CN110368927A - A kind of preparation method of manganese oxide/active carbon denitrating catalyst - Google Patents
A kind of preparation method of manganese oxide/active carbon denitrating catalyst Download PDFInfo
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- CN110368927A CN110368927A CN201910662076.3A CN201910662076A CN110368927A CN 110368927 A CN110368927 A CN 110368927A CN 201910662076 A CN201910662076 A CN 201910662076A CN 110368927 A CN110368927 A CN 110368927A
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- manganese
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- active carbon
- denitrating catalyst
- manganese oxide
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- 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
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- 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 manganese oxide/active carbon denitrating catalyst preparation methods, comprising steps of preparing hydrated manganese colloidal sol first, then gelling agent is added in carbon precursor solution and hydrated manganese colloidal sol after mixing, obtain carbon precursor-hydrated manganese gel, gained gel is calcined again, and manganese oxide/active carbon denitrating catalyst can be obtained.Invention significantly improves active component dispersibility in the carrier and its with the bond strength of carrier.Catalyst low-temperature denitration prepared by the present invention is had excellent performance, and is had broad application prospects in industrial smoke denitration field.
Description
Technical field
The invention belongs to atmosphere pollution Treatment process fields, are related to a kind of catalyst system that can be used for flue gas low-temperature denitration
A kind of Preparation Method, and in particular to preparation method of manganese oxide/active carbon denitrating catalyst.
Background technique
Industrial pot (kiln) kiln gas denitration is the emphasis that atmosphere pollution is administered in recent years.Common method of denitration mainly has
Low nitrogen burning method, SNCR method and low-temperature SCR method.Since low nitrogen burning method and SNCR method denitration efficiency are low, it is difficult to meet environmental protection and wants
Ask, especially nitrogen oxides minimum discharge requirement, thus develop efficient low temperature SCR denitration technology seem it is particularly necessary with again
It wants.
Catalyst is the core technology of low temperature SCR denitration.Currently, low-temperature SCR catalyst is mainly with manganese oxide or oxidation
Cerium is active component, and titanium dioxide or active carbon are carrier, is formed by process combining appropriate.TiO 2-based catalyst is low
Warm poor activity, denitration temperature window usually require flue gas heating when applying on industrial pot (kiln) furnace between 180~300 DEG C,
Cause denitrating technique complexity, denitration at high cost.Absorbent charcoal based catalyst low temperature active is high, and denitration temperature can be down to 100 DEG C, with work
Industry pot (kiln) furnace exhaust gas temperature coincide, and has broad application prospects, but influenced (predominantly infusion process) by preparation process, living
Property component disperse in the carrier uneven and weak with carrier bond strength, lead to absorbent charcoal based catalyst in practical engineering applications
Denitration effect is poor, therefore, explores novel active carbon based denitration catalyst preparation method and is of great significance.
Summary of the invention
It is an object of the invention to overcome the above-mentioned prior art, provides a kind of manganese oxide/active carbon denitration and urge
The preparation method of agent.
To achieve the above object, the present invention realizes by following technical solution:
A kind of preparation method of manganese oxide/active carbon denitrating catalyst, comprising the following steps:
(1) preparation of hydrated manganese colloidal sol
Sodium hydroxide solution is added dropwise in manganese chloride solution, until by gained sediment centrifugation, washing when pH is 8, so
Gained precipitating is dispersed in water afterwards, obtains dispersion liquid, and dodecyl sodium sulfate is added, while being carried out after adding water to adjust pH value
Colloidal sol 1~3 hour, obtain hydrated manganese colloidal sol；
(2) activated carbon precursor-hydrated manganese gel preparation
It is added in hydrated manganese colloidal sol after activated carbon precursor is dissolved, is stirred at room temperature uniformly, gelling agent is then added,
It is placed 1~2 hour at 40~50 DEG C, obtains activated carbon precursor-hydrated manganese gel；
(3) activated carbon precursor-hydrated manganese gel drying and calcining
Activated carbon precursor-hydrated manganese gel is dried and is calcined, manganese oxide/active carbon denitrating catalyst is obtained.
