CN112264039A - Preparation method and application of medium-high temperature flue gas denitration catalyst - Google Patents
Preparation method and application of medium-high temperature flue gas denitration catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 130
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000003546 flue gas Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 40
- 238000000576 coating method Methods 0.000 claims abstract description 40
- 239000000919 ceramic Substances 0.000 claims abstract description 31
- 239000007789 gas Substances 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003245 coal Substances 0.000 claims abstract description 21
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 18
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010937 tungsten Substances 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 10
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims description 56
- 150000001875 compounds Chemical class 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- 239000006255 coating slurry Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002912 waste gas Substances 0.000 claims description 10
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 6
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 6
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000004364 calculation method Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 4
- 238000007598 dipping method Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 229910052750 molybdenum Inorganic materials 0.000 abstract 1
- 239000011733 molybdenum Substances 0.000 abstract 1
- 229910052763 palladium Inorganic materials 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- JUBNUQXDQDMSKL-UHFFFAOYSA-N palladium(2+);dinitrate;dihydrate Chemical compound O.O.[Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JUBNUQXDQDMSKL-UHFFFAOYSA-N 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- PJVWKTKQMONHTI-UHFFFAOYSA-N warfarin Chemical compound OC=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 PJVWKTKQMONHTI-UHFFFAOYSA-N 0.000 description 1
- 229960005080 warfarin Drugs 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- 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
-
- B01J35/56—
-
- B01J35/61—
Abstract
The invention relates to the technical field of nitrogen oxide control in environmental protection, in particular to a preparation method and application of a medium-high temperature flue gas denitration catalyst applied to discharge of a coal bed gas power plant. The denitration catalyst comprises a catalyst coating and honeycomb ceramics, wherein a carrier of the catalyst coating is a mesoporous silica molecular sieve and coated alumina, active components comprise iron elements and/or cerium elements, and cocatalyst components comprise molybdenum elements, tungsten elements and palladium elements; the catalyst coating is coated on honeycomb ceramics through dipping, drying and roasting methods to obtain the industrial denitration catalyst, the prepared honeycomb denitration catalyst can be effectively applied to medium-high temperature flue gas denitration discharged by a coal bed gas power plant, the efficiency of removing nitric oxide at 500 ℃ reaches 99%, and the catalyst coating is nontoxic and has excellent durability.
Description
Technical Field
The invention relates to the technical field of nitrogen oxide control in environmental protection, in particular to a preparation method of a medium-high temperature flue gas denitration catalyst and application of the medium-high temperature flue gas denitration catalyst in medium-high temperature flue gas denitration treatment of coal bed gas power plant emission.
Background
Since the 21 st century, the nation has continuously encouraged and developed green recycling economy, advocated the construction of resource-saving and environment-friendly society, and further deepened the understanding of energy utilization and ecological environment protection. The coal bed gas power generation is used as a novel energy utilization field and has wide development prospect. However, high-temperature exhaust gas discharged from coal bed methane power generation contains Nitrogen Oxides (NO)x) Sulfur Oxide (SO)x) And the like, which cause serious pollution and harm to the atmospheric environment and cause secondary pollution such as photochemical smog and the like. Referring to the emission requirement of 'boiler or gas turbine unit using gas as fuel' in 'emission standard of atmospheric pollutants for thermal power plant' (GB 13223-xThe concentration should be controlled at 120mg/m3The following.
Among the numerous denitration techniques, Selective Catalytic Reduction (SCR) is the most widely used NO processxTreatment technology, where catalysts are the core of SCR technology. Commercial denitration catalyst is mostly V2O5-WO3/TiO2Base system, has been widely usedIn coal-fired power plants, glass furnaces, cement plants and other industries. However, the application temperature window of the catalyst is narrow, the application temperature is mostly 320-400 ℃, the temperature of the waste gas discharged by a coal bed gas power plant is about 500 ℃, and the conventional commercial vanadium titanium-based catalyst is difficult to meet the denitration requirement. Moreover, the smoke temperature is over 450 ℃ for a long time, which is easy to cause the sintering of the vanadium-titanium based catalyst and leads TiO in the catalyst to2The crystal form of the catalyst is changed, the particles are enlarged, and the specific surface area is reduced, so that the catalyst is deactivated; and the main active ingredient V of the vanadium-titanium-like catalyst2O5It is toxic and the spent catalyst needs to be treated separately as a hazardous waste.
