CN102626653A - Preparation method of SAPO-18-carried Cu-Fe catalyst for ammonia-selective catalytic elimination of NOx - Google Patents
Preparation method of SAPO-18-carried Cu-Fe catalyst for ammonia-selective catalytic elimination of NOx Download PDFInfo
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Abstract
The invention discloses a preparation method of a SAPO-18-carried Cu-Fe catalyst for ammonia-selective catalytic elimination of NOx. The SAPO-18-carried Cu-Fe catalyst is used for selective catalytic elimination of nitric oxides. The preparation method is characterized in that SAPO-18 foraminate molecular sieve carriers having high specific surface areas of 400 to 550m<2>/g are prepared by a soft template synthesis method; and a FeCl3-CuCl2 mixed solution and the SAPO-18 foraminate molecular sieve carriers are prepared into the SAPO-18-carried Cu-Fe catalyst by an ion exchange method. In a wide temperature range of 150 to 550 DEG C, the SAPO-18-carried Cu-Fe catalyst has high catalytic elimination effects on pollutants having a high airspeed of 120000 to 360000mL.(g.h)<-1>, a high O2 concentration of 10 to 20vl.%, high H2O content of 5 to 10wt% and a low NO concentration of 300 to 1000ppm, and has high stability. After adding a hydrocarbon (300 to 1000ppm of propylene) into a reaction system, the SAPO-18-carried Cu-Fe catalyst has high carbon deposition resistance and high hydrothermal stability.
Description
Technical field
The present invention relates to the preparation method of the molecular sieve carried Cu-Fe composite catalyst of a kind of SAPO-18 and be used for selectivity catalysis eliminate nitrogen oxide.
Background technology
Nitrogen oxide (is commonly called as NO
xMainly contain NO) be a kind of major pollution thing in the atmosphere; It has huge harm to ecological environment and health; It not only causes acid rain, also is the presoma that forms the pollution of surface layer atmospheric ozone, the pollution of secondary subparticle and surface water eutrophication, and the environmental problem that causes thus becomes the most outstanding atmospheric environment hot issue with depletion of the ozone layer, Global climate change.Nitrogen oxide is mainly derived from the coal-burning boiler (stationary source) in vehicle exhaust (moving source) and power plant.In recent years, for improving the utilization rate of fuel, internal combustion engine uses the oxygen enrichment fuel-lean type mostly at present, and the major pollutants of this internal combustion engine are nitrogen oxide, and therefore research nitrogen oxides reduction under excess oxygen has crucial meaning., the atmospheric emission standard of countries in the world all carries out the strictness restriction to it.Because it is big to administer the nitrogen oxide difficulty, control and improvement nitrogen oxides pollution have become one of most active problem in the current environmental protection research.According to estimates, the nitrogen oxide emission annual growth is 5.0%-8.0%; To the year two thousand thirty China's nitrogen oxide emission will reach 3,540 ten thousand tons, so, press for the pollution problem that solves nitrogen oxide at present.
The method that multiple elimination nitrogen oxide is arranged at present both at home and abroad, wherein NH
3The method comparative maturity of selective catalyst reduction of nitrogen oxides has been applied to the improvement of vehicle exhaust (stationary source) and thermal power plant (moving source) nitrogen oxides pollution.Present this class methods effect catalyst preferably is mainly Cu/ZSM-5.But this kind catalyst anti-carbon performance and hydrothermal stability are relatively poor.And in vehicle exhaust and power-plant flue gas, hydrocarbon and existence water is inevitably, the key issue of these 2 current just SCR method purifying nitrogen oxides.It is carrier that this patent is selected the higher SAPO-18 molecular sieve of hydrothermal stability (1000 ℃～1200 ℃) for use; Copper and iron are loaded on the SAPO-18 molecular sieve carrier simultaneously, and nitrogen oxide high activity, hydrothermal stability and high anti-carbon performance are eliminated in the catalysis that obtains in the good wide temperature range.At present use the research of copper iron supported catalyst less simultaneously both at home and abroad; The document of just present all reports; Though also have active preferably; But great majority use copper or iron supported catalyst, and the report of while Cu and Fe supported catalyst catalytic treatment nitrogen oxide is few, uses the SAPO-18 molecular sieve as the rarely seen especially report of carrier.