A further improvement of the present invention lies in that the concentration of sodium hydroxide solution is 0.1~0.2mol/L in step (1)；Chlorine
The concentration for changing manganese solution is 0.2~0.8mol/L.
A further improvement of the present invention lies in that adding water to adjust pH value is 6.2~7.4 in step (1).
A further improvement of the present invention lies in that carrying out colloidal sol at 40~60 DEG C in step (1).
A further improvement of the present invention lies in that the quality of dodecyl sodium sulfate is the 1 of dispersion liquid quality in step (1)
~2%.
A further improvement of the present invention lies in that activated carbon precursor is siliceous aryne resin, benzoxazine in step (2)
Any one of resin and phenolic resin.
A further improvement of the present invention lies in that the mass ratio of activated carbon precursor and hydrated manganese colloidal sol is (5 in step (2)
~7): 1.
A further improvement of the present invention lies in that gelling agent is organic amine in step (2), the dosage of gelling agent is hydrated manganese
The 2%~3% of colloidal sol quality.
A further improvement of the present invention lies in that organic amine is diethylamine or triethylamine in step (2).
A further improvement of the present invention lies in that drying condition is in step (3): with the heating rate of≤3 DEG C/min from room
Temperature is warming up to 110~120 DEG C, and keeps the temperature 8~10 hours；The condition of calcining are as follows: with the heating rate of≤3 DEG C/min from room temperature liter
Temperature keeps the temperature 6~8 hours to 1000~1200 DEG C.Compared with prior art, the present invention has following beneficial technical effect:
(1) first by support precursor (siliceous aryne resin, benzoxazine resin and phenolic resin) and active component forerunner
Body (hydrated manganese colloidal sol) is mixed in solution state, then drying and calcining, is made active component is synchronous with carrier situ to generate, in this way may be used
From molecular level guarantee active component dispersibility in the carrier and its with the bond strength of carrier.Therefore, with prior art phase
Than catalyst activity component dispersion prepared by the present invention is more evenly, bigger with the bond strength of carrier.
(2) in the present invention, active component and carrier in-situ synchronization generates, as a kind of inorganic particulate, active component tool
Play the role of enhancing carrier, therefore, compared with prior art, its physical mechanical property of catalyst prepared by the present invention is more excellent.
Specific embodiment
The present invention is made further instructions with reference to embodiments.
The present invention provides a kind of preparation method of manganese oxide/active carbon denitrating catalyst, includes the following steps:
(1) preparation of hydrated manganese colloidal sol
0.1~0.2mol/L sodium hydroxide solution is added dropwise in 0.2~0.8mol/L manganese chloride solution, until pH is 8
When by gained sediment centrifugation, washing, then gained precipitating is dispersed in water, obtains dispersion liquid, and is added and accounts for dispersion liquid matter
The dodecyl sodium sulfate of amount 1~2%, at the same add water adjust pH value to after 6.2~7.4, carried out at 40~60 DEG C colloidal sol 1~
3 hours, obtain hydrated manganese colloidal sol.
(2) activated carbon precursor-hydrated manganese gel preparation
It is added in hydrated manganese colloidal sol after activated carbon precursor is dissolved, wherein activated carbon precursor and hydrated manganese colloidal sol
Mass ratio is (5~7): 1.After being stirred at room temperature uniformly, the gelling agent for accounting for hydrated manganese colloidal sol quality 2%~3% is added,
40~50 DEG C are placed 1~2 hour, and activated carbon precursor-hydrated manganese gel is obtained.
Wherein, activated carbon precursor is any one of siliceous aryne resin, benzoxazine resin and phenolic resin.Gel
Agent is organic amine, is any one of diethylamine and triethylamine.