Therefore, how to develop a novel catalyst for medium-high temperature waste gas discharged by a coal bed gas power plant can be efficiently and stably applied to medium-high temperature section flue gas denitration, avoid energy waste caused by heat exchange and temperature reduction, and become a difficult point which needs to be researched urgently in the field of technology.
Disclosure of Invention
Aiming at medium-high temperature waste gas discharged by a coal bed gas power plant, the invention provides a medium-high temperature flue gas denitration catalyst applied to the discharge of the coal bed gas power plant and a preparation method and application thereof, aiming at overcoming the problems of low efficiency, easy inactivation and the like of the existing commercial denitration catalyst under medium-high temperature conditions and solving the disposal problem of the waste catalyst.
In order to achieve the purpose, firstly, the invention prepares medium-high temperature flue gas denitration catalyst coating slurry applied to discharge of a coal bed gas power plant, which comprises a carrier, an active component and a cocatalyst component, wherein the carrier comprises a molecular sieve, alumina and a mixture thereof; the active component comprises iron and/or cerium; the catalyst promoter comprises molybdenum element, tungsten element and palladium element, and is shown in steps (1) to (5). Secondly, the catalyst is coated on the honeycomb ceramics by methods of blowing, dipping, calcining and the like to adapt to industrial operation conditions, see steps (6) to (8).
The following technical scheme is adopted specifically: a preparation method of a medium-high temperature flue gas denitration catalyst comprises the following steps:
(1) weighing a proper amount of mesoporous silica molecular sieve and coated alumina, mixing, adding a proper amount of deionized water, and uniformly stirring to obtain a carrier solution, wherein the mesoporous silica molecular sieve and the coated alumina account for 20-35% of the carrier solution by mass percent;
(2) weighing a proper amount of an iron element precursor compound or/and a cerium element precursor compound, adding a proper amount of deionized water, and stirring until the mixture is completely dissolved to obtain an active component precursor solution, wherein the iron element precursor compound or/and the cerium element precursor compound account for 5% of the active component precursor solution in percentage by mass;
(3) mixing the active component precursor solution with the carrier solution, and stirring for 1 h;
(4) weighing a proper amount of a molybdenum element precursor compound, a tungsten element precursor compound and a palladium element precursor compound, adding a proper amount of deionized water, uniformly stirring, adding the mixed solution obtained in the step (3), and stirring for 24 hours to obtain a catalyst coating mixed solution, wherein the total mass of the molybdenum element precursor compound, the tungsten element precursor compound and the palladium element precursor compound accounts for 5% of the mass of the catalyst coating mixed solution obtained in the step (4);
(5) transferring the catalyst coating mixed solution obtained in the step (4) to a ball mill, and performing ball milling for 24-72 h to obtain catalyst coating slurry;
(6) dipping the honeycomb ceramic into the catalyst coating slurry for 5-20 min, and blowing the surface of the honeycomb ceramic by high-pressure air after uniform mixing;
(7) drying the honeycomb ceramic coated with the catalyst coating for 8 hours at 120 ℃ in an air drying oven;
(8) and calcining the dried honeycomb ceramic at the high temperature of 550 ℃ for 5 hours to obtain the molded industrial denitration catalyst.
Further, the aperture of the mesoporous silica molecular sieve selected in the step (1) is 8 nm-30 nm.
Further, the iron element precursor compound or/and the cerium element precursor compound selected in the step (2) is ferric nitrate nonahydrate, and the cerium element precursor compound is cerium nitrate hexahydrate.
Further, the molybdenum element precursor compound selected in the step (3) is ammonium molybdate tetrahydrate, the tungsten element precursor compound is ammonium tungstate, and the palladium element precursor compound is palladium nitrate.
Further, the molar ratio of molybdenum element, tungsten element and palladium element of the molybdenum element precursor compound, the tungsten element precursor compound and the palladium element precursor compound in the step (4) is (20-80): (50-200): 1.
