CN102151585B - Melamine-supported denitration catalyst and preparation method thereof - Google Patents

Melamine-supported denitration catalyst and preparation method thereof Download PDF

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Publication number
CN102151585B
CN102151585B CN2011100690268A CN201110069026A CN102151585B CN 102151585 B CN102151585 B CN 102151585B CN 2011100690268 A CN2011100690268 A CN 2011100690268A CN 201110069026 A CN201110069026 A CN 201110069026A CN 102151585 B CN102151585 B CN 102151585B
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melamine
carrier
catalyst
weighing
supports
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CN102151585A (en
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乔文明
王志
潘磊
凌立成
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East China University of Science and Technology
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Abstract

The invention relates to a melamine-supported denitration catalyst and a preparation method thereof. The catalyst comprises the following components in percentage by weight: 49 to 89.99 percent of carrier, 10 to 50 percent of metal oxide and 0.01 to 1 percent of melamine. The method comprises the following steps of: weighing the carrier and a metal inorganic salt precursor, mixing and stirring the solution of the carrier and the metal salt uniformly, soaking and drying, calcining the prepared solid by introducing nitrogen, weighing and dissolving the melamine, mixing and stirring the calcined solid and the melamine solution uniformly, and drying the product to obtain the melamine-supported denitration catalyst. The prepared catalyst is filled in a fixed bed reactor, normal pressure flue gas is introduced into the fixed bed reactor, and the NOx in the flue gas is reacted with the supported melamine to generate N2, CO2 and H2O under the catalytic effect of the carrier. The catalyst has the characteristics of no ammonia, environmental friendliness, no secondary pollution, high denitration efficiency, economical efficiency, energy conservation, wide application range and the like, and represents the development direction of a new denitration technology.

Description

A kind of denitrating catalyst that supports melamine and preparation method thereof
Technical field
The present invention relates to a kind of denitrating catalyst, especially relate to a kind of denitrating catalyst that supports melamine and preparation method thereof.
Background technology
NOx is one of atmosphere major pollutants, is mainly derived from the burning of fossil fuels such as employed coal, oil, natural gas in production, the life, and wherein about 70% comes from the direct burning of coal.The discharging of NOx increases the aerial oxygen voltinism; Cause serious environmental problem; Health and ecological environment are constituted huge threat, and for example: NOx can make human body poison, make the plant growth to suffer damage, can cause acid rain and acid mist, cause photochemical fog, damage the ozone layer etc.At present China NOx discharge capacity is estimated at more than 1,000 ten thousand tons, but will constantly increase with expanding economy from now in view of the energy-output ratio of China, so the NOx discharge capacity also will continue to increase.According to the estimation of relevant research, by 2010, the NOx discharge capacity of China will reach 2,194 ten thousand tons.This shows that China NOx discharge capacity will be very huge from now on, if do not tighten control, NOx will cause serious pollution to China's atmospheric environment, restriction society and economic sustainable development.Therefore, researching and developing efficiently, denitration technology has very important practical sense.
Advantages such as selective catalytic reduction is because to have a denitration efficiency higher, and reaction temperature is lower, and the selection of catalysts scope is wide, and the life-span is long become one of present best denitration technology that can find.Such as, document 1 (Z Wang etc., Industrial & Engineering Chemistry Research; 2010; The 49th volume, the 6317th~6312 page) reported having the urea supported selective catalytic reduction reaction that is used for catalyzing N Ox on asphalt-base globular active carbon oxygen to exist and supporting 8wt% urea; Reaction temperature is that catalytic activity is the highest under 30 ℃ the situation.Document 2 (Chinese patent CN101428237A) has been reported a kind of urea supported carbon based denitration catalyst and the methods for making and using same thereof of East China University of Science's exploitation.Document 3 (Japan Patent JP04-322004A) has reported that a kind of usefulness is urea supported with NACF, and at room temperature, the denitration rate reaches 80%, and this method does not have the NH3 interpolation and reveals.
From above typical relevant denitration paper and patent, can find out that the method that removes NOx through urea supported realization SCR has obtained research both at home and abroad.It has characteristics such as the ammonia of having or not environmental protection, non-secondary pollution than ammonia-method denitration.But because the urea heat endurance is relatively poor, can not under near the window temperature of industrial waste gas, carry out direct denitration, must improve energy resource consumption and running cost the industrial waste gas processing of lowering the temperature earlier.And the melamine Heat stability is good; There is not the problem of decomposing under the window temperature of industrial waste gas; Therefore on different carriers, supporting melamine is used for removing of NOx, is the denitration technology of a no ammonia environmental protection, clean energy-saving, is representing the developing direction of a denitration new technology.
