CN103480271A - Smoke treatment method - Google Patents
Smoke treatment method Download PDFInfo
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- CN103480271A CN103480271A CN201310431994.8A CN201310431994A CN103480271A CN 103480271 A CN103480271 A CN 103480271A CN 201310431994 A CN201310431994 A CN 201310431994A CN 103480271 A CN103480271 A CN 103480271A
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- hydrogen peroxide
- catalyst
- ruthenium
- processing method
- flue gas
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Abstract
The invention provides a smoke treatment method which comprises the following steps: under the condition that the smoke is subjected to denitration and demercuration, the smoke is contacted with a catalyst, wherein the catalyst is prepared through the following steps: a ruthenium-containing substance, a ti-based denitration catalyst and hydrogen peroxide are mixed and contacted, and the contacted mixture is roasted after being dried or not dried. The catalyst prepared with the method disclosed by the invention is used for smoke treatment, so that denitration and demercuration can be carried out simultaneously with the method disclosed by the invention, the NOx removal efficiency is obviously improved in comparison with that achieved by using the traditional ti-based denitration catalyst with a single function, and the oxygenation efficiency of HgO (zero-valent Hg) is high, that is, the mercury removal efficiency is high.
Description
Technical field
The present invention relates to a kind of processing method of flue gas.
Background technology
The pollutant discharged in the power generation process of thermal power plant causes serious environmental pollution, and present stage, China administered the coal-fired SO produced
2pollution problem has obtained certain achievement, be devoted to administer the NOx pollution problem, and the coal-fired mercury pollution problem produced also is about to become the new environment protection treating difficult problem of China, the General Office of the State Council forwards Environmental Protection Department " about strengthening the notice of Heavy Metal Pollution job guide suggestion ", focus all classified the mercury pollution control as by files such as " about advancing the work of atmosphere pollution groupcontrol, improving the notice of regional air quality instruction ", " heavy metal pollution integrated control planning ", " about carrying out coal-burning power plant's Mercury In The Air, the polluting the notice of controlling pilot work " of " planning of " 12 " key area atmosphere pollution groupcontrol " and in September, 2010 Environmental Protection Department issue all arranges coal-burning power plant's Mercury In The Air emission control work." fossil-fuel power plant atmospheric pollutant emission standard " of new issue of in July, 2011 (GB13223-2011), proposed requirement to Air Pollutant Emission, set up the Mercury In The Air pollutant emission limit, and the regulation mercury and mercuric compounds is no more than 30 μ g/m
3, can business-like demercuration method and technology but there is no at present.
At present, administering thermal power plant NOx pollutant effective method is to adopt denitration technology (selective reduction technology) or SNCR technology (non-selective reduction technique), adopts the Ti-base catalyst NO_x removal.Conventional titanium based denitration catalyst is to the N in flue gas and Hg
0(nonvalent mercury) has certain catalysed oxidn, thereby NOx is removed in the denitration denitrification apparatus, Hg
0in electric cleaner and desulfurizer, part removes, and its oxidation effectiveness is poor, and the Hg removal efficiency is not high, generally less than 25%, can't meet the requirement of environmental protection, and therefore the urgent need exploitation is a kind of can NO_x removal and Hg
0catalyst, for meeting environmental requirement and requirement that can low-cost batch production.
Summary of the invention
The objective of the invention is in order to meet the new environmental requirement of country, overcome denitrating catalyst function singleness of the prior art, the demercuration catalyst function is single, can not realize the function of not only denitration but also demercuration simultaneously, and the preparation method of two kinds of catalyst is complicated, cost is high, the method step complexity that causes flue gas to process can't realize the defect of not only denitration but also demercuration simultaneously, and the flue gas processing method that can simultaneously realize not only denitration but also demercuration is provided.
For realizing aforementioned purpose, the invention provides a kind of processing method of flue gas, the method comprises: under denitrating flue gas demercuration condition, flue gas is contacted with catalyst, wherein, described catalyst prepares as follows: will mix and contact with hydrogen peroxide containing ruthenium material, titanium based denitration catalyst, by the drying of the mixture after contact or moist after carry out roasting.
