CN111686712B - SCR flue gas denitration catalyst and preparation method thereof - Google Patents

SCR flue gas denitration catalyst and preparation method thereof Download PDF

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CN111686712B
CN111686712B CN202010573638.XA CN202010573638A CN111686712B CN 111686712 B CN111686712 B CN 111686712B CN 202010573638 A CN202010573638 A CN 202010573638A CN 111686712 B CN111686712 B CN 111686712B
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张新堂
张瑞宇
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Qingdao Zhengda Kaite New Material Technology Co ltd
Shandong University of Science and Technology
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Abstract

The invention discloses an SCR flue gas denitration catalyst and a preparation method thereof, and belongs to the technical field of catalyst preparation. The invention takes industrial coal slag as main raw material to prepare the catalyst carrier, and then CeO is utilized2‑La2O3‑Cr2O3/TiO2Inorganic oxide catalyst slurry coating a layer of CeO on the surface of catalyst carrier2‑La2O3‑Cr2O3/TiO2And obtaining the SCR flue gas denitration catalyst by using the catalyst. The SCR flue gas denitration catalyst prepared by the invention has excellent catalytic activity, the catalytic conversion rate can reach 95.7% at 260 ℃, and the SCR flue gas denitration catalyst prepared by the invention has a wider reaction window and has a catalytic conversion rate of about 90% at 220-300 ℃.

Description

SCR flue gas denitration catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to an SCR flue gas denitration catalyst and a preparation method thereof.
Background
According to the data of the national statistical bureau, in 2018, the yield and the consumption of the coal in China respectively account for 46.0 percent and 50.5 percent of the total global quantity, and in the period of 2006-plus-2018, the consumption of the coal in China accounts for more than 57 percent of the total energy consumption. According to the energy status of China, coal still occupies an absolute dominance in the energy structure of China for a long time. More than 80% of the coal in China is directly used for combustion, and pollutants such as sulfur oxides (SOx), nitrogen oxides (NOx), smoke dust and the like generated in the coal combustion process can cause serious harm to the ecological environment and human health after entering the atmosphere.
The nitrogen oxide is one of main pollution gases of the atmospheric environment in China, not only causes environmental problems such as acid rain, photochemical pollution and the like, but also is a main component of PM 2.5. The most effective treatment for nitrogen oxides is ammonia selective catalytic reduction (NH)3SCR), which is the most widely used for the worldwide removal of NOx of a fixed source, the main core technology of which SCR catalysts are currently mainly V2O5/TiO2Catalyst, TiO2The content of the catalyst carrier in the catalyst is more than 95 percent. At present, the demand of SCR catalysts in China is huge, more than 100 ten thousand cubic SCR catalysts are needed for a single-fire power generation boiler in China, and a large amount of titanium dioxide resources are consumed. Thus, a TiO has been invented2A catalyst having a small content and excellent catalytic activity is a problem to be solved urgently at present.
Disclosure of Invention
The invention aims to provide TiO with high catalytic activity2A novel SCR flue gas denitration catalyst with low content.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a preparation method of an SCR flue gas denitration catalyst, which comprises the following steps:
(1) placing industrial coal cinder into a roasting furnace, roasting at constant temperature, and then crushing the roasted industrial coal cinder to obtain industrial coal cinder powder;
(2) dissolving ethanolamine and ammonia water in water to obtain a solution a, and dissolving paper pulp, sodium carboxymethyl cellulose and polyethylene oxide in water to obtain a solution b;
(3) uniformly mixing industrial coal cinder powder, glass fiber and stearic acid, adding the solution a and the solution b for kneading, and after kneading, pre-extruding, ageing, molding, drying and roasting to obtain a catalyst carrier;
(4) adding cerium nitrate, chromium nitrate and lanthanum nitrate into water to prepare a solution c, then adding titanium dioxide into the solution c, uniformly mixing, standing, drying, roasting and crushing to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst;
(5) adding CeO2-La2O3-Cr2O3/TiO2Mixing inorganic oxide catalyst and adhesive, adding water and stirring to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst slurry;
(6) adding the catalyst carrier to CeO2-La2O3-Cr2O3/TiO2And soaking the inorganic oxide catalyst slurry, taking out, drying and roasting to obtain the SCR flue gas denitration catalyst.