This project implementation obtains state natural sciences fund, Beijing's nature fund and Beijing University of Technology's basis fund (X4005011201101) and subsidizes the subsidy of project, also is the research contents of these projects.
Summary of the invention
The purpose of this invention is to provide the preparation of the molecular sieve carried Cu-Fe composite catalyst of a kind of SAPO-18 and be used for catalysis and eliminate nitrogen oxide, be primarily aimed at the main component NO in the nitrogen oxide.
The catalyst that is provided can efficiently be eliminated NO (60%～90% NO conversion ratio) under wide reaction temperature (100 ℃～550 ℃).And after adding hydrocarbon (300ppm～1000ppm propylene), this catalyst has higher anti-carbon performance.The hydrothermal aging experiment shows that this catalyst is through extreme temperature (700 ℃～800 ℃) and high-load water (10wt%-20wt%H
2O) behind the hydrothermal aging, catalyst activity is stable, has higher hydrothermal stability.And this catalyst preparation process is simple.
The present invention provides a kind of preparation method that the molecular sieve carried Cu-Fe composite catalyst of SAPO-18 of nitrogen oxide is eliminated in catalysis that is used for.
(1) preparation of SAPO-18 molecular sieve
Aluminium hydroxide is joined phosphoric acid solution, evenly stir, room temperature left standstill 5 days～10 days, again with SiO
2And N, N-diisopropylethylamine (C
8H
19N) join in the above mixed solution, stir, obtain colloidal sol at last and form (molar ratio) as follows:
(0.93～2.48)C
8H
19N∶(0.33～1.00)SiO
2∶(0.44～2.21)Al
2O
3∶(0.35～1.74)P
2O
5∶(33～55)H
2O；
This colloidal sol room temperature in closed container was left standstill 5 days～10 days, join subsequently in the stainless steel cauldron of inner liner polytetrafluoroethylene, be heated to 160 ℃～180 ℃, constant temperature 5 days～10 days.Subsequently with solid product filter, washing, and in air 30 ℃～80 ℃ dryings.With 400 ℃～600 ℃ roastings 15～20 hours in oxygen atmosphere of gained solid matter.Above-mentioned made SAPO-18 molecular sieve carrier, specific area is 400～550m
2/ g, total pore volume 0.25～0.40cm
3/ g.
(2) NH
4The preparation of crossover SAPO-18 molecular sieve carrier
With made SAPO-18 molecular sieve and 0.2mol.L
-1～0.8mol.L
-1NH
4Ion-exchange is 12～36 hours under the Cl room temperature, wherein SAPO-18 and NH
4The ratio of Cl is 150g: (0.5～1.5) mol, exchange again 2 times according to said process, and the distilled water washing, 120 ℃ of dryings obtain NH
4Crossover SAPO-18 molecular sieve; With NH
4Crossover SAPO-18 molecular sieve joins 0.05mol.L
-1～0.15mol.L
-1FeCl
2.4H
2O and 0.05～0.15mol.L
-1CuCl
2.2H
2In the O mixed solution, NH wherein
4Crossover SAPO-18 molecular sieve and FeCl
2.4H
2The ratio of O is 40g: (0.5～1.5) mol, FeCl
2.4H
2O and CuCl
2.2H
2The mol ratio of O is (0.1～10.0): 1, and room-temperature ion exchange 24 hours exchanges once subsequent filtration, washing and 120 ℃ of dryings again according to last process; 400 ℃～600 ℃ roastings 4～8 hours make the molecular sieve carried Cu-Fe composite catalyst of SAPO-18.
Said Application of Catalyst is placed on above-mentioned catalyst in the continuous-flow fixed bed device and feeds 300ppm～1000ppmNH
3, 300ppm～1000ppmNO, 10vl.%～20vl.%O
2Content and 5wt %～10wt%H
2The gaseous mixture of O content reacts, and the remaining gas of above gaseous mixture is He or N
2, NH in the reaction gas
3Equate with the concentration of NO; Reaction pressure is 1atm, and reaction velocity is 120,000mL. (g.h)
-1～360,000mL. (g.h)
-1, reaction temperature is 150 ℃～550 ℃.
