CN103351024A - Production process of ultrafine titanium dioxide especially used in flue gas denitration catalyst - Google Patents
Production process of ultrafine titanium dioxide especially used in flue gas denitration catalyst Download PDFInfo
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- CN103351024A CN103351024A CN 201310235466 CN201310235466A CN103351024A CN 103351024 A CN103351024 A CN 103351024A CN 201310235466 CN201310235466 CN 201310235466 CN 201310235466 A CN201310235466 A CN 201310235466A CN 103351024 A CN103351024 A CN 103351024A
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- titanium dioxide
- metatitanic acid
- flue gas
- vanadium
- catalyst
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Abstract
The invention belongs to the technical field of titanium dioxide preparation, forming, and processing, and specifically relates to a production process of ultrafine titanium dioxide especially used in a flue gas denitration catalyst. The process comprises the steps of titanium oxide sulfate preparation, precipitation, filtration, drying, and roasting. A roasting temperature is commonly 550-650 DEG C. During normal sintering, an oxygen concentration is 4-7%; the ratio of oxygen to fuel gas is adjusted every 3h, wherein the concentration of oxygen is maintained at below 2% for 15min. The process is advantages in that: when an active component vanadium is loaded, the denitration catalyst is formed. The titanium dioxide carrier has high specific surface area, a porous structure, and a large amount of acidic centers on the surface. When vanadium is loaded on titanium dioxide, titanium dioxide is subjected to interaction with vanadium, such that vanadium catalytic activity is increased, vanadium catalyst sulfur resistance and poisoning resistance are increased, the activity is high, and catalytic efficiency is high.
Description
Technical field
The invention belongs to the standby forming processing technology field of superfine titanium white system, specifically refer to a kind of catalyst for denitrating flue gas specialized superfine titanium white production technique.
Background technology
Selective catalytic reduction reaction mainly is to remove oxynitride.Oxynitride forms in the high-temp combustion process, is considered to a kind of to environment and human harmful poisonous gas, such as nitrogen protoxide, nitrogen peroxide, forms photo-chemical smog and acid rain.Titanium dioxide is applied to power plant and chemical industry, oil refining, coking, glassworks the inside Denitration in Boiler, the manufacturing of smoke gas treatment and automobile, the required denitrating catalyst of steamer vent gas treatment.But the denitration titanium dioxide activity of prior art is relatively poor, and catalytic efficiency is low, and the oxidizing sulfur dioxide rate is high, reduces catalyst activity.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, and a kind of titanium dioxide that activity is good, catalytic efficiency is high that has is provided.
The present invention is achieved through the following technical solutions, and 1). the titanyl sulfate preparation: stirring was 2-3 hour under 100-120 ℃ with metatitanic acid, the vitriol oil, water mixing in 1: 2: 1 in mass ratio, made the metatitanic acid dissolving form titanyl sulfate;
Ti(OH)
2+H
2SO4→Ti(SO
4)
2+H
2O。
2). precipitation: alkaline silica sol and ammoniacal liquor are put into agitator, splash into titanyl sulfate solution, the order of primary deposition is positive metatitanic acid, silicon sol; After primary deposition was finished, pH value was about 6, and continue to add the sulphuric acid soln of titanyl sulfate this moment, makes PH be adjusted to 2-3, realized the again dissolving of the positive metatitanic acid of part; Then adjust pH value to 5-7 with ammoniacal liquor, the positive metatitanic acid of dissolving is precipitated again, this process can realize that metatitanic acid is deposited in the surface of silicon gel; At last, ammonium metawolframate is joined in the metatitanic acid slurries after the cleaning, stir, adjust pH value to 4 with acid, make it become the wolframic acid precipitation.
3). filter: because the metatitanic acid particle that is settled out is little, use the encryption filter cloth in vacuum filter, to filter;
TiOSO
4+NH
4OH→Ti(OH)
4+(NH
4)
2SO
4。
4). drying: adopt middling speed dry, and dry more than 90 ℃, can obtain so better carrier pore volume aperture.
