Weigh a certain amount of manganese salt and cerium salt is placed in 200 mL water, be stirred at room temperature to being completely dissolved, subsequent Deca 30mL carbonic acid
Ammonium salt solution, makes solution precipitate completely, continues to stir 1 ~ 3 hour, and the suspension for obtaining is carried out to be put into 60-80 DEG C after filtration washing
It is dried 12 hours in baking oven, is then placed in Muffle furnace 400-600 DEG C of roasting 3 ~ 5 hours, cerium Mn oxide is obtained；
By salt solubility in deionized water, cobalt liquor is obtained, in being added dropwise to 1.0 grams of cerium manganese composite oxides, impregnate 6-
After 12 hours, it is put in 60-80 DEG C of baking oven and is dried 12 hours, then in 400-600 DEG C of roasting 3-5 hour, obtains the load of cerium manganese
The mass fraction of cobalt oxide catalyst, wherein cobalt is 2.5-10%.
Described cerium salt is cerous nitrate, the one kind in ammonium ceric nitrate, and described manganese salt is manganese nitrate, in manganese acetate
Kind, described cobalt salt is cobalt nitrate, the one kind in cobaltous acetate.
Described manganese salt is 0.11 with the mol ratio of cerium salt:1 ~ 9.0:1, described sal volatile concentration is 2.0 ~
3.0 mol/L.
It is a kind of that cerium manganese load cobalt oxide catalyst is prepared by above-mentioned any one methods described.
A kind of cerium manganese loads application of the cobalt oxide catalyst in the SCR of environmental contaminants NO, in NH3-
Application in SCR reactions, it is characterised in that concrete reaction condition is as follows：Reaction temperature 20-400 DEG C, the mL/ of total gas flow rate 500
Min, reaction gas consists of 100-500 ppm nitric oxide, 100-500 ppm ammonias, 3-10% oxygen, and remaining is nitrogen.
In the present invention, cerium manganese load cobalt oxide catalyst is used for nitric oxide production SCR, with preferable
Performance, manganese oxide multivalent state makes it have good redox ability in the catalyst.When nitric oxide and nitrogen dioxide
Mol ratio is 1:When 1, the efficiency optimization of SCR, and cerium oxide has and excellent stores oxygen ability, simultaneous oxidation cobalt in the catalyst
Also possess certain oxidability, so as to promote the generation of nitrogen dioxide to a certain extent reaction efficiency is improved.Reaction temperature
For 125 DEG C when, nitric oxide production conversion ratio can reach more than 99%, and the present invention prepares the raw material of catalyst and is easy to get, technique
Simply, cost is relatively low, it is easy to accomplish industrialized production.
In the present invention, it is proposed that cerium manganese loads cobalt oxide catalyst, for nitric oxide production SCR, has
Preferable performance, manganese oxide multivalent state makes it have good redox ability in the catalyst.When nitric oxide and dioxy
The mol ratio for changing nitrogen is 1:When 1, the efficiency optimization of SCR, and in the catalyst cerium oxide have it is excellent store oxygen ability, while
Cobalt oxide also possesses certain oxidability, and so as to promote the generation of nitrogen dioxide to a certain extent reaction efficiency is improved.
Description of the drawings
Fig. 1 is the NH of catalyst described in the embodiment of the present invention 1 ~ 53- SCR reactivity figures.
Specific embodiment
It is described in detail with reference to specific embodiment：The present embodiment is carried out under premised on technical solution of the present invention
Implement, give detailed embodiment and specific operation process, but protection scope of the present invention is not limited to following embodiments.
Embodiment 1
1.79 gram of 50% manganese nitrate solution is weighed, 19.5 grams of cerous nitrates in being dissolved in 200 milliliters of water, are stirred at room temperature dissolving, dripped
Plus the ammonium carbonate solution of 30 milliliter of 2.9 mol/L, filtration washing after continuing to stir 2 hours, 12 are dried in 70 DEG C of baking ovens little
When, then 500 DEG C of roastings 4 hours in Muffle furnace, obtain cerium Mn oxide Ce9Mn1.
Weigh 0.09 gram of cobalt nitrate to be dissolved in 1.00 ml deionized waters, obtain cobalt liquor and be added dropwise to 1.0 grams
In Ce9Mn1 catalyst, impregnate 6 hours, be put in 70 DEG C of baking ovens and be dried 12 hours, be then placed in 500 DEG C of roastings 4 in Muffle furnace
Hour, obtain 2.5%Co/Ce9Mn1 catalyst.
Embodiment 2
Compared with Example 1 compared with, except for the difference that the quality of 50% manganese nitrate solution is 5.37 grams, and the quality of cerous nitrate is 15.2 grams,
The concentration of ammonium carbonate solution is 2.7 mol/Ls, and other operating conditions are same as Example 1, obtain 2.5%Co/Ce7Mn3 and urge
Agent.