Preferably, in the step (1), the constant-temperature roasting temperature is 500 ℃, and the constant-temperature roasting time is 3 hours.
Preferably, in the step (2), the amount of ethanolamine in the solution a is 1.20kg, the amount of ammonia water is 5kg, and the amount of water is 10 kg; the dosage of the paper pulp in the solution b is 0.18kg, the dosage of the sodium carboxymethyl cellulose is 0.35kg, the dosage of the polyethylene oxide is 0.35kg, and the dosage of the water is 26 kg.
Preferably, in the step (3), the amount of the industrial coal cinder is 100kg, the amount of the glass fiber is 5kg, and the amount of the stearic acid is 0.50 kg; the kneading time is 60min, the ageing time is 24h, the drying temperature is 70 ℃, the drying time is 10h, the roasting temperature is 680 ℃, and the roasting time is 3 h.
Preferably, in the step (4), the amount of the cerium nitrate is as follows by mass: the dosage of the chromium nitrate: the dosage of lanthanum nitrate is 10-60:5.5-22:1.5-6, the dosage of water is 300ml, and the addition amount of titanium dioxide is 966g-993 g; the standing time is 24 hours, the drying temperature is 70 ℃, the drying time is 10 hours, the roasting temperature is 680 ℃, and the roasting time is 3 hours.
Preferably, in the step (5), the binder is a mixture of polyvinyl alcohol, OP-10 and carboxymethyl cellulose; according to the mass ratio, the polyvinyl alcohol: OP-10: the ratio of carboxymethyl cellulose to cellulose is 2-3:0.5-1: 1-2.
Preferably, in the step (5), the CeO is calculated according to a mass ratio2-La2O3-Cr2O3/TiO2Inorganic oxide catalyst: the binder is 50: 1.
Preferably, in the step (6), the drying temperature is 60-100 ℃, the drying time is 5h, the roasting temperature is 460-500 ℃, and the roasting time is 3h according to the mass ratio.
In addition, the invention provides an SCR flue gas denitration catalyst, which is prepared by the preparation method.
Preferably, the catalyst core is a catalyst carrier prepared from industrial coal slag, and the surface of the catalyst is coated with CeO2-La2O3-Cr2O3/TiO2(ii) a The CeO2-La2O3-Cr2O3/TiO2The coating amount of (2) is 6.2% -7.4%; the CeO2-La2O3-Cr2O3/TiO2CeO in2In an amount of 0.4-2.4%, the CeO2-La2O3-Cr2O3/TiO2Middle La2O3The content of the CeO is 0.1 to 0.4 percent2-La2O3-Cr2O3/TiO2Medium Cr2O30.2 to 0.8 percent of CeO2-La2O3-Cr2O3/TiO2 Medium TiO 22The content is 96.6-99.3%.
The invention has the beneficial effects that:
in the invention, CeO is added2-La2O3-Cr2O3/TiO2The formula composition of the catalyst is directly coated on a catalyst carrier prepared from industrial coal slag to prepare the SCR flue gas denitration catalyst. The catalyst prepared by the invention has excellent performanceThe highest catalytic conversion rate reaches 94.9 percent at 260 ℃. Meanwhile, the catalyst prepared by the method has a wider temperature window, and has about 90% of catalytic conversion rate at 220-300 ℃. Secondly, the catalyst carrier is prepared from industrial coal cinder, so that the industrial waste coal cinder is effectively utilized while the catalytic activity of the catalyst is ensured, and TiO in the SCR denitration catalyst is reduced2The use of the catalyst effectively saves the production cost of the catalyst.
Drawings
FIG. 1 schematic diagram of a denitration apparatus
1-oxygen standard gas, 2-Nitric Oxide (NO) standard gas, 3-ammonia standard gas, 4-flowmeter, 5-gas mixer, 6-catalyst filling layer, 7-electric furnace temperature controller, 8-absorption liquid and 9-flue gas analyzer.
Detailed Description
The invention is further described below with reference to specific examples, it being understood that the examples are illustrative of the invention only and are not intended to be limiting.