5). roasting: the temperature of roasting, intensification rate of temperature fall and atmosphere all affect the performance that denitrating catalyst is used titanium dioxide.In the process of roasting titanium dioxide, by regulating the ratio of oxygen and combustion gas, change the redox condition of atmosphere, make that the interaction of auxiliary agent and titanium dioxide further improves in the titanium dioxide, and then the denitration performance behind the raising titanium dioxide load vanadium.The maturing temperature root is generally at 550-650 ℃.The concentration of oxygen is about 4-7% when normally burning till, every interval 3 hours, and the ratio of regulating oxygen and combustion gas makes oxygen concentration less than 2%, and kept 15 minutes;
Ti(OH)
4→TiO
2+H
2O。
In practice, usually adopt the catalyzer of polynuclear plane.For the ease of processing, a plurality of independent components are made into catalyst module, then with the catalyst layer in these module composition hydrogen-catalyst reactors.Between turnoff time, can dismantle and change each catalyst module from the ingress of reactor.The demand of ammoniacal liquor is to be determined by the content of nitrogen oxides in effluent in this reaction.Then, ammonia is injected in the flue gas of reactor upstream, enters the catalyst reaction layer equably with after flue gas mixes.Flue gas itself also can be evenly distributed in the hydrogen-catalyst reactor by flow deflector, and several catalyst layer surface of then flowing through are reacted, and can realize like this optimum performance of ammonia.The injection ammonia originally be to be stored in the micropore of catalyzer, subsequently with flue gas in the oxynitride molecule react.
Advantage of the present invention is namely to become denitrating catalyst behind the load active component vanadium.Because the titanium dioxide carrier has higher specific surface, pore structure, the surface has more acid sites, so behind load vanadium on this titanium dioxide, can interact with vanadium, and then strengthen the catalytic activity of vanadium, and strengthen anti-sulphur and the anti-poisoning capability of vanadium catalyst.
Embodiment
Comprise following production stage:
1). the titanyl sulfate preparation: stirring was 2-3 hour under 100-120 ℃ with metatitanic acid, the vitriol oil, water mixing in 1: 2: 1 in mass ratio, made the metatitanic acid dissolving form titanyl sulfate;
Ti(OH)
2+H
2SO4→Ti(SO
4)
2+H
2O。
2). precipitation: alkaline silica sol and ammoniacal liquor are put into agitator, splash into titanyl sulfate solution, the order of primary deposition is positive metatitanic acid, silicon sol; After primary deposition was finished, pH value was about 6, and continue to add the sulphuric acid soln of titanyl sulfate this moment, makes PH be adjusted to 2-3, realized the again dissolving of the positive metatitanic acid of part; Then adjust pH value to 5-7 with ammoniacal liquor, the positive metatitanic acid of dissolving is precipitated again, this process can realize that metatitanic acid is deposited in the surface of silicon gel; At last, ammonium metawolframate is joined in the metatitanic acid slurries after the cleaning, stir, adjust pH value to 4 with acid, make it become the wolframic acid precipitation.
3). filter: because the metatitanic acid particle that is settled out is little, use the encryption filter cloth in vacuum filter, to filter;
TiOSO
4+NH
4OH→Ti(OH)
4+(NH
4)
2SO
4。
4). drying: adopt middling speed dry, and dry more than 90 ℃, can obtain so better carrier pore volume aperture.
5). roasting: the temperature of roasting, intensification rate of temperature fall and atmosphere all affect the performance that denitrating catalyst is used titanium dioxide.In the process of roasting titanium dioxide, by regulating the ratio of oxygen and combustion gas, change the redox condition of atmosphere, make that the interaction of auxiliary agent and titanium dioxide further improves in the titanium dioxide, and then the denitration performance behind the raising titanium dioxide load vanadium.The maturing temperature root is generally at 550-650 ℃.The concentration of oxygen is about 4-7% when normally burning till, every interval 3 hours, and the ratio of regulating oxygen and combustion gas makes oxygen concentration less than 2%, and kept 15 minutes;
Ti(OH)
4→TiO
2+H
2O。
Embodiment one, the general range of application of waste material and waste incineration:
Flue gas flow: 15,000-200,000 m
3/ h;
Undressed amount of nitrogen oxides: 200-600 mg/m
3
The amount of nitrogen oxides that purifies: 50-100 mg/m
3
Amount of ammonia slip:＜5 mg/m
3
Reductive agent: such as 25% ammoniacal liquor.