Summary of the invention
The object of the invention be exactly provide in order to overcome the defective that above-mentioned prior art exists a kind of realize environmental protection, non-secondary pollution, denitration efficiency high support denitrating catalyst of melamine and preparation method thereof.
The object of the invention can be realized through following technical scheme:
A kind of denitrating catalyst that supports melamine is characterized in that, this catalyst comprises following component and weight percentage:
Carrier 49~89.99%,
Metal oxide 10~50%,
Melamine 0.01~1%.
Described carrier can be charcoal-aero gel, NACF, spheric active carbon, aluminium oxide or molecular sieve.
Described metal oxide is one or more in the oxide of Mn, Cu, V or Ce.
Described metal oxide obtains through the oxidation of metal inorganic salt precursor.
Described metal inorganic salt precursor is manganese acetate, manganese nitrate, copper chloride, copper nitrate, ammonium metavanadate, cerous nitrate or cerium chloride.
A kind of preparation method who supports the denitrating catalyst of melamine is characterized in that, this method may further comprise the steps:
(1) takes by weighing carrier;
The weight ratio of (2) pressing carried metal and carrier is (0.01~0.3): 1, and the metal inorganic salt precursor that takes by weighing metal active constituent is soluble in water, is mixed with the solution that concentration is 0.01~0.15g/ml;
(3) be 1 by volume with the metal inorganic salt precursor solution that obtains in the carrier that takes by weighing in the step (1) and the step (2): mix (1~2), stirs, and dipping 4~24h is then in 60~100 ℃ of drying 10~24h;
(4) with the logical nitrogen calcining of the solid that makes in the step (3);
(5) take by weighing melamine and be dissolved in 80~100 ℃ of water, be mixed with the solution of melamine;
(6) solid that step (4) calcining is made is 1 with the middle melamine solution of step (5) by volume: mix (1~2); Wherein melamine is (0.01~0.3) with the weight ratio of calcining the solid that makes: 1; It is stirred, then at 80~150 ℃ of dry down denitrating catalysts that support melamine that promptly make.
Described logical nitrogen calcining may further comprise the steps:
(1) solid that makes in the step (3) is placed tube furnace and logical nitrogen, furnace temperature is warmed up to 150~250 ℃ from room temperature, time spent 1~2h;
(2) with tube furnace constant temperature 0.2~1h;
(3) tube furnace is warmed up to 300~800 ℃, time spent 1.5~4h;
(4) constant temperature 5~7h naturally cools to room temperature with continued under nitrogen protection.
A kind of application that supports the denitrating catalyst of melamine; It is characterized in that, the denitrating catalyst that supports melamine is loaded in the fixed bed reactors that the control reaction temperature is at 120~220 ℃; Feed the normal pressure flue gas, the melamine that supports on NOx in the flue gas and denitrating catalyst reaction generates N 2, CO 2And H 2O.
Compared with prior art, the present invention has following advantage:
(1) the present invention as reducing agent, has avoided the use of ammonia with melamine, the environmental protection of whole denitrating technique process, non-secondary pollution;
(2) catalyst denitration efficiency of the present invention is high, can reach 99.00~99.99% the conversion ratio of NOx;
(3) catalyst of the present invention can carry out denitration under operating temperature is 120~220 ℃ condition, can directly under the window temperature of industrial waste gas, carry out denitration, has avoided the use of heat exchanger, has economy, characteristics such as energy-conservation;
(4) the present invention can be used for the denitrating flue gas of station boiler, Industrial Boiler, gas fired-boiler, internal combustion engine, chemical plant and steel mill etc., has applied range, extensive market, characteristics such as economic benefit height.
The specific embodiment
Below in conjunction with specific embodiment the present invention is elaborated.
Embodiment 1
Taking by weighing particle diameter is the carbon aerogels 0.5g of 0.2~2.0mm, adopts the incipient impregnation method, carbon aerogels impregnated in the mixed solution of cerous nitrate and manganese acetate, and wherein manganese metal content is the 12wt% of carrier quality, and Mn: Ce is 1: 1.Dipping 6h, subsequent drying is calcined 6h in 400 ℃ of following nitrogen atmospheres.Impregnated in 6h in the melamine aqueous solution (melamine is the 15wt% of carrier quality) then, dry 24h under 80 ℃ can make catalyst subsequently, and wherein the loading of melamine is 14.55%.