Further, the coating amount calculation method of the catalyst is as follows: w ═ m1-m0)/m0X 100%, W is the coating amount of the catalyst, m0The mass (in g) of the blank honeycomb ceramics before the catalyst coating is described as m1The catalyst coating amount is 8 to 15% by mass of the honeycomb ceramic after coating the catalyst and firing.
The invention also provides application of the denitration catalyst obtained by the preparation method in denitration of medium-high temperature flue gas discharged by a coal bed gas power plant, and is characterized in that the denitration catalyst is added into an SCR (selective catalytic reduction) denitration device for nitrogen oxide treatment in treatment of waste gas of the coal bed gas power plant.
Further, NO is contained at a high temperature of 400-600 DEG CxIn the denitration reaction of the flue gas, NO is introducedxAmmonia gas as reducing agent in the same concentration, NOxThe removal rate is stabilized at more than 90%, and the high-temperature stability is excellent.
The denitration catalyst provided by the application contains NO at medium and high temperaturexThe main chemical reactions for SCR denitration in the flue gas environment are as follows:
4NO+O2+4NH3→4N2+6H2O；
2NO2+O2+4NH3→3N2+6H2O。
compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the catalyst has stronger catalytic activity in a medium-high temperature waste gas interval discharged by a coal bed gas power plant, the denitration catalyst prepared by the preparation method provided by the invention takes mesoporous silica doped coated alumina as a carrier of a coating, has ordered pore diameter and permeable pores, forms a nano reactor with infinite space limited areas, and has ultrahigh specific surface area which is beneficial to the ultrahigh uniform dispersion of an active component and a catalysis-assisting component, thereby forming the active component with extremely small particle size. And the coating has excellent thermal stability, and can effectively prevent the catalyst sintering effect caused by medium-high temperature flue gas denitration.
(2) The catalyst can endure medium-high temperature flue gas for a long time, and simultaneously ensures higher denitration activity;
(3) the active components and the carrier of the catalyst are nontoxic and do not produce secondary pollution.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The coated alumina used in the denitration catalyst provided by the invention is amorphous alumina, has a particle size of nanometer level, is purchased from Ziboxinxin Industrial and trade Co., Ltd, and other raw materials are purchased from the market.
Example 1
(1) Weighing 15g of mesoporous silica molecular sieve and 5g of coated alumina, mixing, adding a proper amount of deionized water, and uniformly stirring to obtain a carrier solution;
(2) weighing 5g of ferric nitrate nonahydrate, adding a proper amount of deionized water, and stirring until the ferric nitrate nonahydrate is completely dissolved to obtain an active component precursor solution;
(3) mixing the active component precursor solution with the carrier solution, and stirring for 1 h;
(4) weighing a proper amount of ammonium molybdate tetrahydrate, ammonium tungstate and palladium nitrate dihydrate (5 g in total) as cocatalyst components according to a molar ratio of Mo to W to Pd of 20 to 50 to 1, adding a proper amount of deionized water, uniformly stirring, adding the active component precursor and carrier mixed solution, and stirring for 24 hours to obtain a catalyst coating mixed solution;
(5) transferring the catalyst coating mixed solution obtained by the scheme to a ball mill, and performing ball milling for 24 hours to obtain catalyst coating slurry;
(6) soaking the honeycomb ceramic in the catalyst coating slurry for 5min, and blowing the surface of the honeycomb ceramic by high-pressure air after uniform mixing;
(7) drying the honeycomb ceramic coated with the catalyst coating for 8 hours at 120 ℃ in an air drying oven;
(8) and (3) calcining the dried honeycomb ceramic at the high temperature of 550 ℃ for 5 hours to obtain the formed industrial denitration catalyst, wherein the catalyst coating accounts for 8% of the total mass of the catalyst.
Medium-high temperature NO-containing device for simulating discharge of coal bed gas power plant in SCR denitration experimentxAnd (3) removing waste gas:
in the denitration system, NOxThe inlet volume concentration is 1000ppm, the volume concentration of the reducing agent ammonia is 1000ppm, the volume concentration of the oxygen is 5 percent, the balance gas is nitrogen, and the space velocity is designed to be 10000h-1. The prepared catalyst has NO at 400-600 deg.cxThe outlet volume concentration is less than 100ppm, the denitration efficiency is higher than 90%, and the catalytic denitration efficiency of the catalyst at 400 ℃ is 93% at the best. After 500h durability test, the activity of the catalyst remained stable.
