CN107812537A - A kind of preparation method of denitrating catalyst - Google Patents
A kind of preparation method of denitrating catalyst Download PDFInfo
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- CN107812537A CN107812537A CN201711216899.0A CN201711216899A CN107812537A CN 107812537 A CN107812537 A CN 107812537A CN 201711216899 A CN201711216899 A CN 201711216899A CN 107812537 A CN107812537 A CN 107812537A
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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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
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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Abstract
The present invention provides a kind of denitrating catalyst preparation method, weighs the raw material of following percentage by weight：Urea 25~35%, triethanolamine 8~12%, citric acid 8~12%, sodium citrate 8~12%, water 35~45%, catalyst 0.4~0.6%, the catalyst is made up of Methacrylamide and hydrogen peroxide, and the quality proportioning of Methacrylamide and hydrogen peroxide is 1~2.5:1.Water is added in a kettle, then add urea, it is well mixed after add triethanolamine, after being heated to 50 55 DEG C, add citric acid and catalyst, 70 DEG C are progressively warming up to again, temperature-rise period 3 3.5 hours, 100 140min are then cured at 70 75 DEG C, cool to less than 40 DEG C and add sodium citrate, mix.The preparation method of the present invention can make each raw material fully be linked into multiple aggregation amine, and for product denitration rate up to more than 90%, the concentration of emission of nitrogen oxide in tail gas is less than 200（mg/m3）, relative to traditional ammonia denitration, cost reduces by more than 30%.And it also has combustion-supporting effect, more than 5% can be economized on coal.
Description
Technical field
The present invention relates to denitration technology field, more particularly to removes nitrogen oxidation for fields such as coal fired power generation, manufacture of cement
The preparation method of the catalyst of thing.
Background technology
During coal fired power generation, manufacture of cement etc., environment, reply are polluted to prevent from producing after coal combustion excessive NOx
Coal carries out denitration process, is divided into denitration after denitration before burning, combustion process denitration, burning.Denitration in existing so burning, is mainly adopted
With low-temperature burning, low oxygen combustion, FBC combustion technologies, using low-NOx combustor, coal powder light-dark separation, flue gas recirculating technique etc.
Technology, effect be not highly desirable.SNCR and SCR is current widely used denitration technology, and SNCR is in 850~1100 DEG C of temperature
In the range of reduce NOx method, most-often used medicine is ammonia and urea.In general, SNCR denitration efficiency is to large-scale fire coal
Unit is up to 25%~40%, to small unit up to 80%.SCR is gas denitrifying technology most ripe at present, and it is one
Denitration after kind stove.The catalyst used in SCR is mostly with TiO2For carrier, with V2O5Or V2 O5 -WO3Or V2O5-MoO3For work
Property composition, honeycomb fashion, board-like or corrugated three types are made.It can be divided into high temperature applied to the SCR catalyst in denitrating flue gas
Catalyst (345 DEG C~590 DEG C), middle temperature catalyst (260 DEG C~380 DEG C) and low temperature catalyst (80 DEG C~300 DEG C), it is different
The suitable reaction temperature of catalyst it is different.Domestic and international SCR system uses high temperature mostly, and reaction temperature section is 315 DEG C~400
℃." a kind of cement industry low temperature SCR denitration catalyst and preparation method thereof " disclosed in Chinese patent（CN106076358A）,
Using oxygen using lanthana and/or iron oxide as catalytic active component, with manganese oxide either yittrium oxide and/or praseodymium oxide and manganese oxide
Mixture be co-catalyst, using titanium dioxide and/or aluminum oxide as carrier；On the basis of carrier quality, the matter of active component
It is 0.5%~15% to measure percentage composition, and the weight/mass percentage composition of co-catalyst is 5%~35%.By active component, co-catalysis from
Sub- presoma composite solution, carrier and organic forming agent stir, are kneaded, be old, extrusion molding, are made through drying, roasting.
The catalytic component is environment-friendly, low temperature removing NOxEfficiency high, active temperature windows are wide, high mechanical strength, preparation technology letter
Single, cost is low.But it is due to being denitration after a kind of burning, add denitration link in process, the relative increase process time,
So as to increase production cost.And its composition is inorganic matter, do not possess combustion-supporting effect, therefore fire coal can not be saved.
The content of the invention
It is an object of the invention to provide a kind of preparation method of denitrating catalyst, its denitrating catalyst produced is used for water
In the production technologies such as mud, the denitration in burning, and have combustion-supporting effect, so as to effectively reduce the discharge of nitrogen oxides, reduce
Production cost.