The catalyst that makes is loaded in the fixed bed reactors, is warming up to 185 ℃ of ventilations, its simulated flue gas consists of: 1000ppmNO, 8vol%O 2, N 2As balance gas, atmospheric operation, air speed is 6000h -1Result of the test is: the stable conversion rate of NO is 99.99%, duration 12h.
Embodiment 2
Taking by weighing particle diameter is the carbon aerogels 0.5g of 0.2~2.0mm, adopts the incipient impregnation method, carbon aerogels impregnated in the mixed solution of cerous nitrate and manganese acetate, and wherein manganese metal content is the 20wt% of carrier quality, and Mn: Ce is 1: 1.Dipping 6h, subsequent drying is calcined 6h in 400 ℃ of following nitrogen atmospheres.Impregnated in 6h in the melamine aqueous solution (melamine is the 15wt% of carrier quality) then, dry 24h under 80 ℃ can make catalyst subsequently, and wherein the loading of melamine is 14.75%.
The catalyst that makes is loaded in the fixed bed reactors, is warming up to 185 ℃ of ventilations, its simulated flue gas consists of: 1000ppmNO, 8vol%O 2, N 2As balance gas, atmospheric operation, air speed is 6000h -1Result of the test is: the stable conversion rate of NO is 99.98%, duration 15h.
Embodiment 3
Taking by weighing particle diameter is the carbon aerogels 0.5g of 0.2~2.0mm, adopts the incipient impregnation method, carbon aerogels impregnated in the mixed solution of cerous nitrate and manganese acetate, and wherein manganese metal content is the 12wt% of carrier quality, and Mn: Ce is 1: 1.Dipping 6h, subsequent drying is calcined 6h in 500 ℃ of following nitrogen atmospheres.Impregnated in 6h in the melamine aqueous solution (melamine is the 15wt% of carrier quality) then, dry 24h under 80 ℃ can make catalyst subsequently, and wherein the loading of melamine is 14.69%.
The catalyst that makes is loaded in the fixed bed reactors, is warming up to 185 ℃ of ventilations, its simulated flue gas consists of: 1000ppmNO, 8vol%O 2, N 2As balance gas, atmospheric operation, air speed is 6000h -1Result of the test is: the stable conversion rate of NO is 99.99%, duration 8h.
Embodiment 4
Taking by weighing particle diameter is the carbon aerogels 0.5g of 0.2~2.0mm, adopts the incipient impregnation method, carbon aerogels impregnated in the mixed solution of cerous nitrate and manganese acetate, and wherein manganese metal content is the 12wt% of carrier quality, and Mn: Ce is 1: 1.Dipping 6h, subsequent drying is calcined 6h in 400 ℃ of following nitrogen atmospheres.Impregnated in 6h in the melamine aqueous solution (melamine is the 15wt% of carrier quality) then, dry 24h under 80 ℃ can make catalyst subsequently, and wherein the loading of melamine is 14.85%.
The catalyst that makes is loaded in the fixed bed reactors, is warming up to 165 ℃ of ventilations, its simulated flue gas consists of: 1000ppmNO, 8vol%O 2, N 2As balance gas, atmospheric operation, air speed is 6000h -1Result of the test is: the stable conversion rate of NO is 99.99%, duration 8h.
Embodiment 5
Taking by weighing particle diameter is the carbon aerogels 1.0g of 0.2~2.0mm, adopts the incipient impregnation method, carbon aerogels impregnated in the mixed solution of cerous nitrate and manganese acetate, and wherein manganese metal content is the 12wt% of carrier quality, and Mn: Ce is 1: 1.Dipping 6h, subsequent drying is calcined 6h in 400 ℃ of following nitrogen atmospheres.Impregnated in 6h in the melamine aqueous solution (melamine is the 15wt% of carrier quality) then, dry 24h under 80 ℃ can make catalyst subsequently, and wherein the loading of melamine is 14.91%.
The catalyst that makes is loaded in the fixed bed reactors, is warming up to 185 ℃ of ventilations, its simulated flue gas consists of: 1000ppmNO, 8vol%O 2, N 2As balance gas, atmospheric operation, air speed is 6000h -1Result of the test is: the stable conversion rate of NO is 99.97%, duration 23h.
Embodiment 6
Taking by weighing particle diameter is the carbon aerogels 0.2g of 0.2~2.0mm, adopts the incipient impregnation method, carbon aerogels impregnated in the mixed solution of cerous nitrate and manganese acetate, and wherein manganese metal content is the 12wt% of carrier quality, and Mn: Ce is 1: 1.Dipping 6h, subsequent drying is calcined 6h in 400 ℃ of following nitrogen atmospheres.Impregnated in 6h in the melamine aqueous solution (melamine is the 15wt% of carrier quality) then, dry 24h under 80 ℃ can make catalyst subsequently, and wherein the loading of melamine is 14.83%.