Catalyst of the present invention, and under high-speed (120,000mL. (g.h)
-1～360,000mL. (g.h)
-1), high O
2Concentration (10vl.%～20vl.%) and high H
2O content is (under the condition of 5wt%～10wt%); In wide temperature range (150 ℃～550 ℃); Have high catalysis and eliminate low concentration of NO (300ppm～1000ppm) activity (NO conversion ratio=60%～90%), and its anti-carbon performance, hydrothermal stability and stable higher: 1) under above reaction condition, in reaction system, add hydrocarbon (300ppm～1000ppm third is rare) again; For the molecular sieve carried Cu-Fe composite catalyst of SAPO-18; Constant in low-temperature zone (150 ℃～250 ℃) and high temperature section (400 ℃～550 ℃) reactivity, less in the active decline of middle-temperature section (300 ℃ and 350 ℃), and in 100 hours; Catalytic activity still keeps high stability, shows high anti-carbon performance; 2) to the molecular sieve carried Cu-Fe composite catalyst of SAPO-18, containing 10wt%～20wt%H
2In the air atmosphere of O, after aging 12～24 hours, catalyst property is stable, shows high anti-hydrothermal stability in extreme temperature (700 ℃～850 ℃); 3) SAPO-18 molecular sieve carrier has simple, the low price of preparation process, the used metal oxide Cu of load and Fe compound price cheapness, characteristics such as environmental friendliness; 4) the present invention is at O
2In the higher air atmosphere of concentration, NH
3Directly NO is reduced into N
2But the use energy consumption is low, easy and simple to handle, reaction condition is gentle, can reduce advantages such as secondary pollution and continuous operation, and this catalyst is applicable to the elimination of NO pollutants such as vehicle exhaust and power plant.
Description of drawings
Fig. 1 is the XRD figure of Cu-Fe/SAPO-18-I, Cu-Fe/SAPO-18-I, Cu-Fe/SAPO-18-II, Cu-Fe/SAPO-18-III and the Cu-Fe/SAPO-18-IV of the embodiment of the invention 1,2,3 and 4 preparations.
Fig. 2 is the N of Cu-Fe/SAPO-18-I, Cu-Fe/SAPO-18-I, Cu-Fe/SAPO-18-II, Cu-Fe/SAPO-18-III and the Cu-Fe/SAPO-18-IV of the embodiment of the invention 1,2,3 and 4 preparations
2-absorption/desorption figure.
Fig. 3 is the NH of Cu-Fe/SAPO-18-I (A), Cu-Fe/SAPO-18-II (B), Cu-Fe/SAPO-18-III (C) and the Cu-Fe/SAPO-1g-IV (D) of the embodiment of the invention 1,2,3 and 4 preparations
3Active and the anti-carbon performance of Selective Catalytic Reduction of NO.
Fig. 4 is the NH of Cu-Fe/SAPO-18-I (A), Cu-Fe/SAPO-18-II (B), Cu-Fe/SAPO-18-III (C) and the Cu-Fe/SAPO-1g-IV (D) of this embodiment of the invention 1,2,3 and 4 preparations
3Selective Catalytic Reduction of NO activity and hydrothermal stability.
Fig. 5 is at NH
3Add the 700ppm third rare and 5%H in the Selective Catalytic Reduction of NO reaction system
2Behind the O, the stability of Cu-Fe/SAPO-18-I (A), Cu-Fe/SAPO-18-II (B), Cu-Fe/SAPO-18-III (C) and Cu-Fe/SAPO-18-IV (D) catalyst of the embodiment of the invention 1,2,3 and 4 preparations.