(3) activated carbon precursor-hydrated manganese gel drying and calcining
By activated carbon precursor-hydrated manganese gel with the heating rate of≤3 DEG C/min from room temperature to 110~120 DEG C,
And 8~10 hours are kept the temperature, drying terminates, then with the heating rate of≤3 DEG C/min from room temperature to 1000~1200 DEG C, and protects
Temperature 6~8 hours, calcining terminates, and finally obtains manganese oxide/active carbon denitrating catalyst and (is denoted as MnOx/AC)。
By gained manganese oxide/active carbon denitrating catalyst on catalyst activity is test bed, using simulated flue gas into
Row low-temperature denitration performance evaluation.Initial flue gas condition is: 150 DEG C of smoke temperature, total gas flow rate 1L/min, O2Concentration is 6 (v/
V) %, NO concentration are 350ppm, NH3Concentration is 350ppm, SO2Concentration is 1000ppm, H2O concentration is 10 (v/v) %, air speed
4000h-1, denitration efficiency tested with 350 flue gas analyzer of Testo.
The results are shown in Table 1 for embodiment.
The result of 1 embodiment of table
Claims (10)
1. a kind of manganese oxide/active carbon denitrating catalyst preparation method, which comprises the following steps:
(1) preparation of hydrated manganese colloidal sol
Sodium hydroxide solution is added dropwise in manganese chloride solution, until then will by gained sediment centrifugation, washing when pH is 8
Gained precipitating is dispersed in water, and obtains dispersion liquid, and dodecyl sodium sulfate is added, while carrying out colloidal sol after adding water to adjust pH value
1~3 hour, obtain hydrated manganese colloidal sol；
(2) activated carbon precursor-hydrated manganese gel preparation
It is added in hydrated manganese colloidal sol after activated carbon precursor is dissolved, is stirred at room temperature uniformly, gelling agent is then added, 40
~50 DEG C are placed 1~2 hour, and activated carbon precursor-hydrated manganese gel is obtained；
(3) activated carbon precursor-hydrated manganese gel drying and calcining
Activated carbon precursor-hydrated manganese gel is dried and is calcined, manganese oxide/active carbon denitrating catalyst is obtained.
2. a kind of preparation method of manganese oxide/active carbon denitrating catalyst according to claim 1, which is characterized in that step
Suddenly in (1), the concentration of sodium hydroxide solution is 0.1~0.2mol/L；The concentration of manganese chloride solution is 0.2~0.8mol/L.
3. a kind of preparation method of manganese oxide/active carbon denitrating catalyst according to claim 1, which is characterized in that step
Suddenly in (1), adding water to adjust pH value is 6.2~7.4.
4. a kind of preparation method of manganese oxide/active carbon denitrating catalyst according to claim 1, which is characterized in that step
Suddenly in (1), colloidal sol is carried out at 40~60 DEG C.
5. a kind of preparation method of manganese oxide/active carbon denitrating catalyst according to claim 1, which is characterized in that step
Suddenly in (1), the quality of dodecyl sodium sulfate is the 1~2% of dispersion liquid quality.
6. a kind of preparation method of manganese oxide/active carbon denitrating catalyst according to claim 1, which is characterized in that step
Suddenly in (2), activated carbon precursor is any one of siliceous aryne resin, benzoxazine resin and phenolic resin.
7. a kind of preparation method of manganese oxide/active carbon denitrating catalyst according to claim 1, which is characterized in that step
Suddenly in (2), the mass ratio of activated carbon precursor and hydrated manganese colloidal sol is (5~7): 1.
8. a kind of preparation method of manganese oxide/active carbon denitrating catalyst according to claim 1, which is characterized in that step
Suddenly in (2), gelling agent is organic amine, and the dosage of gelling agent is the 2%~3% of hydrated manganese colloidal sol quality.
9. a kind of preparation method of manganese oxide/active carbon denitrating catalyst according to claim 1, which is characterized in that step
Suddenly in (2), organic amine is diethylamine or triethylamine.