The catalyst that makes is loaded in the fixed bed reactors, is warming up to 185 ℃ of ventilations, its simulated flue gas consists of: 1000ppmNO, 8vol%O 2, N 2As balance gas, atmospheric operation, air speed is 6000h -1Result of the test is: the stable conversion rate of NO is 99.98%, duration 10h.
Embodiment 7
Taking by weighing particle diameter is the carbon aerogels 0.5g of 0.2~2.0mm, adopts the incipient impregnation method, carbon aerogels impregnated in the mixed solution of cerous nitrate and manganese acetate, and wherein manganese metal content is the 12wt% of carrier quality, and Mn: Ce is 1: 1.Dipping 6h, subsequent drying is calcined 6h in 400 ℃ of following nitrogen atmospheres.Impregnated in 6h in the melamine aqueous solution (melamine is the 15wt% of carrier quality) then, dry 24h under 80 ℃ can make catalyst subsequently, and wherein the loading of melamine is 14.55%.
The catalyst that makes is loaded in the fixed bed reactors, is warming up to 185 ℃ of ventilations, its simulated flue gas consists of: 1000ppmNO, 2vol%O 2, N 2As balance gas, atmospheric operation, air speed is 6000h -1Result of the test is: the stable conversion rate of NO is 97%, duration 10h.
Embodiment 8
Taking by weighing particle diameter is the carbon aerogels 0.5g of 0.2~2.0mm, adopts the incipient impregnation method, carbon aerogels impregnated in the mixed solution of cerous nitrate and manganese acetate, and wherein manganese metal content is the 12wt% of carrier quality, and Mn: Ce is 1: 1.Dipping 6h, subsequent drying is calcined 6h in 400 ℃ of following nitrogen atmospheres.Impregnated in 6h in the melamine aqueous solution (melamine is the 15wt% of carrier quality) then, dry 24h under 80 ℃ can make catalyst subsequently, and wherein the loading of melamine is 14.55%.
The catalyst that makes is loaded in the fixed bed reactors, is warming up to 185 ℃ of ventilations, its simulated flue gas consists of: 100ppmNO, 8vol%O 2, N 2As balance gas, atmospheric operation, air speed is 6000h -1Result of the test is: the stable conversion rate of NO is 99.98%, duration 100h.
Embodiment 9
A kind of denitrating catalyst that supports melamine; This catalyst comprises following component and weight percentage: carrier 49%, metal oxide 50%, melamine 1%, and wherein, employed carrier is a charcoal-aero gel; Metal oxide is a manganese oxide, obtains for the precursor oxidation through manganese acetate.The preparation method who supports the denitrating catalyst of melamine may further comprise the steps:
(1) takes by weighing a certain amount of charcoal-aero gel as carrier;
(2) weight ratio by carried metal manganese and charcoal-aero gel is 0.3: 1, and the manganese acetate that takes by weighing metal active constituent is soluble in water, and control concentration is 0.01g/ml;
(3) be to mix at 1: 1 by volume with the manganese acetate solution that obtains in the carrier that takes by weighing in the step (1) and the step (2), stir that dipping 4h is then in 60 ℃ of dry 24h;
(4) solid that makes in the solid that makes in the step (3) is placed tube furnace and logical nitrogen, furnace temperature is warmed up to 150 ℃ from room temperature, time spent 1h; With the permanent 0.2h of tube furnace; Tube furnace is warmed up to 300 ℃, time spent 1.5h; Constant temperature 5h naturally cools to room temperature with continued under nitrogen protection;
(5) weight ratio by melamine and charcoal-aero gel is 0.3: 1, takes by weighing melamine and is dissolved in 80 ℃ of water;
(6) solid that step (4) calcining is made and the middle melamine solution of step (5) are to mix at 1: 1 by volume, stir, and can make the denitrating catalyst that supports melamine 80 ℃ of following dryings then.
The denitrating catalyst that supports melamine for preparing is loaded in the fixed bed reactors, and the control reaction temperature feeds the normal pressure flue gas at 120 ℃, and the melamine that supports on NOx in the flue gas and denitrating catalyst reaction generates N 2, CO 2And H 2O has characteristics such as no ammonia environmental protection, non-secondary pollution, denitration efficiency height.