The specific embodiment
Embodiment 1
(1) preparation of SAPO-18 molecular sieve
Aluminium hydroxide is joined phosphoric acid solution, evenly stir, room temperature left standstill 5 days, again with SiO
2And N, N-diisopropylethylamine (C
8H
19N) join in the above mixed solution, stir, obtain colloidal sol at last and form (molar ratio) as follows:
0.93C
8H
19N∶0.33SiO
2∶0.44Al
2O
3∶0.35P
2O
5∶33H
2O
This colloidal sol room temperature in closed container was left standstill 5 days, joins subsequently in the stainless steel cauldron of inner liner polytetrafluoroethylene, be heated to 160 ℃, constant temperature 5 days subsequently with solid product filter, washing, and in air 30 ℃ of dryings.Be to remove template and other impurity, with the 400 ℃ of roastings 15 hours in oxygen atmosphere of gained solid matter.Above-mentioned made SAPO-18 molecular sieve carrier, specific area is 400m
2/ g, total pore volume 0.25cm
3/ g.
(2) NH
4The preparation of crossover SAPO-18 molecular sieve carrier
With SAPO-18 molecular sieve and 0.2mol.L
-1NH
4Ion-exchange is 12 hours under the Cl room temperature, wherein SAPO-18 and NH
4The ratio of Cl is 150g: 0.5mol, exchanges twice again according to said process, the distilled water washing, and 120 ℃ of dryings obtain NH
4Crossover SAPO-18 molecular sieve.
(3) ion-exchange prepares the molecular sieve carried Cu-Fe compound of SAPO-18
With NH
4Crossover SAPO-18 molecular sieve joins 0.05mol.L
-1FeCl
2.4H
2O and 0.05mol.L
-1CuCl
2.2H
2In the O mixed solution, NH wherein
4Crossover SAPO-18 molecular sieve and FeCl
2.4H
2The ratio of O is 40g: 0.5mol, FeCl
2.4H
2O and CuCl
2.2H
2The mol ratio of O is 0.1: 1, and room-temperature ion exchange 24 hours exchanges once subsequent filtration, washing and 120 ℃ of dryings again according to last process.400 ℃ of roastings 4 hours make Cu-Fe/SAPO-18-I.
(4) catalyst of the present invention, 120,000mL. (g.h)
-1Under the air speed, 10vl.%O
2Concentration and 5wt%H
2Under the O concentration conditions, in wide temperature range (150 ℃～550 ℃), 300ppm NO had high catalysis elimination activity (NO conversion ratio=60%～90%); And its anti-carbon performance, hydrothermal stability and stability are higher: 1) under above reaction condition; In reaction system, add the hydrocarbon propylene of 300ppm again, the molecular sieve carried Cu-Fe composite catalyst of SAPO-18 is constant in low-temperature zone (150 ℃～250 ℃) and high temperature section (400 ℃～550 ℃) reactivity; Less in the active decline of middle-temperature section (300 ℃ and 350 ℃); And in 100 hours, catalytic activity still keeps high stability, shows high anti-carbon performance; 2) to the molecular sieve carried Cu-Fe composite catalyst of SAPO-18, containing 10wt%H
2In the air atmosphere of O, at 700 ℃ after aging 12 hours, catalyst property is stable, shows higher anti-hydrothermal stability.
Embodiment 2
(1) preparation of SAPO-18 molecular sieve
Aluminium hydroxide is joined phosphoric acid solution, evenly stir, room temperature left standstill 7 days, again with SiO
2And N, N-diisopropylethylamine (C
8H
19N) join in the above mixed solution, stir, obtain colloidal sol at last and form (molar ratio) as follows:
1.4C
8H
19N∶0.60SiO
2∶Al
2O
3∶0.79P
2O
5∶40H
2O
This colloidal sol room temperature in closed container was left standstill 7 days, join subsequently in the stainless steel cauldron of inner liner polytetrafluoroethylene, be heated to 170 ℃, constant temperature 7 days.Subsequently with solid product filter, washing, and in air 50 ℃ of dryings.Be to remove template and other impurity, with the 500 ℃ of roastings 15 hours in oxygen atmosphere of gained solid matter.Above-mentioned made SAPO-18 molecular sieve carrier, specific area is 440m
2/ g, total pore volume 0.31cm
3/ g.