Embodiment 3
Compared with Example 1 compared with, except for the difference that the quality of 50% manganese nitrate solution is 16.1 grams, and the quality of cerous nitrate is 2.17 grams,
The concentration of ammonium carbonate solution is 2.1 mol/Ls, and other operating conditions are same as Example 1, obtain 2.5%Co/Ce1Mn9 and urge
Agent.
Embodiment 4
Compared with Example 1 compared with except for the difference that the quality of cobalt nitrate is 0.18 gram, and other operating conditions are same as Example 1, obtain
To 5%Co/Ce1Mn9 catalyst.
Embodiment 5
Compared with Example 1 compared with except for the difference that the quality of cobalt nitrate is 0.36 gram, and other operating conditions are same as Example 1, obtain
To 10%Co/Ce1Mn9 catalyst.
Test case
Respectively take fresh obtained catalyst to be attached separately in crystal reaction tube.Test temperature from 20-400 DEG C, 100-400 DEG C it
Between, a test point is taken every 25 DEG C, respectively kept for 10 minutes in each test point.Nitric oxide production conversion ratio as shown in figure 1, from
As can be seen that keeping the load capacity 2.5% of cobalt constant in figure, the mol ratio of cerium and manganese is adjusted, the activity of catalyst is presented larger
Difference, when the amount of cerium in cerium manganese composite oxides is reduced and the amount of manganese increases, the activity of catalyst gradually rises, and obtains highest
The reaction temperature of activity is gradually lowered, when the mol ratio of cerium and manganese is 1:When 9, nitric oxide production conversion ratio is reachable at 150 DEG C
To 97%.Cerium is kept to be 1 with the mol ratio of manganese:9 is constant, increases the load capacity of cobalt, and the activity of catalyst is presented first to raise and reduced afterwards
Trend, when cobalt load capacity be 5% when, nitric oxide production conversion ratio can reach nearly more than 99% at 125 DEG C.Continue to increase cobalt
Load capacity to 10% when, nitric oxide production conversion ratio is reduced on the contrary, and at 150 DEG C, conversion ratio is 93%.
Claims (4)
1. a kind of cerio catalyst for the low-temperature catalyzed elimination of benzene, it is characterised in that it is the cerium oxide of cobalt doped, wherein rubbing
You are than being Co/Ce=1:9~3:7.
2. a kind of preparation method of the cerio catalyst for the low-temperature catalyzed elimination of benzene according to claim 1, its feature exists
In mainly including the following steps that：
（1）The mixed solution of citric acid and sodium hydroxide is prepared, its total concentration is 8.0mol/L, wherein citric acid and sodium hydroxide
Mol ratio be 5:3, referred to as solution A；
（2）The presoma mixing salt solution of cobalt and cerium is prepared, its total concentration is 0.6mol/L, and wherein the mol ratio of cobalt and cerium is 1:
9~3:7, referred to as solution B；
（3）Kept for 80 ~ 100 DEG C, under conditions of stirring, B solution is dropwise added drop-wise in solution A, stir 24 ~ 48h, wherein A is molten
The volume ratio of liquid and B solution is 2:1；
（4）By the precipitate with deionized water for obtaining washing, 80 ~ 110 DEG C overnight dry, 400 ~ 500 DEG C of 2 ~ 4h of roasting, obtain made
The cerium oxide catalyst of standby cobalt doped.
3. a kind of preparation method of the cerio catalyst for the low-temperature catalyzed elimination of benzene according to claim 2, its feature exists
In step（2）Described in the presoma of cobalt and cerium be one kind in nitrate, acetate or the oxalates of cobalt and cerium.