Example 1
(1) Placing industrial coal cinder into a roasting furnace, roasting for 3 hours at a constant temperature of 500 ℃, and then crushing the roasted industrial coal cinder to obtain industrial coal cinder powder;
(2) dissolving 1.20kg of ethanolamine and 5kg of ammonia water in water to obtain a solution a, and dissolving 0.18kg of pulp, 0.35kg of sodium carboxymethylcellulose and 0.35kg of polyethylene oxide in water to obtain a solution b;
(3) adding 100kg of industrial coal cinder powder, 5.00kg of glass fiber and 0.50kg of stearic acid into a kneader, uniformly mixing, then respectively adding the solution a and the solution b, kneading for 60min, adding the mixture into a filtering pre-extruder after kneading is finished, pre-extruding for 2 times, aging for 24h, molding, drying at 70 ℃ for 10h, and roasting at 680 ℃ for 3h to obtain a catalyst carrier;
(4) adding 20g of cerium nitrate, 11g of chromium nitrate and 3g of lanthanum nitrate into 300ml of water to prepare a solution C, then adding 986g of titanium dioxide into the solution C, uniformly mixing, standing for 24h, drying at 90 ℃ for 5h, roasting at 500 ℃ for 3h, and crushing to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst;
(5) 400.00g of CeO2-La2O3-Cr2O3/TiO2Mixing inorganic oxide catalyst and binder (8.00 g: polyvinyl alcohol: OP-10: carboxymethyl cellulose: 2: 1: 2) uniformly, adding 800.00g of water, stirring strongly for 0.5h to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst slurry;
(6) 300g of the catalyst carrier was added to CeO2-La2O3-Cr2O3/TiO2Soaking the inorganic oxide catalyst slurry for 3 hours, taking out the inorganic oxide catalyst slurry, blowing off redundant slurry by using certain air flow, drying the slurry at 60 ℃ for 5 hours, and roasting the slurry at 500 ℃ for 3 hours to obtain the SCR flue gas denitration catalyst A.
Example 2
(1) Placing industrial coal cinder into a roasting furnace, roasting for 3 hours at a constant temperature of 500 ℃, and then crushing the roasted industrial coal cinder to obtain industrial coal cinder powder;
(2) dissolving 1.20kg of ethanolamine and 5kg of ammonia water in water to obtain a solution a, and dissolving 0.18kg of paper pulp, 0.35kg of sodium carboxymethylcellulose and 0.35kg of polyethylene oxide in water to obtain a solution b;
(3) adding 100kg of industrial coal cinder powder, 5.00kg of glass fiber and 0.50kg of stearic acid into a kneader, uniformly mixing, then respectively adding the solution a and the solution b, kneading for 60min, adding the mixture into a filtering pre-extruder after kneading is finished, pre-extruding for 2 times, ageing for 24 hours, molding, drying for 10 hours at 70 ℃, and roasting for 3 hours at 680 ℃ to obtain a catalyst carrier;
(4) adding 20g of cerium nitrate, 11g of chromium nitrate and 3g of lanthanum nitrate into 300ml of water to prepare a solution C, then adding 986g of titanium dioxide into the solution C, uniformly mixing, standing for 24h, drying at 90 ℃ for 5h, roasting at 500 ℃ for 3h, and crushing to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst;
(5) 400.00g of CeO2-La2O3-Cr2O3/TiO2Inorganic oxide catalyst, 8.00g binder (polyvinyl alcohol: OP-10: carboxymethyl cellulose 2: 1: 2) were mixed well, and then added600.00g of water, stirring vigorously for 0.5h to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst slurry;
(6) 300g of the catalyst carrier was added to CeO2-La2O3-Cr2O3/TiO2And soaking the inorganic oxide catalyst slurry for 3 hours, taking out the inorganic oxide catalyst slurry, blowing off redundant slurry by using a certain air flow, drying the slurry at the temperature of 80 ℃ for 5 hours, and roasting the slurry at the temperature of 560 ℃ for 3 hours to obtain the SCR flue gas denitration catalyst B.