Embodiment of the present invention is：A kind of preparation method of denitrating catalyst, including
（1）Raw material is weighed by following percentage by weight：Urea 25~35%, triethanolamine 8~12%, citric acid 8~12%, lemon
Sour sodium 8~12%, water 35~45%, catalyst 0.4~0.6%, above component sum meet 100%；The catalyst is by methyl-prop
The quality proportioning of acrylamide and hydrogen peroxide composition, Methacrylamide and hydrogen peroxide is 1~2.5:1；
（2）Add water in a kettle, then add urea, it is well mixed after add triethanolamine, be heated to 50-55 DEG C
Afterwards, citric acid and catalyst are added, then is progressively warming up to 70 DEG C, it is temperature-rise period 3-3.5 hours, then ripe at 70-75 DEG C
Change 100-140min, cool to less than 40 DEG C and add sodium citrate, mix.
As the embodiment of optimization, step（1）In, each raw material weight percentage is：Urea 30%, triethanolamine 10%,
Citric acid 10%, sodium citrate 10%, water 39.5%, catalyst 0.5%,
As the embodiment of optimization, step（1）In, the quality proportioning of the Methacrylamide and hydrogen peroxide is 2:1.
As the embodiment of optimization, step（2）In, in the temperature-rise period, per 30min, heating is no more than 5 DEG C.More
Optimize, in the temperature-rise period, per 30min, heating is no more than 3 DEG C, so that each raw material is more sufficiently linked into polynary gather
Close amine.
In the use of the present invention, being directly sprayed onto in stove, usage amount is the 5~10/10000 of coal-fired weight.
In the present invention, urea, triethanolamine inherently have denitration, and urea, triethanolamine, citric acid are in catalyst
Methacrylamide（Bridging agent）, hydrogen peroxide（Initiator）In the presence of, multiple aggregation amine is connected into, sodium citrate is then played and carried
The effect of high and stable multiple aggregation amine activity.The denitration performance of multiple aggregation amine will be far better than single urea and three ethanol
Amine.The preparation method of invention can make each raw material fully be linked into multiple aggregation amine, and its product changes traditional denitration
Mode, for denitration rate up to more than 90%, the concentration of emission of nitrogen oxide in tail gas is less than 200（mg/m3）, taken off relative to traditional ammonia
Nitre, cost reduce by more than 30%.And it also has combustion-supporting effect, more than 5% can be economized on coal.
Embodiment
Embodiments of the invention are given below, describe the present invention in detail.
Embodiment 1：
A kind of preparation method of solid denox catalyst, the raw material of following percentage by weight is weighed first：Urea 25%, triethanolamine
12%th, citric acid 8%, sodium citrate 12%, water 42.5%, catalyst 0.4%, catalyst is made up of Methacrylamide and hydrogen peroxide,
The weight proportion of Methacrylamide and hydrogen peroxide is 1:1.The water weighed is injected in reactor, then adds urea, is mixed
Triethanolamine is added after uniformly, after being heated to 50 DEG C, adds citric acid and catalyst, then is progressively warming up to 70 DEG C, is heated up
Process 3.5 hours.Then 140min hours are cured at 70 DEG C, sodium citrate is added after cooling to less than 40 DEG C, are mixed.
Embodiment 2：
A kind of preparation method of solid denox catalyst, the raw material of following percentage by weight is weighed first：Urea:35%th, triethanolamine
8%th, citric acid 12%, sodium citrate 8%, water 36.4%, catalyst 0.6%, the catalyst is by Methacrylamide and hydrogen peroxide group
Into the weight proportion of Methacrylamide and hydrogen peroxide is 2.5:1.The water weighed is added in a kettle, then adds urea,
Triethanolamine is added after well mixed, after being heated to 55 DEG C, adds citric acid and catalyst, then is progressively warming up to 70 DEG C,
Temperature-rise period 3 hours, in temperature-rise period, per 30min, heating is no more than 5 DEG C and then cures 100min at 70 DEG C, cools to 40
Sodium citrate is added after DEG C, is mixed.
Embodiment 3：
A kind of preparation method of solid denox catalyst, the raw material of following percentage by weight is weighed first：Urea 30%, triethanolamine
10%th, citric acid 10%, sodium citrate 10%, water 39.5%, catalyst 0.5%, catalyst is by Methacrylamide and hydrogen peroxide group
Into the weight proportion of Methacrylamide and hydrogen peroxide is 2:1.The water weighed is added in a kettle, then adds urea, is mixed
Triethanolamine is added after closing uniformly, after being heated to 55 DEG C, adds citric acid and catalyst, then is progressively warming up to 70 DEG C, is risen
Warm process 3.5 hours, in temperature-rise period, per 30min, heating is no more than 3 DEG C, is then cured 2 hours at 70 DEG C, cools to 40
Sodium citrate is added after DEG C, is mixed.