(2) NH
4The preparation of crossover SAPO-18 molecular sieve carrier
With SAPO-18 molecular sieve and 0.4mol.L
-1NH
4Ion-exchange is 20 hours under the Cl room temperature, wherein SAPO-18 and NH
4The ratio of Cl is 150g: 1.0mol, exchanges twice again according to said process, the distilled water washing, and 120 ℃ of dryings obtain NH
4Crossover SAPO-18 molecular sieve.
(3) ion-exchange prepares the molecular sieve carried Cu-Fe compound of SAPO-18
With NH
4Crossover SAPO-18 molecular sieve joins 0.10mol.L
-1FeCl
2.4H
2O and 0.10mol.L
-1CuCl
2.2H
2In the O mixed solution, NH wherein
4Crossover SAPO-18 molecular sieve and FeCl
2.4H
2The ratio of O is 40g: 1.0mol, FeCl
2.4H
2O and CuCl
2.2H
2The mol ratio of O is 1.0: 1, and room-temperature ion exchange 24 hours exchanges once subsequent filtration, washing and 120 ℃ of dryings again according to last process.550 ℃ of roastings 5 hours make Cu-Fe/SAPO-18-II.
(4) catalyst of the present invention, 200,000mL. (g.h)
-1Under the air speed, 15vl.%O
2Concentration and 6wt%H
2Under the O content condition, in wide temperature range (150 ℃～550 ℃), have high catalysis and eliminate low concentration 500ppm NO active (NO conversion ratio=60%～90%); And its anti-carbon performance, hydrothermal stability and stability are higher: 1) under above reaction condition; In reaction system, add the 500ppm propylene again, the molecular sieve carried Cu-Fe composite catalyst of SAPO-18 is constant in low-temperature zone (150 ℃～250 ℃) and high temperature section (400 ℃～550 ℃) reactivity; Less in the active decline of middle-temperature section (300 ℃ and 350 ℃); And in 100 hours, catalytic activity still keeps high stability, shows high anti-carbon performance; 2) to the molecular sieve carried Cu-Fe composite catalyst of SAPO-18, containing 12wt%H
2In the air atmosphere of O, at 750 ℃ after aging 15 hours, catalyst property is stable, shows higher anti-hydrothermal stability.
Embodiment 3
(1) preparation of SAPO-18 molecular sieve
Aluminium hydroxide is joined phosphoric acid solution, evenly stir, room temperature left standstill 8 days, again with SiO
2And N, N-diisopropylethylamine (C
8H
19N) join in the above mixed solution, stir, obtain colloidal sol at last and form (molar ratio) as follows:
1.05C
8H
19N∶0.45SiO
2∶Al
2O
3∶0.78P
2O
5∶28H
2O
This colloidal sol room temperature in closed container was left standstill 8 days, join subsequently in the stainless steel cauldron of inner liner polytetrafluoroethylene, be heated to 170 ℃, constant temperature 8 days.Subsequently with solid product filter, washing, and in air 70 ℃ of dryings.Be to remove template and other impurity, with the 550 ℃ of roastings 18 hours in oxygen atmosphere of gained solid matter.Above-mentioned made SAPO-18 molecular sieve carrier, specific area is 510m
2/ g, total pore volume 0.33cm
3/ g.
(2) NH
4The preparation of crossover SAPO-18 molecular sieve carrier
With SAPO-18 molecular sieve and 0.6mol.L
-1NH
4Ion-exchange is 30 hours under the Cl room temperature, wherein SAPO-18 and NH
4The ratio of Cl is 150g: 1.2mol, exchanges twice again according to said process, the distilled water washing, and 120 ℃ of dryings obtain NH
4Crossover SAPO-18 molecular sieve.
(3) ion-exchange prepares the molecular sieve carried Cu-Fe compound of SAPO-18
With NH
4Crossover SAPO-18 molecular sieve joins 0.12mol.L
-1FeCl
2.4H
2O and 0.12mol.L
-1CuCl
2.2H
2In the O mixed solution, NH wherein
4Crossover SAPO-18 molecular sieve and FeCl
2.4H
2The ratio of O is 40g: 1.2mol, FeCl
2.4H
2O and CuCl
2.2H
2The mol ratio of O is 5.0: 1, and room-temperature ion exchange 24 hours exchanges once subsequent filtration, washing and 120 ℃ of dryings again according to last process.600 ℃ of roastings 6 hours, prepared catalyst is Cu-Fe/SAPO-18-III.