4. being used for the cerio catalyst of the low-temperature catalyzed elimination of benzene according to claim 1 is used for answering for the low-temperature catalyzed elimination of benzene
With.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610953189.5A CN106563464A (en) | 2016-12-23 | 2016-12-23 | Cerium-based catalyst for benzene low-temperature catalytic removal, and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610953189.5A CN106563464A (en) | 2016-12-23 | 2016-12-23 | Cerium-based catalyst for benzene low-temperature catalytic removal, and preparation and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106563464A true CN106563464A (en) | 2017-04-19 |
Family
ID=58535315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610953189.5A Pending CN106563464A (en) | 2016-12-23 | 2016-12-23 | Cerium-based catalyst for benzene low-temperature catalytic removal, and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106563464A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110292838A (en) * | 2019-07-17 | 2019-10-01 | 常州市龙星工业自动化***有限公司 | Improve the method and device of tubular type plasma reactor air purification effect |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244388A (en) * | 2007-02-13 | 2008-08-20 | 大同股份有限公司 | Nano-gold loaded on manganese oxide/cerium oxide catalyst, producing method and application thereof |
| CN102008956A (en) * | 2010-12-27 | 2011-04-13 | 国电科学技术研究院 | Preparation method of low-temperature selective catalytic reduction (SCR) catalyst by removing NOx from flue gas |
| CN102649077A (en) * | 2011-02-24 | 2012-08-29 | 东丽纤维研究所（中国）有限公司 | Catalyst for denitrating smoke at low temperature and production method and application thereof |
| WO2012119299A1 (en) * | 2011-03-07 | 2012-09-13 | 山东众禾环保科技股份有限公司 | Flue gas denitration catalyst, preparation method and use thereof |
| CN105289641A (en) * | 2015-10-30 | 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-load cerium manganese oxide catalyst and preparation method thereof |
-
2016
- 2016-12-23 CN CN201610953189.5A patent/CN106563464A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244388A (en) * | 2007-02-13 | 2008-08-20 | 大同股份有限公司 | Nano-gold loaded on manganese oxide/cerium oxide catalyst, producing method and application thereof |
| CN102008956A (en) * | 2010-12-27 | 2011-04-13 | 国电科学技术研究院 | Preparation method of low-temperature selective catalytic reduction (SCR) catalyst by removing NOx from flue gas |
| CN102649077A (en) * | 2011-02-24 | 2012-08-29 | 东丽纤维研究所（中国）有限公司 | Catalyst for denitrating smoke at low temperature and production method and application thereof |
| WO2012119299A1 (en) * | 2011-03-07 | 2012-09-13 | 山东众禾环保科技股份有限公司 | Flue gas denitration catalyst, preparation method and use thereof |
| CN105289641A (en) * | 2015-10-30 | 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-load cerium manganese oxide catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| GONGSHIN QI等: ""Performance and kinetics study for low-temperature SCR of NO with NH3 over MnOx–CeO2 catalyst"", 《JOURNAL OF CATALYSIS》 * |
| 吴忠标等: "《大气污染控制技术》", 31 May 2002 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110292838A (en) * | 2019-07-17 | 2019-10-01 | 常州市龙星工业自动化***有限公司 | Improve the method and device of tubular type plasma reactor air purification effect |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106540710A (en) | A kind of cerium manganese load cobalt oxide low-temperature denitration catalyst and preparation and application | |
| CN101480611B (en) | Vanadium-doped titanium-base flue gas denitration catalyst material and preparation method thereof | |
| CN107262086B (en) | SCR denitration, the preparation method and application for promoting ammonium hydrogen sulfate to decompose for low-temperature flue gas | |
| CN101590404B (en) | Low-vanadium denitration catalyst and preparation method and application thereof | |
| CN102658161B (en) | Supported iron-based composite oxide catalyst and preparation method thereof | |
| CN102658155B (en) | Preparation method of supported type denitration catalyst | |
| CN101396656A (en) | Power plant flue-gas SCR denitration catalyst capable of preventing sulfur trioxide poisoning and preparation method thereof | |
| CN102259009B (en) | Sulfate radical promoted TiO2 carrier based SCR (Selective Catalytic Reduction) flue gas denitration catalyst and preparation method thereof | |
| CN103769083B (en) | A kind of NO_x Reduction by Effective composite oxide catalysts and its preparation method and application | |
| CN107649116A (en) | Cerium tin composite oxides denitrating catalyst and its preparation method and application | |
| CN109351358A (en) | A kind of transition metal oxide composite catalyst and its preparation method and application | |
| CN107308944A (en) | A kind of TiO 2-based catalyst and its preparation method and application | |
| CN102101048A (en) | Cerium-based denitration catalyst with titanium-silicon compound oxide as carrier and preparation and application thereof | |
| CN101804344A (en) | Manganese/carbon nanotube denitrification catalytic reduction catalyst and preparation method thereof | |
| CN101879452A (en) | Manganese-based low-temperature denitration catalyst and preparation method thereof | |
| CN105944713A (en) | Denitration catalyst containing tungsten-tin-manganese-cerium composite oxide as well as preparation and application of denitration catalyst | |
| CN107570145A (en) | Tin dope cerium zirconium compound oxide Supported Manganese denitrating catalyst preparation method and products thereof and application | |
| CN102989447A (en) | Manganese-tin-titanium type SCR (Selective Catalytic Reduction) NOx removal catalyst and preparation method thereof | |
| CN108704650A (en) | Preparation method of low temperature porous composite oxide denitrating catalyst and products thereof and application | |
| CN106423148A (en) | Zirconium-doped cerium-manganese oxide catalyst as well as preparation and application | |
| CN109513339B (en) | High-temperature catalytic reduction method for cement kiln flue gas denitration | |
| CN105797714A (en) | Holmium modified manganese-titanium complex oxide low-temperature denitrification catalyst and preparation method thereof | |
| CN107185523A (en) | Preparation method of denitrating catalyst that a kind of holmium is modified and products thereof | |
| CN112295555B (en) | Cerium-titanium composite nanorod catalyst for fixed source flue gas denitration reaction and preparation method thereof | |
| CN106362733A (en) | High-temperature resistant manganite catalyst and preparation method 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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170419 |
|
| WD01 | Invention patent application deemed withdrawn after publication |