In the present invention, raw material proportioning has a direct impact to product denitration performance.Therefore, the present invention is with regard to same fire coal（Nitrogen
Content (Ndaf) 1.56%）, contrast test has been carried out to above-described embodiment 1-3 denitration effect.As a result such as table 1.
Influence of the raw material proportioning of table 1 to denitration effect
As known from Table 1, raw material proportioning has a significant impact to the denitration performance of product, the denitration rate highest of embodiment 3, effect of coal saving
It is best.Therefore, embodiment 3 is preferred scheme of the present invention.
Claims (5)
- A kind of 1. preparation method of denitrating catalyst, it is characterised in that including：（1）Raw material is weighed by following percentage by weight：Urea 25~35%, triethanolamine 8~12%, citric acid 8~12%, lemon Sour sodium 8~12%, water 35~45%, catalyst 0.4~0.6%, above component sum meet 100%；The catalyst is by methyl-prop The quality proportioning of acrylamide and hydrogen peroxide composition, Methacrylamide and hydrogen peroxide is 1~2.5:1；（2）Add water in a kettle, then add urea, it is well mixed after add triethanolamine, be heated to 50-55 DEG C Afterwards, citric acid and catalyst are added, then is progressively warming up to 70 DEG C, temperature-rise period 3~3.5 hours, then at 70~75 DEG C 100~140min is cured, sodium citrate is added after cooling to less than 40 DEG C, is mixed.
- 2. the preparation method of denitrating catalyst according to claim 1, it is characterised in that step（1）In, each raw material weight Percentage is：Urea 30%, triethanolamine 10%, citric acid 10%, sodium citrate 10%, water 39.5%, catalyst 0.5%.
- 3. the preparation method of denitrating catalyst according to claim 1, it is characterised in that step（1）In, the methyl-prop Acrylamide and the quality proportioning of hydrogen peroxide are 2:1.
- 4. the preparation method of denitrating catalyst according to claim 1, it is characterised in that step（2）In, it is described to heat up Cheng Zhong, per 30min, heating is no more than 5 DEG C.
- 5. the preparation method of the denitrating catalyst according to claim 1 or 4, it is characterised in that in the temperature-rise period, often 30min heatings are no more than 3 DEG C.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102847418A (en) * | 2011-07-01 | 2013-01-02 | 湖南晟通科技集团有限公司 | Additive for limestone-gypsum wet flue gas desulfurization and denitration process |
| CN103433080A (en) * | 2013-08-27 | 2013-12-11 | 广州高成环保科技有限公司 | Denitrating catalyst |
| CN103691288A (en) * | 2014-01-21 | 2014-04-02 | 高同柱 | Manufacturing method for desulfurization and denitrification agent additive by limestone-gypsum method |
| CN106031844A (en) * | 2015-03-20 | 2016-10-19 | 江西永丰博源实业有限公司 | Agent for desulphurization and denitration |
| CN107149867A (en) * | 2017-06-07 | 2017-09-12 | 四川施利旺农业科技开发有限公司 | Combustion product gases environment-friendly low-temperature composite denitration agent and preparation method thereof |
-
2017
- 2017-11-28 CN CN201711216899.0A patent/CN107812537A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102847418A (en) * | 2011-07-01 | 2013-01-02 | 湖南晟通科技集团有限公司 | Additive for limestone-gypsum wet flue gas desulfurization and denitration process |
| CN103433080A (en) * | 2013-08-27 | 2013-12-11 | 广州高成环保科技有限公司 | Denitrating catalyst |
| CN103691288A (en) * | 2014-01-21 | 2014-04-02 | 高同柱 | Manufacturing method for desulfurization and denitrification agent additive by limestone-gypsum method |
| CN106031844A (en) * | 2015-03-20 | 2016-10-19 | 江西永丰博源实业有限公司 | Agent for desulphurization and denitration |
| CN107149867A (en) * | 2017-06-07 | 2017-09-12 | 四川施利旺农业科技开发有限公司 | Combustion product gases environment-friendly low-temperature composite denitration agent and preparation method thereof |
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Application publication date: 20180320 |