(4) catalyst of the present invention, 300,000mL. (g.h)
-1Under the air speed, 15vl.%O
2Concentration and 8wt%H
2Under the O content condition, in wide temperature range (150 ℃～550 ℃), have high catalysis and eliminate low concentration 700ppm NO active (NO conversion ratio=60%～90%); And its anti-carbon performance, hydrothermal stability and stability are higher: 1) under above reaction condition; In reaction system, add the 700ppm propylene again, the molecular sieve carried Cu-Fe composite catalyst of SAPO-18 is constant in low-temperature zone (150 ℃～250 ℃) and high temperature section (400 ℃～550 ℃) reactivity; Less in the active decline of middle-temperature section (300 ℃ and 350 ℃); And in 100 hours, catalytic activity still keeps high stability, shows high anti-carbon performance; 2) to the molecular sieve carried Cu-Fe composite catalyst of SAPO-18, containing 15wt%H
2In the air atmosphere of O, at 800 ℃ after aging 20 hours, catalyst property is stable, shows higher anti-hydrothermal stability.
Embodiment 4
(1) preparation of SAPO-18 molecular sieve
Aluminium hydroxide is joined phosphoric acid solution, evenly stir, room temperature left standstill 10 days, again with SiO
2And N, N-diisopropylethylamine (C
8H
19N) join in the above mixed solution, stir, obtain colloidal sol at last and form (molar ratio) as follows:
2.48C
8H
19N∶1.00SiO
2∶2.21Al
2O
3∶1.74P
2O
5∶55H
2O
This colloidal sol room temperature in closed container was left standstill 10 days, join subsequently in the stainless steel cauldron of inner liner polytetrafluoroethylene, be heated to 180 ℃, constant temperature 10 days.Subsequently with solid product filter, washing, and in air 80 ℃ of dryings.Be to remove template and other impurity, with the 600 ℃ of roastings 20 hours in oxygen atmosphere of gained solid matter.Above-mentioned made SAPO-18 molecular sieve carrier, specific area is 550m
2/ g, total pore volume 0.40cm
3/ g.
(2) NH
4The preparation of crossover SAPO-18 molecular sieve carrier
With SAPO-18 molecular sieve and 0.8mol.L
-1NH
4Ion-exchange is 36 hours under the Cl room temperature, wherein SAPO-18 and NH
4The ratio of Cl is 150g: 1.5mol, exchanges twice again according to said process, the distilled water washing, and 120 ℃ of dryings obtain NH
4Crossover SAPO-18 molecular sieve.
(3) ion-exchange prepares the molecular sieve carried Cu-Fe compound of SAPO-18
With NH
4Crossover SAPO-18 molecular sieve joins 0.15mol.L
-1FeCl
2.4H
2O and 0.15mol.L
-1CuCl
2.2H
2In the O mixed solution, NH wherein
4Crossover SAPO-18 molecular sieve and FeCl
2.4H
2The ratio of O is 40g: 1.5mol, FeCl
2.4H
2O and CuCl
2.2H
2The mol ratio of O is 10.0: 1, and room-temperature ion exchange 24 hours exchanges once subsequent filtration, washing and 120 ℃ of dryings again according to last process.600 ℃ of roastings 8 hours make the Cu-Fe/SAPO-18-IV catalyst.