Example 3
(1) Placing industrial coal cinder into a roasting furnace, roasting for 3 hours at a constant temperature of 500 ℃, and then crushing the roasted industrial coal cinder to obtain industrial coal cinder powder;
(2) dissolving 1.20kg of ethanolamine and 5kg of ammonia water in water to obtain a solution a, and dissolving 0.18kg of pulp, 0.35kg of sodium carboxymethylcellulose and 0.35kg of polyethylene oxide in water to obtain a solution b;
(3) adding 100kg of industrial coal cinder powder, 5.00kg of glass fiber and 0.50kg of stearic acid into a kneader, uniformly mixing, then respectively adding the solution a and the solution b, kneading for 60min, adding the mixture into a filtering pre-extruder after kneading is finished, pre-extruding for 2 times, aging for 24h, molding, drying at 70 ℃ for 10h, and roasting at 680 ℃ for 3h to obtain a catalyst carrier;
(4) adding 40g of cerium nitrate, 22g of chromium nitrate and 6g of lanthanum nitrate into 300ml of water to prepare a solution C, then adding 972g of titanium dioxide into the solution C, uniformly mixing, standing for 24 hours, drying at 90 ℃ for 5 hours, roasting at 500 ℃ for 3 hours, and crushing to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst;
(5) 400.00g of CeO2-La2O3-Cr2O3/TiO2Mixing inorganic oxide catalyst and binder (8.00 g: OP-10: carboxymethyl cellulose 2: 1: 2), adding water 800.00g, stirring vigorously for 0.5 hr to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst slurry;
(6) 300g of the catalyst carrier was added to CeO2-La2O3-Cr2O3/TiO2Soaking the inorganic oxide catalyst slurry for 3 hours, taking out the inorganic oxide catalyst slurry, blowing off redundant slurry by using certain air flow, drying the slurry at 100 ℃ for 5 hours, and roasting the slurry at 460 ℃ for 3 hours to obtain the SCR flue gas denitration catalyst C.
Example 4
(1) Placing industrial coal cinder into a roasting furnace, roasting for 3 hours at a constant temperature of 500 ℃, and then crushing the roasted industrial coal cinder to obtain industrial coal cinder powder;
(2) dissolving 1.20kg of ethanolamine and 5kg of ammonia water in water to obtain a solution a, and dissolving 0.18kg of pulp, 0.35kg of sodium carboxymethylcellulose and 0.35kg of polyethylene oxide in water to obtain a solution b;
(3) adding 100kg of industrial coal cinder powder, 5.00kg of glass fiber and 0.50kg of stearic acid into a kneader, uniformly mixing, then respectively adding the solution a and the solution b, kneading for 60min, adding the mixture into a filtering pre-extruder after kneading is finished, pre-extruding for 2 times, aging for 24h, molding, drying at 70 ℃ for 10h, and roasting at 680 ℃ for 3h to obtain a catalyst carrier;
(4) adding 40g of cerium nitrate, 22g of chromium nitrate and 6g of lanthanum nitrate into 300ml of water to prepare a solution C, then adding 972g of titanium dioxide into the solution C, uniformly mixing, standing for 24 hours, drying at 90 ℃ for 5 hours, roasting at 500 ℃ for 3 hours, and crushing to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst;
(5) 400.00g of CeO2-La2O3-Cr2O3/TiO2Mixing inorganic oxide catalyst 8.00g binder (polyvinyl alcohol: OP-10: carboxymethyl cellulose: 2: 1: 2), adding 600.00g water, stirring vigorously for 0.5h to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst slurry;
(6) 300g of the catalyst carrier was added to CeO2-La2O3-Cr2O3/TiO2And soaking the inorganic oxide catalyst slurry for 3 hours, taking out the inorganic oxide catalyst slurry, blowing off redundant slurry by using a certain air flow, drying the slurry at 60 ℃ for 5 hours, and roasting the slurry at 500 ℃ for 3 hours to obtain the SCR flue gas denitration catalyst D.
