CN112717921A - SCR denitration catalyst and preparation process thereof - Google Patents
SCR denitration catalyst and preparation process thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000003756 stirring Methods 0.000 claims abstract description 47
- 238000000498 ball milling Methods 0.000 claims abstract description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000012153 distilled water Substances 0.000 claims abstract description 29
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000314 lubricant Substances 0.000 claims abstract description 27
- 239000004014 plasticizer Substances 0.000 claims abstract description 27
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920001131 Pulp (paper) Polymers 0.000 claims abstract description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 21
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 21
- 239000003365 glass fiber Substances 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 14
- 230000004913 activation Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 239000010431 corundum Substances 0.000 claims description 7
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 claims 1
- 238000005299 abrasion Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- -1 and simultaneously Chemical compound 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—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
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
The invention relates to an SCR denitration catalyst. The invention also relates to a preparation process of the SCR denitration catalyst, which mainly comprises the following steps: (1) putting anatase type titanium dioxide, tungsten trioxide and silicon powder into a planetary ball mill for ball milling for 15-20 minutes, introducing high-temperature steam at 100-120 ℃ into the planetary ball mill, and performing ball milling and activation to prepare a carrier; (2) sequentially adding a lubricant, distilled water, ammonia water, an ammonium metavanadate water solution, a plasticizer, a binder, wood pulp and glass fiber into the carrier, feeding the mixture into a stirrer, adding the distilled water while stirring, and uniformly stirring to prepare slurry; (3) introducing oxygen at 350-400 ℃ and calcining for 1 hour, and then calcining for 3 hours at 450-500 ℃ in nitrogen atmosphere to obtain the SCR denitration catalyst. According to the SCR denitration catalyst and the preparation process thereof, the prepared catalyst has good activity and abrasion resistance and long service life.
Description
Technical Field
The invention relates to the technical field of denitration catalysts, in particular to an SCR denitration catalyst and a preparation process thereof.
Background
Nitrogen oxides are one of main pollution sources of air pollution, and are also important factors directly causing haze weather, ozone damage and air pollution in various parts of China, nitrogen oxides in industrial tail gas are main sources of nitrogen oxides in the atmosphere, such as flue gas of coal-fired power plants, glass kilns, cement kilns, coke ovens and the like, and selective catalytic reduction (NH3-SCR) technology taking ammonia as a reducing agent is mostly used in the tail gas denitration technology of the coal-fired power plants at present. However, the temperature of industrial exhaust gas such as industrial boiler exhaust gas and coke oven flue gas is mostly below 300 ℃, so the denitration catalyst for coal-fired power plants is not suitable for the medium-low temperature flue gas, because the denitration efficiency of the vanadium-titanium catalyst used is low under the condition of medium-low temperature flue gas, and simultaneously, sulfate substances formed by SOx in the flue gas are adsorbed on the surface of the catalyst and are difficult to decompose, thereby occupying the active site of the catalyst and causing the catalyst to be poisoned and inactivated.
Chinese patent with publication number CN107262119B discloses a medium-low temperature sulfur-tolerant flue gas denitration catalyst and a preparation method thereof. The catalyst comprises a carrier, an active component and an auxiliary agent, wherein the carrier is anatase titanium dioxide, the active component is a salt or an oxide of Mn, and the auxiliary agent is a salt, an oxide or a simple substance of Te and Pt. The denitration catalyst can achieve the denitration efficiency of more than 80 percent in the whole temperature range of 150-400 ℃ under the condition of no SO2, and has excellent low-temperature sulfur resistance. Under the conditions of the temperature of 150 ℃ and 400 ℃ and the content of SO2 not higher than 300ppm, the denitration efficiency is not attenuated by more than 1% within 20h, and the attenuation is not continued. Moreover, after the SO2 content is reduced, the denitration efficiency can be raised back to the original level, i.e., the denitration catalyst of the present invention is not permanently affected by sulfur. However, the denitration catalyst cannot satisfy the use condition with a large temperature fluctuation range, and can only exert high performance within a certain temperature range.
In view of the above problems, it is desirable to provide an SCR denitration catalyst and a preparation process thereof.
Disclosure of Invention
The invention aims to provide an SCR denitration catalyst and a preparation process thereof, and aims to overcome the defects of the prior art.
In order to achieve the aim of the invention, the SCR denitration catalyst comprises the following components in percentage by weight: 35-45 parts of anatase titanium dioxide, 5-6 parts of tungsten trioxide, 3-4 parts of silicon powder, 9-14 parts of ammonia water, 17-35 parts of distilled water, 11-13 parts of an ammonium metavanadate aqueous solution, 3-4 parts of a lubricant, 3-4 parts of a plasticizer, 5-8 parts of a binder, 1-3 parts of wood pulp and 5-7 parts of glass fiber.
Preferably, the lubricant is glycerol or triethanolamine, the plasticizer is terephthalic acid or dioctyl phthalate, and the adhesive is polyvinyl alcohol.