10. a kind of preparation method of manganese oxide/active carbon denitrating catalyst according to claim 1, which is characterized in that step
Suddenly in (3), drying condition is: with the heating rate of≤3 DEG C/min from room temperature to 110~120 DEG C, and it is small to keep the temperature 8~10
When；The condition of calcining are as follows: with the heating rate of≤3 DEG C/min from room temperature to 1000~1200 DEG C, and keep the temperature 6~8 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111203209A (en) * | 2020-03-04 | 2020-05-29 | 中国科学院过程工程研究所 | Embedded catalyst, preparation method thereof and reactor |
| CN112844374A (en) * | 2021-01-22 | 2021-05-28 | 上海应用技术大学 | Mn-Ce-Ti oxide aerogel denitration catalyst and preparation method and application thereof |
| CN113636548A (en) * | 2020-05-11 | 2021-11-12 | 中冶长天国际工程有限责任公司 | Activated carbon with high sulfur resistance and high denitration rate and preparation method thereof |
| CN116328758A (en) * | 2021-12-22 | 2023-06-27 | 中国科学院过程工程研究所 | Fly ash-based manganese catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103050702A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Application of carbon material containing in-situ doped component with catalytic activity to lithium-air battery |
| CN106731581A (en) * | 2017-01-20 | 2017-05-31 | 中国科学院城市环境研究所 | A kind of activated carbon supported MnO2Preparation method, the equipment and technique of industrial smoke denitration |
| CN106807363A (en) * | 2017-03-20 | 2017-06-09 | 常州大学 | A kind of manganese systems supported titanium doping nano-tube SCR catalyst and preparation method thereof |
| CN109092325A (en) * | 2018-09-11 | 2018-12-28 | 东北大学 | A kind of catalyst and the preparation method and application thereof for low-temperature denitration of flue gas |
| CN109999829A (en) * | 2019-04-30 | 2019-07-12 | 常州大学 | A kind of bimetallic manganese iron low temperature SCR denitration catalyst, preparation method and applications |
-
2019
- 2019-07-22 CN CN201910662076.3A patent/CN110368927A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103050702A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Application of carbon material containing in-situ doped component with catalytic activity to lithium-air battery |
| CN106731581A (en) * | 2017-01-20 | 2017-05-31 | 中国科学院城市环境研究所 | A kind of activated carbon supported MnO2Preparation method, the equipment and technique of industrial smoke denitration |
| CN106807363A (en) * | 2017-03-20 | 2017-06-09 | 常州大学 | A kind of manganese systems supported titanium doping nano-tube SCR catalyst and preparation method thereof |
| CN109092325A (en) * | 2018-09-11 | 2018-12-28 | 东北大学 | A kind of catalyst and the preparation method and application thereof for low-temperature denitration of flue gas |
| CN109999829A (en) * | 2019-04-30 | 2019-07-12 | 常州大学 | A kind of bimetallic manganese iron low temperature SCR denitration catalyst, preparation method and applications |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111203209A (en) * | 2020-03-04 | 2020-05-29 | 中国科学院过程工程研究所 | Embedded catalyst, preparation method thereof and reactor |
| CN111203209B (en) * | 2020-03-04 | 2021-12-14 | 中国科学院过程工程研究所 | Embedded catalyst, preparation method thereof and reactor |
| CN113636548A (en) * | 2020-05-11 | 2021-11-12 | 中冶长天国际工程有限责任公司 | Activated carbon with high sulfur resistance and high denitration rate and preparation method thereof |
| CN112844374A (en) * | 2021-01-22 | 2021-05-28 | 上海应用技术大学 | Mn-Ce-Ti oxide aerogel denitration catalyst and preparation method and application thereof |
| CN116328758A (en) * | 2021-12-22 | 2023-06-27 | 中国科学院过程工程研究所 | Fly ash-based manganese catalyst and preparation method and application thereof |
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