Example 2
(1) Weighing 25g of mesoporous silica molecular sieve and 10g of coated alumina, mixing, adding a proper amount of deionized water, and uniformly stirring to obtain a carrier solution;
(2) weighing 5g of ferric nitrate nonahydrate, adding a proper amount of deionized water, and stirring until the ferric nitrate nonahydrate is completely dissolved to obtain an active component precursor solution;
(3) mixing the active component precursor solution with the carrier solution, and stirring for 1 h;
(4) weighing a proper amount of ammonium molybdate tetrahydrate, ammonium tungstate and palladium nitrate dihydrate (5 g in total) as cocatalyst components according to a molar ratio of Mo to W to Pd of 40 to 100 to 1, adding a proper amount of deionized water, uniformly stirring, adding the active component precursor and carrier mixed solution, and stirring for 24 hours to obtain a catalyst coating mixed solution;
(5) transferring the catalyst coating mixed solution obtained by the scheme to a ball mill, and carrying out ball milling for 36h to obtain catalyst coating slurry;
(6) soaking the honeycomb ceramic in the catalyst coating slurry for 10min, and blowing the surface of the honeycomb ceramic by high-pressure air after uniform mixing;
(7) drying the honeycomb ceramic coated with the catalyst coating for 8 hours at 120 ℃ in an air drying oven;
(8) and (3) calcining the dried honeycomb ceramic at the high temperature of 550 ℃ for 5 hours to obtain the formed industrial denitration catalyst, wherein the catalyst coating accounts for 12% of the total mass of the catalyst.
Medium-high temperature NO-containing device for simulating discharge of coal bed gas power plant in SCR denitration experimentxAnd (3) removing waste gas:
in the denitration system, NOxThe inlet volume concentration is 1000ppm, the volume concentration of the reducing agent ammonia is 1000ppm, the volume concentration of the oxygen is 5 percent, the balance gas is nitrogen, and the space velocity is designed to be 10000h-1. The prepared catalyst has NO at 400-600 deg.cxThe outlet volume concentration is less than 90ppm, the denitration efficiency is higher than 91%, and the catalytic denitration efficiency of the catalyst at 450 ℃ is the best 95%. After 500h durability test, the activity of the catalyst remained stable.
Example 3
(1) Weighing 20g of mesoporous silica molecular sieve and 7.5g of coated alumina, mixing, adding a proper amount of deionized water, and uniformly stirring to obtain a carrier solution;
(2) weighing 5g of a mixture of cerium nitrate hexahydrate and ferric nitrate nonahydrate at a molar ratio of Ce to Fe being 5:1, adding a proper amount of deionized water, and stirring until the mixture is completely dissolved to obtain an active component precursor solution;
(3) mixing the active component precursor solution with the carrier solution, and stirring for 1 h;
(4) weighing a proper amount of ammonium molybdate tetrahydrate, ammonium tungstate and palladium nitrate dihydrate (5 g in total) as cocatalyst components according to a molar ratio of Mo to W to Pd of 60 to 150 to 1, adding a proper amount of deionized water, uniformly stirring, adding the active component precursor and carrier mixed solution, and stirring for 24 hours to obtain a catalyst coating mixed solution;
(5) transferring the catalyst coating mixed solution obtained by the scheme to a ball mill, and performing ball milling for 48 hours to obtain catalyst coating slurry;
(6) soaking the honeycomb ceramic in the catalyst coating slurry for 15min, and blowing the surface of the honeycomb ceramic by high-pressure air after uniform mixing;
(7) drying the honeycomb ceramic coated with the catalyst coating for 8 hours at 120 ℃ in an air drying oven;
(8) and (3) calcining the dried honeycomb ceramic at the high temperature of 550 ℃ for 5 hours to obtain the molded industrial denitration catalyst, wherein the catalyst coating accounts for 14% of the total mass of the catalyst.