Example 5
(1) Placing industrial coal cinder into a roasting furnace, roasting for 3 hours at a constant temperature of 500 ℃, and then crushing the roasted industrial coal cinder to obtain industrial coal cinder powder;
(2) dissolving 1.20kg of ethanolamine and 5kg of ammonia water in water to obtain a solution a, and dissolving 0.18kg of pulp, 0.35kg of sodium carboxymethylcellulose and 0.35kg of polyethylene oxide in water to obtain a solution b;
(3) adding 100kg of industrial coal cinder powder, 5.00kg of glass fiber and 0.50kg of stearic acid into a kneader, uniformly mixing, then respectively adding the solution a and the solution b, kneading for 60min, adding the mixture into a filtering pre-extruder after kneading is finished, pre-extruding for 2 times, ageing for 24 hours, molding, drying for 10 hours at 70 ℃, and roasting for 3 hours at 680 ℃ to obtain a catalyst carrier;
(4) adding 10g of cerium nitrate, 5.5g of chromium nitrate and 1.5g of lanthanum nitrate into 300ml of water to prepare a solution C, then adding 993g of titanium dioxide into the solution C, uniformly mixing, standing for 24h, drying at 90 ℃ for 5h, roasting at 500 ℃ for 3h, and crushing to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst;
(5) 400.00g of CeO2-La2O3-Cr2O3/TiO2Mixing inorganic oxide catalyst and binder (8.00 g: OP-10: carboxymethyl cellulose 2: 1: 2), adding water 800.00g, stirring vigorously for 0.5 hr to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst slurry;
(6) 300g of the catalyst carrier was added to CeO2-La2O3-Cr2O3/TiO2Soaking the inorganic oxide catalyst slurry for 3 hours, taking out the inorganic oxide catalyst slurry, blowing off redundant slurry by using certain air flow, drying the slurry at 60 ℃ for 5 hours, and roasting the slurry at 500 ℃ for 3 hours to obtain the SCR flue gas denitration catalyst E.
Example 6
(1) Placing industrial coal cinder into a roasting furnace, roasting for 3 hours at a constant temperature of 500 ℃, and then crushing the roasted industrial coal cinder to obtain industrial coal cinder powder;
(2) dissolving 1.20kg of ethanolamine and 5kg of ammonia water in water to obtain a solution a, and dissolving 0.18kg of paper pulp, 0.35kg of sodium carboxymethylcellulose and 0.35kg of polyethylene oxide in water to obtain a solution b;
(3) adding 100kg of industrial coal cinder powder, 5.00kg of glass fiber and 0.50kg of stearic acid into a kneader, uniformly mixing, then respectively adding the solution a and the solution b, kneading for 60min, adding the mixture into a filtering pre-extruder after kneading is finished, pre-extruding for 2 times, ageing for 24 hours, molding, drying for 10 hours at 70 ℃, and roasting for 3 hours at 680 ℃ to obtain a catalyst carrier;
(4) adding 10g of cerium nitrate, 5.5g of chromium nitrate and 1.5g of lanthanum nitrate into 300ml of water to prepare a solution C, then adding 993g of titanium dioxide into the solution C, uniformly mixing, standing for 24h, drying at 90 ℃ for 5h, roasting at 500 ℃ for 3h, and crushing to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst;
(5) 400.00g of CeO2-La2O3-Cr2O3/TiO2Inorganic oxide catalyst, 8.00g binder (polyvinyl alcohol: OP-10: carboxymethyl cellulose: 2: 1: 2) were mixed well, 600.00g water was added, and strong stirring was carried out for 0.5h to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst slurry;
(6) 300g of the catalyst carrier was added to CeO2-La2O3-Cr2O3/TiO2Soaking the inorganic oxide catalyst slurry for 3h, taking out, blowing off redundant slurry by using a certain air flow, drying at 60 ℃ for 5h, and roasting at 500 ℃ for 3h to obtain the SCR flue gas denitration catalyst F.