The present invention, by using the catalyst prepare according to method of the present invention to carry out the flue gas processing, makes according to method of the present invention denitration simultaneously and demercuration, and than the NO of the titanium based denitration catalyst that uses traditional simple function
xremoval efficiency obviously improves, and Hg
0(nonvalent mercury) oxygenation efficiency is very high, and the efficiency that removes mercury is very high.Supposition be due to containing ruthenium material, titanium based denitration catalyst with after the hydrogen peroxide mixing contacts, make containing the ruthenium material and can be good at disperseing, and caused the structural change of titanium based denitration catalyst, thereby caused the catalyst that the prepares NO than the titanium based denitration catalyst of simple function
xremoval efficiency obviously improves, and Hg
0(nonvalent mercury) oxygenation efficiency is very high.And in the present invention, the method for Kaolinite Preparation of Catalyst is not introduced any other foreign ion in the Kaolinite Preparation of Catalyst process, simplified the preparation process of catalyst, thereby can effectively reduce costs.
Other features and advantages of the present invention will partly be described in detail in the specific embodiment subsequently.
The specific embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, the specific embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of processing method of flue gas, the method comprises: under denitrating flue gas demercuration condition, flue gas is contacted with catalyst, wherein, described catalyst prepares as follows: will mix and contact with hydrogen peroxide containing ruthenium material, titanium based denitration catalyst, by the drying of the mixture after contact or moist after carry out roasting.
The treatment in accordance with the present invention method, can well realize purpose of the present invention according to the aforementioned techniques scheme, for the present invention, in order further to improve denitrating flue gas rate and the demercuration rate according to method of the present invention, preferably will mix with hydrogen peroxide the method contacted and comprise containing ruthenium material, titanium based denitration catalyst: will mix with hydrogen peroxide containing the ruthenium material, the mixture obtained is mixed and contacts with the titanium based denitration catalyst.
In the present invention, optional wider range of the temperature of described mixing contact, can be generally room temperature to 60 ℃.Optional wider range of the temperature that will mix with hydrogen peroxide containing the ruthenium material can be generally room temperature to 60 ℃.
The treatment in accordance with the present invention method, can well realize purpose of the present invention according to the aforementioned techniques scheme, for the present invention, in order further to improve denitrating flue gas rate and the demercuration rate according to method of the present invention, preferably the described ruthenium material that contains is in ruthenium-oxide, described hydrogen peroxide is in hydrogen peroxide, and the consumption weight ratio that contains ruthenium material and hydrogen peroxide is 0.02-20:100, more preferably 0.1-5:100.
The treatment in accordance with the present invention method, can well realize purpose of the present invention according to the aforementioned techniques scheme, for the present invention, in order further to improve denitrating flue gas rate and the demercuration rate according to method of the present invention, preferably the described consumption weight ratio containing ruthenium material and described titanium based denitration catalyst is 0.001-0.1:1, is preferably 0.01-0.05:1.
The treatment in accordance with the present invention method, can well realize purpose of the present invention according to the aforementioned techniques scheme, for the present invention, in order further to improve denitrating flue gas rate and the demercuration rate according to method of the present invention, preferably will after the mixture drying after contact, carry out roasting, more preferably the temperature of described drying is 60-300 ℃, and the temperature of described roasting is 300-1000 ℃.More preferably the time of described drying is 0.1-10h, and the time of roasting is 1-10h.
The treatment in accordance with the present invention method, the concentration of preferred described hydrogen peroxide is the 20-70 % by weight, more preferably the 30-50 % by weight, adopt the hydrogen peroxide of aforementioned concentration to prepare catalyst of the present invention, can further improve denitration and the demercuration activity of catalyst.
The treatment in accordance with the present invention method, described titanium based denitration catalyst can be for the various titanium-base flue gas denitration catalyst agent of prior art, and for the present invention, preferred described titanium based denitration catalyst contains carrier and active component, and described carrier is TiO
2, described active component is vanadium-containing compound, Tungstenic compound and containing one or more in manganese compound, and described vanadium-containing compound can be for example vanadium oxide, and described Tungstenic compound can be for example tungsten oxide, and described can be for example manganese oxide containing manganese compound.