Medium-high temperature NO-containing device for simulating discharge of coal bed gas power plant in SCR denitration experimentxAnd (3) removing waste gas:
in the denitration system, NOxThe inlet volume concentration is 1000ppm, the volume concentration of the reducing agent ammonia is 1000ppm, the volume concentration of the oxygen is 5 percent, the balance gas is nitrogen, and the space velocity is designed to be 10000h-1. The prepared catalyst has NO at 400-600 deg.cxThe outlet volume concentration is less than 50ppm, the denitration efficiency is higher than 95%, and the catalytic denitration efficiency of the catalyst is optimal at 500 ℃ and is 99%. After 500h durability test, the activity of the catalyst remained stable.
Example 4
(1) Weighing 25g of mesoporous silica molecular sieve and 10g of coated alumina, mixing, adding a proper amount of deionized water, and uniformly stirring to obtain a carrier solution;
(2) weighing 5g of a mixture of cerium nitrate hexahydrate and ferric nitrate nonahydrate at a molar ratio of Ce to Fe being 1:1, adding a proper amount of deionized water, and stirring until the mixture is completely dissolved to obtain an active component precursor solution;
(3) mixing the active component precursor solution with the carrier solution, and stirring for 1 h;
(4) weighing a proper amount of ammonium molybdate tetrahydrate, ammonium tungstate and palladium nitrate dihydrate (5 g in total) as cocatalyst components according to a molar ratio of Mo to W to Pd of 80 to 200 to 1, adding a proper amount of deionized water, uniformly stirring, adding the active component precursor and carrier mixed solution, and stirring for 24 hours to obtain a catalyst coating mixed solution;
(5) transferring the catalyst coating mixed solution obtained by the scheme to a ball mill, and carrying out ball milling for 72h to obtain catalyst coating slurry;
(6) soaking the honeycomb ceramic in the catalyst coating slurry for 20min, and blowing the surface of the honeycomb ceramic by high-pressure air after uniform mixing;
(7) drying the honeycomb ceramic coated with the catalyst coating for 8 hours at 120 ℃ in an air drying oven;
(8) and (3) calcining the dried honeycomb ceramic at the high temperature of 550 ℃ for 5 hours to obtain the formed industrial denitration catalyst, wherein the catalyst coating accounts for 15% of the total mass of the catalyst.
Medium-high temperature NO-containing device for simulating discharge of coal bed gas power plant in SCR denitration experimentxAnd (3) removing waste gas:
in the denitration system, NOxThe inlet volume concentration is 1000ppm, the volume concentration of the reducing agent ammonia is 1000ppm, the volume concentration of the oxygen is 5 percent, the balance gas is nitrogen, and the space velocity is designed to be 10000h-1. The prepared catalyst has NO at 400-600 deg.cxThe outlet volume concentration is less than 80ppm, the denitration efficiency is higher than 92%, and the catalytic denitration efficiency of the catalyst is the best 96% at 600 ℃. After 500h durability test, the activity of the catalyst remained stable.
Comparative example 1
The catalyst was tested for denitration performance and high temperature stability with reference to a common commercial vanadium titanium based denitration catalyst used in literature (warfarin, chenghua, wejingle, huangbi pure, raney bright, vanadium titanium based SCR denitration catalyst deactivation cause analysis [ J ]. thermal power generation, 2014,43(01): 90-95).
When the temperature is lower than 400 ℃, the commercial vanadium-titanium based catalyst has better thermal stability, but after 450 ℃, the thermal weight loss degree of the commercial vanadium-titanium based catalyst is very fast, and the denitration performance is obviously reduced; in addition, the specific surface area, pore channels and total pore volume of the commercial vanadium titanium-based catalyst after durability test are obviously reduced, and the performance of the catalyst is influenced.