(4) catalyst of the present invention, 360,000mL. (g.h)
-1Under the air speed, 20vl.%O
2Concentration and 10wt%H
2Under the O content condition, in wide temperature range (150 ℃～550 ℃), have high catalysis and eliminate 1000ppm low concentration of NO active (NO conversion ratio=60%～90%); And its anti-carbon performance, hydrothermal stability and stability are higher: 1) under above reaction condition; In reaction system, add the 1000ppm propylene again, the molecular sieve carried Cu-Fe composite catalyst of SAPO-18 is constant in low-temperature zone (150 ℃～250 ℃) and high temperature section (400 ℃～550 ℃) reactivity; Less in the active decline of middle-temperature section (300 ℃ and 350 ℃); And in 100 hours, catalytic activity still keeps high stability, shows high anti-carbon performance; 2) to the molecular sieve carried Cu-Fe composite catalyst of SAPO-18, containing 20wt%H
2In the air atmosphere of O, at 850 ℃ after aging 24 hours, catalyst property is stable, shows higher anti-hydrothermal stability.
Claims (2)
1. be used for ammine selective catalysis and eliminate SAPO-18 loaded Cu-Fe Preparation of catalysts method of NOx, it is characterized in that step is following:
1), is used for the preparation that the SAPO-18 molecular sieve carrier of nitrogen oxide is eliminated in catalysis
Aluminium hydroxide is joined phosphoric acid solution, evenly stir, room temperature leaves standstill and obtained mixed solution in 5 days～10 days, again with SiO
2And N, N-diisopropylethylamine C
8H
19N joins in the above mixed solution, stirs, and obtains the colloidal sol constitutive molar ratio for example down:
(0.93～2.48)C
8H
19N∶(0.33～1.00)SiO
2∶(0.44～2.21)Al
2O
3∶(0.35～1.74)P
2O
5∶(33～55)H
2O；
This colloidal sol room temperature in closed container was left standstill 5 days～10 days, join subsequently in the stainless steel cauldron of inner liner polytetrafluoroethylene, be heated to 160 ℃～180 ℃, constant temperature 5 days～10 days; Subsequently with solid product filter, washing, and in air 30 ℃～80 ℃ dryings; 400 ℃～600 ℃ roastings in oxygen atmosphere of gained solid matter were made the SAPO-18 molecular sieve in 15～20 hours;
2), ion-exchange prepares the molecular sieve carried Cu-Fe complex catalyst of SAPO-18
With made SAPO-18 molecular sieve and 0.2mol.L
-1～0.8mol.L
-1NH
4Ion-exchange is 12～36 hours under the Cl room temperature, wherein SAPO-18 and NH
4The ratio of Cl is 150g: (0.5～1.5) mol, exchange again 2 times according to said process, and the distilled water washing, 120 ℃ of dryings obtain NH
4Crossover SAPO-18 molecular sieve; With NH
4Crossover SAPO-18 molecular sieve joins 0.05mol.L
-1～0.15mol.L
-1FeCl
2.4H
2O and 0.05～0.15mol.L
-1CuCl
2.2H
2In the O mixed solution, NH wherein
4Crossover SAPO-18 molecular sieve and FeCl
2.4H
2The ratio of O is 40g: (0.5～1.5) mol, FeCl
2.4H
2O and CuCl
2.2H
2The mol ratio of O is (0.1～10.0): 1, and room-temperature ion exchange 24 hours exchanges once subsequent filtration, washing and 120 ℃ of dryings again according to last process; 400 ℃～600 ℃ roastings 4～8 hours make the molecular sieve carried Cu-Fe composite catalyst of SAPO-18.