Example 7
(1) Placing industrial coal cinder into a roasting furnace, roasting for 3 hours at a constant temperature of 500 ℃, and then crushing the roasted industrial coal cinder to obtain industrial coal cinder powder;
(2) dissolving 1.20kg of ethanolamine and 5kg of ammonia water in water to obtain a solution a, and dissolving 0.18kg of paper pulp, 0.35kg of sodium carboxymethylcellulose and 0.35kg of polyethylene oxide in water to obtain a solution b;
(3) adding 100kg of industrial coal cinder powder, 5.00kg of glass fiber and 0.50kg of stearic acid into a kneader, uniformly mixing, then respectively adding the solution a and the solution b, kneading for 60min, adding the mixture into a filtering pre-extruder after kneading is finished, pre-extruding for 2 times, ageing for 24 hours, molding, drying for 10 hours at 70 ℃, and roasting for 3 hours at 680 ℃ to obtain a catalyst carrier;
(4) adding 20g of cerium nitrate, 11g of chromium nitrate and 3g of lanthanum nitrate into 300ml of water to prepare a solution C, then adding 986g of titanium dioxide into the solution C, uniformly mixing, standing for 24 hours, drying at 90 ℃ for 5 hours, roasting at 500 ℃ for 3 hours, and crushing to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst;
(5) 400.00g of CeO2-La2O3-Cr2O3/TiO2Inorganic oxide catalyst, 8.00g binder (polyvinyl alcohol: OP-10: carboxymethyl cellulose: 2: 1: 1) were mixed well, 800.00g water was added, and stirring was vigorously carried out for 0.5h to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst slurry;
(6) 300g of the catalyst carrier was added to CeO2-La2O3-Cr2O3/TiO2Soaking the inorganic oxide catalyst slurry for 3h, taking out, blowing off redundant slurry by using a certain air flow, drying at 60 ℃ for 5h, and roasting at 500 ℃ for 3h to obtain the SCR flue gas denitration catalyst G.
Example 8
(1) Placing industrial coal cinder into a roasting furnace, roasting for 3 hours at a constant temperature of 500 ℃, and then crushing the roasted industrial coal cinder to obtain industrial coal cinder powder;
(2) dissolving 1.20kg of ethanolamine and 5kg of ammonia water in water to obtain a solution a, and dissolving 0.18kg of paper pulp, 0.35kg of sodium carboxymethylcellulose and 0.35kg of polyethylene oxide in water to obtain a solution b;
(3) adding 100kg of industrial coal cinder powder, 5.00kg of glass fiber and 0.50kg of stearic acid into a kneader, uniformly mixing, then respectively adding the solution a and the solution b, kneading for 60min, adding the mixture into a filtering pre-extruder after kneading is finished, pre-extruding for 2 times, ageing for 24 hours, molding, drying for 10 hours at 70 ℃, and roasting for 3 hours at 680 ℃ to obtain a catalyst carrier;
(4) 20g of cerium nitrate, 11g of chromium nitrate and 3g of lanthanum nitrate were added to 300ml of water to prepare a solution c, and 986g of titanium dioxide was added to this solutionUniformly mixing the solution C, standing for 24h, drying at 90 ℃ for 5h, roasting at 500 ℃ for 3h, and crushing to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst;
(5) 400.00g of CeO2-La2O3-Cr2O3/TiO2Mixing inorganic oxide catalyst 8.00g binder (polyvinyl alcohol: OP-10: carboxymethyl cellulose: 3: 0.5: 2), adding 800.00g water, stirring vigorously for 0.5h to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst slurry;
(6) 300g of the catalyst carrier was added to CeO2-La2O3-Cr2O3/TiO2Soaking the inorganic oxide catalyst slurry for 3H, taking out, blowing off redundant slurry by using a certain air flow, drying at 60 ℃ for 5H, and roasting at 500 ℃ for 3H to obtain the SCR flue gas denitration catalyst H.
Example 9
(1) Placing industrial coal cinder into a roasting furnace, roasting for 3 hours at a constant temperature of 500 ℃, and then crushing the roasted industrial coal cinder to obtain industrial coal cinder powder;
(2) dissolving 1.20kg of ethanolamine and 5kg of ammonia water in water to obtain a solution a, and dissolving 0.18kg of pulp, 0.35kg of sodium carboxymethylcellulose and 0.35kg of polyethylene oxide in water to obtain a solution b;
(3) adding 100kg of industrial coal cinder powder, 5.00kg of glass fiber and 0.50kg of stearic acid into a kneader, uniformly mixing, then respectively adding the solution a and the solution b, kneading for 60min, adding the mixture into a filtering pre-extruder after kneading is finished, pre-extruding for 2 times, aging for 24h, molding, drying at 70 ℃ for 10h, and roasting at 680 ℃ for 3h to obtain a catalyst carrier;
(4) adding 40g of cerium nitrate, 11g of chromium nitrate and 6g of lanthanum nitrate into 300ml of water to prepare a solution C, then adding 976g of titanium dioxide into the solution C, uniformly mixing, standing for 24 hours, drying at 90 ℃ for 5 hours, roasting at 500 ℃ for 3 hours, and crushing to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst;
(5) 400.00g of CeO2-La2O3-Cr2O3/TiO2Mixing inorganic oxide catalyst 8.00g binder (polyvinyl alcohol: OP-10: carboxymethyl cellulose: 2: 1: 2), adding 600.00g water, stirring vigorously for 0.5h to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst slurry;
(6) 300g of the catalyst carrier was added to CeO2-La2O3-Cr2O3/TiO2Soaking the inorganic oxide catalyst slurry for 3h, taking out, blowing off redundant slurry by using a certain air flow, drying at 60 ℃ for 5h, and roasting at 500 ℃ for 3h to obtain the SCR flue gas denitration catalyst I.