The treatment in accordance with the present invention method, optional wider range of the described kind containing the ruthenium material, can be for example ruthenium simple substance, one or more in ru oxide and ruthenium salt, for the present invention, in order further to improve denitrating flue gas rate and the demercuration rate according to method of the present invention, preferably described is one or more in ruthenic oxide and/or ruthenic chloride containing the ruthenium material.
In the present invention, optional wider range of described denitrating flue gas demercuration condition, for the present invention, preferred described denitrating flue gas demercuration condition comprises: temperature is 250-450 ℃, and pressure is 500-1500Pa.
In the present invention, described flue gas can be the various coal-fired flue gases that produce of the employing of prior art, and it forms the general kind according to coal-fired raw material and determines, and generally speaking, in described flue gas, contains N
220-80 volume %, O
22-10 volume %, CO
210-20 volume %, H
2o1-30 volume %, SO
21-10 volume % and NO1-10 volume %.
Below by embodiment, the present invention will be described in detail, but the present invention is not limited to this.
In embodiments of the invention, the denitration rate refers to the NO that denitrification apparatus removes
xnO in amount (nitrogen-containing oxide in flue gas) and SCR reactor inlet flue gas
xthe ratio of content, computing formula is as follows:
In formula: η---denitration rate, %;
C
1---NO in SCR reactor inlet flue gas
xconcentration (mark state, butt 6%O
2under state), mg/m
3;
C
2---NO in SCR reactor outlet flue gas
xconcentration (mark state, butt 6%O
2under state), mg/m
3.
In the present invention, the demercuration rate refers to Hg in amount that demercuration equipment removes and demercuration equipment entrance flue gas
tthe ratio of (being total mercury element) content, computing formula is as follows:
In formula: η---demercuration rate, %;
Hg in D1---demercuration equipment (being denitrification apparatus in the present invention) inlet flue gas
tconcentration (mark state, butt, 6%O
2under state), mg/m
3;
Hg in D2---demercuration equipment (being denitrification apparatus in the present invention) outlet flue gas
tconcentration (mark state, butt, 6%O
2under state), mg/m
3.
Embodiment 1
Under room temperature (20 ℃), by ruthenium-oxide RuO
2mix with hydrogen peroxide (concentration is 40 % by weight), the mixture and the titanium based denitration catalyst (honeycomb fashion forms: 92 % by weight titanium dioxide, 8 % by weight vanadic anhydrides) that obtain are mixed to contact, will after the mixture drying after contact, carry out roasting; Wherein, ruthenium-oxide is in ruthenium-oxide, and hydrogen peroxide is in hydrogen peroxide, and the consumption weight ratio of ruthenium-oxide and hydrogen peroxide is 0.1:100, and ruthenium-oxide RuO
2with the consumption weight ratio of titanium based denitration catalyst be 0.01:1, dry temperature is 100 ℃, the time is 3h, the temperature of roasting is 400 ℃, the time is 4h, obtains catalyst C1.
Embodiment 2
Under room temperature (20 ℃), ruthenium-oxide is mixed with hydrogen peroxide (concentration is 30 % by weight), by mixture and titanium based denitration catalyst (honeycomb fashion, the composition: 92 % by weight titanium dioxide obtained, 8 % by weight manganese oxide) mix contact, will after the mixture drying after contact, carry out roasting; Wherein, hydrogen peroxide is in hydrogen peroxide, and the consumption weight ratio of ruthenium-oxide and hydrogen peroxide is 5:100, and the consumption weight ratio of ruthenium-oxide and titanium based denitration catalyst is 0.03:1, dry temperature is 300 ℃, and the time is 5h, the temperature of roasting is 1000 ℃, and the time is 2h, obtains catalyst C2.