Embodiment 10
A kind of denitrating catalyst that supports melamine comprises following component and weight percentage: carrier 89.99%, metal oxide 10%; Melamine 0.01%; Wherein carrier is a molecular sieve, and metal oxide is a cupric oxide, and oxidation obtains as precursor through copper chloride.Support the preparation method of the denitrating catalyst of melamine, it is characterized in that, this method may further comprise the steps:
(1) takes by weighing a certain amount of molecular sieve carrier;
(2) weight ratio by carried metal and carrier is 0.01: 1, and the copper chloride that takes by weighing metal active constituent is soluble in water, and control concentration is 0.15g/ml
(3) be to mix at 1: 2 by volume with the copper chloride solution that obtains in the carrier that takes by weighing in the step (1) and the step (2), stir that dipping 24h is then in 100 ℃ of dry 10h;
(4) solid that makes in the solid that makes in the step (3) is placed tube furnace and logical nitrogen, furnace temperature is warmed up to 250 ℃ from room temperature, time spent 2h; With tube furnace constant temperature 1h; Tube furnace is warmed up to 800 ℃, time spent 4h; Constant temperature 7h naturally cools to room temperature with continued under nitrogen protection;
(5) weight ratio by melamine and carrier is 0.01: 1, takes by weighing melamine and is dissolved in 100 ℃ the water;
(6) solid that step (4) calcining is made and the middle melamine solution of step (5) are to mix at 1: 2 by volume, stir, and can make the denitrating catalyst that supports melamine 150 ℃ of following dryings then.
The denitrating catalyst that supports melamine for preparing is loaded in the fixed bed reactors, and the control reaction temperature feeds the normal pressure flue gas at 220 ℃, and the melamine that supports on NOx in the flue gas and denitrating catalyst reaction generates N 2, CO 2And H 2O has characteristics such as no ammonia environmental protection, non-secondary pollution, denitration efficiency height.

Claims (5)

1. a denitrating catalyst that supports melamine is characterized in that, this catalyst comprises following component and weight percentage:
Carrier 49 ~ 89.99%,
Metal oxide 10 ~ 50%,
Melamine 0.01 ~ 1%;
Described carrier is charcoal-aero gel, NACF, spheric active carbon, aluminium oxide or molecular sieve;
Described metal oxide is one or more in the oxide of Mn, Cu, V or Ce.
2. a kind of denitrating catalyst that supports melamine according to claim 1 is characterized in that described metal oxide obtains through the oxidation of metal inorganic salt precursor.
3. a kind of denitrating catalyst that supports melamine according to claim 2 is characterized in that described metal inorganic salt precursor is manganese acetate, manganese nitrate, copper chloride, copper nitrate, ammonium metavanadate, cerous nitrate or cerium chloride.
4. preparation method who supports the denitrating catalyst of melamine as claimed in claim 1 is characterized in that this method may further comprise the steps:
(1) takes by weighing carrier;
The weight ratio of (2) pressing carried metal and carrier is (0.01 ~ 0.3): 1, and the metal inorganic salt precursor that takes by weighing metal active constituent is soluble in water, is mixed with the solution that concentration is 0.01 ~ 0.15g/ml;
(3) be 1 by volume with the metal inorganic salt precursor solution that obtains in the carrier that takes by weighing in the step (1) and the step (2): mix (1 ~ 2), stirs, and dipping 4 ~ 24h is then in 60 ~ 100 ℃ of drying 10 ~ 24h;
(4) with the logical nitrogen calcining of the solid that makes in the step (3);
(5) take by weighing melamine and be dissolved in 80 ~ 100 ℃ of water, be mixed with the solution of melamine;
(6) solid that step (4) calcining is made is 1 with the middle melamine solution of step (5) by volume: mix (1 ~ 2); Wherein melamine is (0.01 ~ 0.3) with the weight ratio of calcining the solid that makes: 1; It is stirred, then at 80 ~ 150 ℃ of dry down denitrating catalysts that support melamine that promptly make.
5. a kind of preparation method who supports the denitrating catalyst of melamine according to claim 4 is characterized in that, described logical nitrogen calcining may further comprise the steps:
(1) solid that makes in the step (3) is placed tube furnace and logical nitrogen, furnace temperature is warmed up to 150 ~ 250 ℃ from room temperature, time spent 1 ~ 2h;
(2) with tube furnace constant temperature 0.2 ~ 1h;
(3) tube furnace is warmed up to 300 ~ 800 ℃, time spent 1.5 ~ 4h;
(4) constant temperature 5 ~ 7h naturally cools to room temperature with continued under nitrogen protection.
CN2011100690268A 2011-03-22 2011-03-22 Melamine-supported denitration catalyst and preparation method thereof Expired - Fee Related CN102151585B (en)

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