Example 10
(1) Placing industrial coal cinder into a roasting furnace, roasting for 3 hours at a constant temperature of 500 ℃, and then crushing the roasted industrial coal cinder to obtain industrial coal cinder powder;
(2) dissolving 1.20kg of ethanolamine and 5kg of ammonia water in water to obtain a solution a, and dissolving 0.18kg of pulp, 0.35kg of sodium carboxymethylcellulose and 0.35kg of polyethylene oxide in water to obtain a solution b;
(3) adding 100kg of industrial coal cinder powder, 5.00kg of glass fiber and 0.50kg of stearic acid into a kneader, uniformly mixing, then respectively adding the solution a and the solution b, kneading for 60min, adding the mixture into a filtering pre-extruder after kneading is finished, pre-extruding for 2 times, ageing for 24 hours, molding, drying for 10 hours at 70 ℃, and roasting for 3 hours at 680 ℃ to obtain a catalyst carrier;
(4) adding 60g of cerium nitrate, 22g of chromium nitrate and 3g of lanthanum nitrate into 300ml of water to prepare a solution C, then adding 966g of titanium dioxide into the solution C, uniformly mixing, standing for 24h, drying at 90 ℃ for 5h, roasting at 500 ℃ for 3h, and crushing to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst;
(5) 400.00g of CeO2-La2O3-Cr2O3/TiO2Mixing inorganic oxide catalyst and binder (8.00 g: polyvinyl alcohol: OP-10: carboxymethyl cellulose: 2: 1: 2) uniformly, adding 800.00g of water, stirring strongly for 0.5h to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst slurry;
(6) 300g of the catalyst carrier was added to CeO2-La2O3-Cr2O3/TiO2Soaking the inorganic oxide catalyst slurry for 3h, taking out, blowing off redundant slurry by using a certain air flow, drying at 60 ℃ for 5h, and roasting at 500 ℃ for 3h to obtain the SCR flue gas denitration catalyst J.
Experimental methods
Determination of denitration activity of coating type SCR denitration catalyst A-J
The denitration activity evaluation of the catalyst is carried out in a continuous flow fixed bed catalytic reactor, and the whole evaluation device comprises three parts of gas distribution, reaction and flue gas analysis and test.
The gas distribution part consists of a high-pressure steel cylinder gas cylinder, a polytetrafluoroethylene material pipe, a flowmeter, a gas mixer and a heat preservation belt. NH in gas cylinders3Has a concentration of 20% and a concentration of 10% NO. N is a radical of hydrogen2Using industrial nitrogen, O2Is industrial oxygen. The simulated flue gas enters the gas mixer through the flowmeter and then enters the reactor after being mixed.
The reaction pressure is normal pressure, N (NO) in raw material process gas3) 1:1, the process gas space velocity is 19000h-1, and the reaction temperature range is 220-.
The NOx conversion was calculated from the NOx concentrations before and after the reaction:
η＝(C0-C1)/C0*100％
in the formula: eta-represents the denitrification rate in units: by%
C0-for the concentration of NO before reaction, unit: ppm of
C1-for the concentration of NO after reaction, unit: ppm of
The experimental results are as follows:
TABLE 1 catalyst composition
Figure BDA0002550266300000131
TABLE 2 results of catalyst Activity measurement
Figure BDA0002550266300000141
The experimental results show that the SCR flue gas denitration catalyst prepared by the invention has excellent catalytic activity, the catalytic conversion rate can reach 95.7% at 260 ℃, the SCR flue gas denitration catalyst prepared by the invention has a wider reaction window, and the catalytic conversion rate is about 90% at 220-300 ℃.