Embodiment 3
Under room temperature (20 ℃), ruthenic chloride is mixed with hydrogen peroxide (concentration is 50 % by weight), by mixture and titanium based denitration catalyst (honeycomb fashion, the composition: 92 % by weight titanium dioxide obtained, 8 % by weight tungsten oxides) mix contact, will after the mixture drying after contact, carry out roasting; Wherein, ruthenic chloride is in ruthenium-oxide, hydrogen peroxide is in hydrogen peroxide, the consumption weight ratio of ruthenic chloride and hydrogen peroxide is 2:100, and the consumption weight ratio of ruthenic chloride and titanium based denitration catalyst is 0.05:1, and dry temperature is 200 ℃, time is 2h, the temperature of roasting is 600 ℃, and the time is 5h, obtains catalyst C3.
Embodiment 4
According to the method Kaolinite Preparation of Catalyst of embodiment 2, different, hydrogen peroxide is in hydrogen peroxide, and the consumption weight ratio of ruthenic chloride and hydrogen peroxide is 0.02:100, obtains catalyst C4.
Embodiment 5
According to the method Kaolinite Preparation of Catalyst of embodiment 2, different, the consumption weight ratio of ruthenium-oxide and titanium based denitration catalyst is 0.1:1, obtains catalyst C5.
Embodiment 6
According to the method Kaolinite Preparation of Catalyst of embodiment 2, different, the concentration of hydrogen peroxide is 60 % by weight, obtains catalyst C6.
Embodiment 7
According to the method Kaolinite Preparation of Catalyst of embodiment 2, different, not carry out drying and directly carry out roasting, all the other conditions are all identical, obtain catalyst C7.
Embodiment 8
According to the method Kaolinite Preparation of Catalyst of embodiment 2, different, directly ruthenium-oxide, titanium based denitration catalyst are mixed and contact with hydrogen peroxide, the mixture that then will mix contact carries out drying and roasting, and all the other conditions are all identical, obtain catalyst C8.
Embodiment 9
According to the method Kaolinite Preparation of Catalyst of embodiment 2, different, ruthenium-oxide is replaced by the carbonic acid ruthenium, and the carbonic acid ruthenium to take ruthenium-oxide be 0.03:1 with the consumption weight ratio of titanium based denitration catalyst, obtain catalyst C9.
Comparative Examples 1
According to the method Kaolinite Preparation of Catalyst of embodiment 2, different, whole hydrogen peroxide are replaced by water, and all the other conditions are all identical, obtain catalyst D1.
Comparative Examples 2
According to the method Kaolinite Preparation of Catalyst of embodiment 2, different, ruthenic chloride is not mixed with hydrogen peroxide, it directly with after the titanium based denitration catalyst mixes is carried out to roasting, the condition of roasting is constant, and all the other conditions are all identical, obtain catalyst D2.
EXPERIMENTAL EXAMPLE
The catalyst C1-C7 that embodiment 1-8 is prepared is placed in the denitration demercuration reactor, denitration demercuration reactor inlet Gas Parameters is in Table 1, pass into flue gas (forming in Table 1) to contact with catalyst in reactor, the condition of contact comprises: temperature is 350 ℃, pressure is 1200Pa, and gas hourly space velocity is 7800h
-1, the results are shown in Table 2.
The experiment Comparative Examples
Method according to EXPERIMENTAL EXAMPLE is carried out the flue gas processing, different, and the catalyst of use is D1-D2, and the titanium based denitration catalyst that uses of embodiment 2 Kaolinite Preparation of Catalysts, the results are shown in Table 2.
Table 1
Table 2
| Catalyst | Denitration rate/% | Demercuration rate/% |
| C1 | 84.5 | 75.2 |
| C2 | 87.0 | 76.5 |
| C3 | 92.5 | 80.3 |
| C4 | 82.6 | 73.3 |
| C5 | 85.0 | 74.6 |
| C6 | 83.3 | 75.4 |
| C7 | 84.8 | 72.9 |
| C8 | 85,4 | 73.8 |
| C9 | 84.3 | 74.7 |
| D1 | 51.3 | 20 |
| D2 | 45.5 | 13.4 |
| The titanium based denitration catalyst | 60.1 | 0 |
Can be found out the catalyst n O prepared according to preparation method of the present invention by table 2 result
xremoval efficiency obviously improves, and Hg
0(nonvalent mercury) oxygenation efficiency is that the demercuration rate is very high.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in the above-mentioned specific embodiment, in reconcilable situation, can be combined by any suitable mode.