2. application rights requires the 1 said Application of Catalyst that the SAPO-18 loaded Cu-Fe Preparation of catalysts method prepares that is used for catalysis elimination nitrogen oxide, it is characterized in that: above-mentioned catalyst is placed in the continuous-flow fixed bed device feeds 300ppm～1000ppmNH
3, 300ppm～1000ppmNO, 10vl.%～20vl.%O
2Content and 5wt%～10wt%H
2The gaseous mixture of O content reacts, and the remaining gas of above gaseous mixture is He or N
2, NH in the reaction gas
3Equate with the concentration of NO; Reaction pressure is 1atm, and reaction velocity is 120,000mL. (g.h)
-1～360,000mL. (g.h)
-1, reaction temperature is 150 ℃～550 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210071983.9A CN102626653B (en) | 2012-03-16 | 2012-03-16 | Preparation method of SAPO-18-carried Cu-Fe catalyst for ammonia-selective catalytic elimination of NOx |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210071983.9A CN102626653B (en) | 2012-03-16 | 2012-03-16 | Preparation method of SAPO-18-carried Cu-Fe catalyst for ammonia-selective catalytic elimination of NOx |
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| CN102626653A true CN102626653A (en) | 2012-08-08 |
| CN102626653B CN102626653B (en) | 2014-01-01 |
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| CN201210071983.9A Expired - Fee Related CN102626653B (en) | 2012-03-16 | 2012-03-16 | Preparation method of SAPO-18-carried Cu-Fe catalyst for ammonia-selective catalytic elimination of NOx |
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| CN103785420A (en) * | 2014-02-17 | 2014-05-14 | 中国科学院生态环境研究中心 | Catalyst for surface sulfation of ferric oxide, as well as preparation method and application thereof |
| CN104069861A (en) * | 2014-07-07 | 2014-10-01 | 大连理工大学 | Mesoporous iron-based compound oxide catalyst, preparation method and use thereof to ammonia selective catalytic reduction of nitric oxide |
| JP2015044720A (en) * | 2013-08-29 | 2015-03-12 | 三菱樹脂株式会社 | Metal-containing copper-sapo zeolite |
| CN104888851A (en) * | 2015-06-03 | 2015-09-09 | 中国科学院生态环境研究中心 | CuCe-SAPO-34 molecular sieve catalyst, as well as preparation method and use thereof |
| CN105289707A (en) * | 2015-11-06 | 2016-02-03 | 中国第一汽车股份有限公司 | Method for preparing novel Cu-Fe molecular sieve catalyst for diesel vehicle tail gas |
| CN105396610A (en) * | 2015-11-06 | 2016-03-16 | 中国第一汽车股份有限公司 | Composite copper-based molecular sieve catalyst and preparation method thereof |
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| CN105749960A (en) * | 2016-03-10 | 2016-07-13 | 镇江翰宏新材料科技有限公司 | Preparation method of catalyst for removing NOx by ammonia selective catalytic reduction |
| CN107185589A (en) * | 2017-05-24 | 2017-09-22 | 华中科技大学 | A kind of preparation method and application of the catalyst of Cu SAPO 18 of promoter metal doping |
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| CN104069861A (en) * | 2014-07-07 | 2014-10-01 | 大连理工大学 | Mesoporous iron-based compound oxide catalyst, preparation method and use thereof to ammonia selective catalytic reduction of nitric oxide |
| CN104888851A (en) * | 2015-06-03 | 2015-09-09 | 中国科学院生态环境研究中心 | CuCe-SAPO-34 molecular sieve catalyst, as well as preparation method and use thereof |
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| CN105289707A (en) * | 2015-11-06 | 2016-02-03 | 中国第一汽车股份有限公司 | Method for preparing novel Cu-Fe molecular sieve catalyst for diesel vehicle tail gas |
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| CN105749960A (en) * | 2016-03-10 | 2016-07-13 | 镇江翰宏新材料科技有限公司 | Preparation method of catalyst for removing NOx by ammonia selective catalytic reduction |
| CN107185589A (en) * | 2017-05-24 | 2017-09-22 | 华中科技大学 | A kind of preparation method and application of the catalyst of Cu SAPO 18 of promoter metal doping |
| CN110292944A (en) * | 2019-07-31 | 2019-10-01 | 北京工业大学 | A kind of ultra-wide temperature window SCR denitration and preparation method thereof |
| CN110292944B (en) * | 2019-07-31 | 2022-11-08 | 北京工业大学 | SCR denitration catalyst with ultra-wide temperature window and preparation method thereof |
| CN112439448A (en) * | 2019-08-30 | 2021-03-05 | 大连海事大学 | Copper-containing or iron-based SAPO molecular sieve SCR catalyst and preparation method and application thereof |
| CN112439448B (en) * | 2019-08-30 | 2023-11-03 | 大连海事大学 | Copper-containing or iron-based SAPO molecular sieve SCR catalyst, and preparation method and application thereof |
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