Claims (3)

1. A preparation method of an SCR flue gas denitration catalyst is characterized by comprising the following steps:
(1) placing the industrial coal cinder into a roasting furnace, roasting at constant temperature, and then crushing the roasted industrial coal cinder to obtain industrial coal cinder powder;
(2) dissolving ethanolamine and ammonia water in water to obtain a solution a, and dissolving paper pulp, sodium carboxymethyl cellulose and polyethylene oxide in water to obtain a solution b;
(3) uniformly mixing industrial coal cinder powder, glass fiber and stearic acid, adding the solution a and the solution b for kneading, and after kneading, pre-extruding, ageing, molding, drying and roasting to obtain a catalyst carrier;
(4) adding cerium nitrate, chromium nitrate and lanthanum nitrate into water to prepare a solution c, then adding titanium dioxide into the solution c, uniformly mixing, standing, drying, roasting and crushing to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst;
(5) adding CeO2-La2O3- Cr2O3/TiO2Mixing inorganic oxide catalyst and adhesive, adding water and stirring to obtain CeO2-La2O3-Cr2O3/TiO2An inorganic oxide catalyst slurry;
(6) adding the catalyst carrier to CeO2-La2O3-Cr2O3/TiO2Inorganic oxide catalyst slurrySoaking the materials, taking out, drying and roasting to obtain the SCR flue gas denitration catalyst;
in the step (1), the constant-temperature roasting temperature is 500 ℃, and the constant-temperature roasting time is 3 hours;
in the step (2), the amount of ethanolamine in the solution a is 1.20kg, the amount of ammonia water is 5.00kg, and the amount of water is 10 kg; the dosage of paper pulp in the solution b is 0.18kg, the dosage of sodium carboxymethylcellulose is 0.35kg, the dosage of polyoxyethylene is 0.35kg, and the dosage of water is 26 kg;
in the step (3), the amount of the industrial coal cinder is 100kg, the amount of the glass fiber is 5kg, and the amount of the stearic acid is 0.50 kg; the kneading time is 60min, the ageing time is 24h, the drying temperature is 70 ℃, the drying time is 10h, the roasting temperature is 680 ℃, and the roasting time is 3 h;
in the step (4), the dosage of the cerium nitrate is as follows according to the mass ratio: the dosage of the chromium nitrate: the dosage of lanthanum nitrate is 10-60:5.5-22:1.5-6, the dosage of water is 300mL, and the addition amount of titanium dioxide is 966g-993 g; the standing time is 24 hours, the drying temperature is 70 ℃, the drying time is 10 hours, the roasting temperature is 680 ℃, and the roasting time is 3 hours;
in the step (5), the binder is a mixture of polyvinyl alcohol, OP-10 and carboxymethyl cellulose; the weight ratio of the polyvinyl alcohol: OP-10: the ratio of carboxymethyl cellulose to cellulose is 2-3:0.5-1: 1-2;
in the step (5), the CeO is calculated according to the mass ratio2-La2O3-Cr2O3/TiO2Inorganic oxide catalyst: the binder is 50: 1;
in the step (6), the drying temperature is 60-100 ℃, the drying time is 5h, the roasting temperature is 460-500 ℃, and the roasting time is 3 h.
2. An SCR flue gas denitration catalyst, characterized in that the catalyst is prepared by the preparation method according to claim 1.
3. The SCR flue gas denitration catalyst of claim 2, wherein the catalyst core is a catalyst carrier prepared from industrial coal slag, and CeO is coated on the surface of the catalyst2-La2O3-Cr2O3/TiO2(ii) a The CeO2-La2O3-Cr2O3/TiO2The coating amount of (2) is 6.2% -7.4%; the CeO2-La2O3-Cr2O3/TiO2CeO in2In an amount of 0.4 to 2.4% by weight, with the CeO2-La2O3-Cr2O3/TiO2Middle La2O3The content of the CeO is 0.1 to 0.4 percent2-La2O3-Cr2O3/TiO2Middle Cr2O30.2 to 0.8 percent of CeO2-La2O3-Cr2O3/ TiO2Medium TiO 22The content is 96.6-99.3%.
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