In addition, between various embodiment of the present invention, also can carry out any combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (12)
1. the processing method of a flue gas, the method comprises: under denitrating flue gas demercuration condition, flue gas is contacted with catalyst, it is characterized in that, described catalyst prepares as follows: will mix and contact with hydrogen peroxide containing ruthenium material, titanium based denitration catalyst, by the drying of the mixture after contact or moist after carry out roasting.
2. processing method according to claim 1, wherein, will mix with hydrogen peroxide the method contacted and comprise containing ruthenium material, titanium based denitration catalyst: will mix with hydrogen peroxide containing the ruthenium material, the mixture obtained is mixed and contacts with the titanium based denitration catalyst.
3. processing method according to claim 1 and 2, wherein, described containing the ruthenium material in ruthenium-oxide, described hydrogen peroxide is in hydrogen peroxide, containing the consumption weight ratio of ruthenium material and hydrogen peroxide, is 0.02-20:100.
4. processing method according to claim 3, wherein, described containing the ruthenium material in ruthenium-oxide, described hydrogen peroxide is in hydrogen peroxide, containing the consumption weight ratio of ruthenium material and hydrogen peroxide, is 0.1-5:100.
5. according to the described processing method of any one in claim 1-4, wherein, the described consumption weight ratio containing ruthenium material and described titanium based denitration catalyst is 0.001-0.1:1.
6. according to the described processing method of any one in claim 1-5, wherein, while after the mixture drying by after contact, carrying out roasting, the temperature of described drying is 60-300 ℃; The temperature of described roasting is 300-1000 ℃.
7. according to the described processing method of any one in claim 6, wherein, the time of described drying is 0.1-10h, and the time of roasting is 1-10h.
8. according to the described processing method of any one in claim 1-7, wherein, the concentration of described hydrogen peroxide is the 20-70 % by weight.
9. according to the described processing method of any one in claim 1-8, wherein, described titanium based denitration catalyst contains carrier and active component, and described carrier is TiO
2, described active component is vanadium-containing compound, Tungstenic compound and containing one or more in manganese compound.
10. according to the described processing method of any one in claim 1-9, wherein, described is one or more in ruthenium simple substance, ru oxide and ruthenium salt containing the ruthenium material.
11., according to the described processing method of any one in claim 1-10, wherein, described denitrating flue gas demercuration condition comprises: temperature is 250-450 ℃, pressure is 500-1500Pa.
12., according to the described processing method of any one in claim 1-11, wherein, in described flue gas, contain N
220-80 volume %, O
22-10 volume %, CO
210-20 volume %, H
2o1-30 volume %, SO
21-10 volume % and NO1-10 volume %.
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|---|---|---|---|
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|---|---|---|---|
| CN201310431994.8A CN103480271A (en) | 2013-09-22 | 2013-09-22 | Smoke treatment method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106984304A (en) * | 2017-04-28 | 2017-07-28 | 华南理工大学 | A kind of Ru Ag bimetal composite denitrating catalysts and its preparation method and application |
| CN107952432A (en) * | 2017-11-29 | 2018-04-24 | 西安元创化工科技股份有限公司 | A kind of preparation method of heavy oil hydrogenating treatment catalyst |
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| CN1806914A (en) * | 2006-02-23 | 2006-07-26 | 华南理工大学 | Method for preparing carbon nanotube supported nanometer hydrated ruthenium oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106984304A (en) * | 2017-04-28 | 2017-07-28 | 华南理工大学 | A kind of Ru Ag bimetal composite denitrating catalysts and its preparation method and application |
| CN107952432A (en) * | 2017-11-29 | 2018-04-24 | 西安元创化工科技股份有限公司 | A kind of preparation method of heavy oil hydrogenating treatment catalyst |
| CN107952432B (en) * | 2017-11-29 | 2021-03-05 | 西安元创化工科技股份有限公司 | Preparation method of hydrogen chloride oxidation catalyst |
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