Embodiment two, the general range of application of cement kiln denitration device:
Flue gas flow: 100,000-500,000 m
3/ h;
Undressed nitrous oxides concentration: 800-2,000 mg/m
3
The amount of nitrogen oxides that purifies: based on present O
2Concentration,＜100-＜200 mg/m
3
Amount of ammonia slip: with current O
2Concentration is the basis,＜5 mg/m
3
Reductive agent: such as 25% ammoniacal liquor.
Claims (2)
1. catalyst for denitrating flue gas specialized superfine titanium white production technique is characterized in that
1). the titanyl sulfate preparation: stirring was 2-3 hour under 100-120 ℃ with metatitanic acid, the vitriol oil, water mixing in 1: 2: 1 in mass ratio, made the metatitanic acid dissolving form titanyl sulfate;
Ti(OH)
2+H
2SO4→Ti(SO
4)
2+H
2O；
2). precipitation: alkaline silica sol and ammoniacal liquor are put into agitator, splash into titanyl sulfate solution, the order of primary deposition is positive metatitanic acid, silicon sol; After primary deposition was finished, pH value was about 6, and continue to add the sulphuric acid soln of titanyl sulfate this moment, makes PH be adjusted to 2-3, realized the again dissolving of the positive metatitanic acid of part; Then adjust pH value to 5-7 with ammoniacal liquor, the positive metatitanic acid of dissolving is precipitated again, this process can realize that metatitanic acid is deposited in the surface of silicon gel; At last, ammonium metawolframate is joined in the metatitanic acid slurries after the cleaning, stir, adjust pH value to 4 with acid, make it become the wolframic acid precipitation;
3). filter: because the metatitanic acid particle that is settled out is little, use the encryption filter cloth in vacuum filter, to filter;
TiOSO
4+NH
4OH→Ti(OH)
4+(NH
4)
2SO
4；
4). drying: adopt middling speed dry, and dry more than 90 ℃;
5). roasting: the maturing temperature root is generally at 550-650 ℃.The concentration of oxygen is about 4-7% when normally burning till, every interval 3 hours, and the ratio of regulating oxygen and combustion gas makes oxygen concentration less than 2%, and kept 15 minutes;
Ti(OH)
4→TiO
2+H
2O。
2. catalyst for denitrating flue gas specialized superfine titanium white production technique according to claim 1 is characterized in that also comprising the catalyst for denitrating flue gas specialized superfine titanium dioxide that makes according to above-mentioned steps.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201310235466 CN103351024A (en) | 2013-06-14 | 2013-06-14 | Production process of ultrafine titanium dioxide especially used in flue gas denitration catalyst |
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|---|---|---|---|
| CN 201310235466 CN103351024A (en) | 2013-06-14 | 2013-06-14 | Production process of ultrafine titanium dioxide especially used in flue gas denitration catalyst |
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|---|---|
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ID=49307467
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445389A (en) * | 2014-11-21 | 2015-03-25 | 广西美之峰科技有限责任公司 | Preparation method of flue gas denitration catalyst nano titanium dioxide |
| CN106466597A (en) * | 2015-08-19 | 2017-03-01 | 中国科学院广州能源研究所 | One kind, with Ludox as crystal seed, hydrolyzes the method obtaining denitrating catalyst titanium silica flour |
| CN109174136A (en) * | 2018-08-21 | 2019-01-11 | 云南纳玉环保科技有限公司 | Catalyst for denitrating flue gas special-purpose nanometer titanium dioxide and preparation method thereof |
-
2013
- 2013-06-14 CN CN 201310235466 patent/CN103351024A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445389A (en) * | 2014-11-21 | 2015-03-25 | 广西美之峰科技有限责任公司 | Preparation method of flue gas denitration catalyst nano titanium dioxide |
| CN106466597A (en) * | 2015-08-19 | 2017-03-01 | 中国科学院广州能源研究所 | One kind, with Ludox as crystal seed, hydrolyzes the method obtaining denitrating catalyst titanium silica flour |
| CN106466597B (en) * | 2015-08-19 | 2019-04-23 | 中国科学院广州能源研究所 | One kind hydrolyzing the method for obtaining denitrating catalyst titanium silicon powder using silica solution as crystal seed |
| CN109174136A (en) * | 2018-08-21 | 2019-01-11 | 云南纳玉环保科技有限公司 | Catalyst for denitrating flue gas special-purpose nanometer titanium dioxide and preparation method thereof |
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Application publication date: 20131016 |