In comparison with examples 1 to 4 of the present invention, in the denitration system, NOxThe inlet volume concentration is 1000ppm, the volume concentration of the reducing agent ammonia is 1000ppm, the volume concentration of the oxygen is 5 percent, the balance gas is nitrogen, and the space velocity is designed to be 10000h-1. Each catalyst prepared in examples 1 to 4 had NO at 400 ℃ to 600 ℃xThe outlet volume concentration is less than 100ppm, the denitration efficiency is higher than 90%, and the catalytic denitration efficiency of the catalyst prepared in example 3 is the best at 500 ℃, and is 99%. After 500h durability test, the activity of the catalyst remained stable. In the medium-high temperature section, the performance and the thermal stability of the denitration catalyst obtained in each embodiment are obviously superior to those of a commercial denitration catalyst, and the denitration catalyst is a very potential denitration catalyst for medium-high temperature flue gas discharged by a coal bed gas power plant.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (8)
1. A preparation method of a medium-high temperature flue gas denitration catalyst is characterized by comprising the following steps:
(1) weighing a proper amount of mesoporous silica molecular sieve and coated alumina, mixing, adding a proper amount of deionized water, and uniformly stirring to obtain a carrier solution, wherein the mesoporous silica molecular sieve and the coated alumina account for 20-35% of the carrier solution by mass percent;
(2) weighing a proper amount of an iron element precursor compound or/and a cerium element precursor compound, adding a proper amount of deionized water, and stirring until the mixture is completely dissolved to obtain an active component precursor solution, wherein the iron element precursor compound or/and the cerium element precursor compound account for 5% of the active component precursor solution in percentage by mass;
(3) mixing the active component precursor solution with the carrier solution, and stirring for 1 h;
(4) weighing a proper amount of a molybdenum element precursor compound, a tungsten element precursor compound and a palladium element precursor compound, adding a proper amount of deionized water, uniformly stirring, adding the mixed solution obtained in the step (3), and stirring for 24 hours to obtain a catalyst coating mixed solution, wherein the total mass of the molybdenum element precursor compound, the tungsten element precursor compound and the palladium element precursor compound accounts for 5% of the mass of the catalyst coating mixed solution obtained in the step (4);
(5) transferring the catalyst coating mixed solution obtained in the step (4) to a ball mill, and performing ball milling for 24-72 h to obtain catalyst coating slurry;
(6) dip-coating the blank honeycomb ceramic in the catalyst coating slurry for 5-20 min, and blowing the surface of the honeycomb ceramic by high-pressure air after uniform mixing;
(7) drying the honeycomb ceramic coated with the catalyst coating for 8 hours at 120 ℃ in an air drying oven;
(8) and calcining the dried honeycomb ceramic at the high temperature of 550 ℃ for 5 hours to obtain the molded industrial denitration catalyst.
2. The preparation method of the medium-high temperature flue gas denitration catalyst according to claim 1, wherein the pore size of the mesoporous silica molecular sieve selected in the step (1) is 8nm to 30 nm.
3. The preparation method of the medium-high temperature flue gas denitration catalyst according to claim 1, wherein the iron element precursor compound or/and the cerium element precursor compound selected in the step (2) is/are ferric nitrate nonahydrate, and the cerium element precursor compound is cerium nitrate hexahydrate.
4. The preparation method of the medium-high temperature flue gas denitration catalyst according to claim 1, wherein the molybdenum element precursor compound selected in the step (3) is ammonium molybdate tetrahydrate, the tungsten element precursor compound is ammonium tungstate, and the palladium element precursor compound is palladium nitrate.
5. The preparation method of the medium-high temperature flue gas denitration catalyst according to claim 1, wherein the molar ratio of molybdenum element, tungsten element and palladium element of the molybdenum element precursor compound, the tungsten element precursor compound and the palladium element precursor compound in the step (4) is (20-80): (50-200): 1.
6. The preparation method of the medium-high temperature flue gas denitration catalyst according to claim 1, wherein the coating amount calculation method of the catalyst is as follows: w ═ m1-m0)/m0X 100%, W is the coating amount of the catalyst, m0The mass (in g) of the blank honeycomb ceramics before the catalyst coating is described as m1The catalyst coating amount is 8 to 15% by mass of the honeycomb ceramic after coating the catalyst and firing.
7. The application of the denitration catalyst obtained by the preparation method according to any one of claims 1 to 6 in denitration of medium-high temperature flue gas emitted by a coal bed gas power plant is characterized in that in treatment of waste gas of the coal bed gas power plant, the denitration catalyst is added into an SCR denitration device for nitrogen oxide treatment.
8. The application of the denitration catalyst according to claim 7 in denitration of medium-high temperature flue gas discharged by a coal bed gas power plant, characterized in that NO is contained at a high temperature of 400-600 ℃xIn the denitration reaction of the flue gas, NO is introducedxAmmonia gas as reducing agent with the same concentration, NOxThe removal rate is stabilized at more than 90%, and the high-temperature stability is excellent.
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