A preparation process of an SCR denitration catalyst mainly comprises the following steps:
(1) putting anatase type titanium dioxide, tungsten trioxide and silicon powder into a planetary ball mill for ball milling for 15-20 minutes, introducing high-temperature steam at 100-120 ℃ into the planetary ball mill, and performing ball milling and activation to prepare a carrier;
(2) sequentially adding a lubricant, distilled water, ammonia water, an ammonium metavanadate water solution, a plasticizer, a binder, wood pulp and glass fiber into the carrier, feeding the mixture into a stirrer, adding the distilled water while stirring, and uniformly stirring to prepare slurry;
(3) introducing oxygen at 350-400 ℃ and calcining for 1 hour, and then calcining for 3 hours at 450-500 ℃ in nitrogen atmosphere to obtain the SCR denitration catalyst.
Preferably, in the step (2), firstly, adding the lubricant, and continuing stirring, wherein the stirring speed is 500-600 r/min, and the stirring time is 10-15 min; then adding distilled water, and adjusting the water content to 36-40%; then adding ammonia water to adjust the pH value to 8-9, wherein the system temperature is 50-60 ℃; and finally, sequentially adding an ammonium metavanadate aqueous solution, a plasticizer, a binder, wood pulp and glass fiber, continuously stirring at the stirring speed of 90-110 r/min for 8min, adjusting the water content to 40-45% and the system temperature to 50-55 ℃.
Preferably, in step (2), the water content of the prepared slurry is below 20%.
Preferably, in the step (3), oxygen is introduced at 380 ℃ for calcination for 1 hour, and then calcination is performed at 475 ℃ for 3 hours in a nitrogen atmosphere, so as to obtain the SCR denitration catalyst.
Preferably, in the step (1), the ball milling balls used in the ball mill pot are corundum balls during the ball milling.
Preferably, the specific surface area of the prepared SCR denitration catalyst is 60-170 m2/g。
Compared with the prior art, the SCR denitration catalyst and the preparation process thereof have the following advantages:
(1) the preparation process is simple, the prepared catalyst has good activity and abrasion resistance, the service life is long, and the production cost of the catalyst is reduced;
(2) the catalyst provided by the invention can adapt to the operation condition with larger temperature fluctuation, and reduces the extra equipment investment and software investment cost;
(3) the specific surface area is large, which is beneficial to improving the internal micropores of the catalyst;
(4) in the mixing process, a sectional stirring mode is adopted, and the curing temperature, the water content and the PH value of the mixed material are controlled, so that the plasticity of the mixed material is ensured.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
The SCR denitration catalyst comprises the following components in percentage by weight: the composite material comprises 35 parts of anatase titanium dioxide, 5 parts of tungsten trioxide, 3 parts of silicon powder, 11 parts of ammonia water, 17 parts of distilled water, 11 parts of an ammonium metavanadate water solution, 3 parts of a lubricant, 3 parts of a plasticizer, 5 parts of a binder, 1 part of wood pulp and 6 parts of glass fiber.
Wherein the lubricant is glycerol or triethanolamine, the plasticizer is terephthalic acid or dioctyl phthalate, and the adhesive is polyvinyl alcohol.
A preparation process of an SCR denitration catalyst mainly comprises the following steps:
(1) putting anatase type titanium dioxide, tungsten trioxide and silicon powder into a planetary ball mill for ball milling for 20 minutes, introducing high-temperature steam at 120 ℃ into the planetary ball mill, and performing ball milling and activation to prepare a carrier;
(2) sequentially adding a lubricant, distilled water, ammonia water, an ammonium metavanadate water solution, a plasticizer, a binder, wood pulp and glass fiber into the carrier, feeding the mixture into a stirrer, adding the distilled water while stirring, and uniformly stirring to prepare slurry;
(3) introducing oxygen at 350 ℃ and calcining for 1 hour, and then calcining for 3 hours at 500 ℃ in a nitrogen atmosphere to obtain the SCR denitration catalyst.
Wherein, in the step (2), firstly, adding the lubricant, and continuing stirring at the stirring speed of 600r/min for 10 min; then adding distilled water, and adjusting the water content to 36%; then adding ammonia water to adjust the pH value to 9, wherein the system temperature is 50 ℃; and finally, sequentially adding an ammonium metavanadate aqueous solution, a plasticizer, a binder, wood pulp and glass fiber, continuously stirring at the stirring speed of 90r/min for 8min, adjusting the water content to 40% and controlling the system temperature to 50 ℃.
Wherein, in the step (2), the water content of the prepared slurry is below 20 percent.
And (3) introducing oxygen at 380 ℃ to calcine for 1 hour, and then calcining for 3 hours at 475 ℃ in a nitrogen atmosphere to obtain the SCR denitration catalyst.
In the step (1), in the ball milling process, the ball milling balls used in the ball milling tank are corundum balls.
Example 2
The SCR denitration catalyst comprises the following components in percentage by weight: anatase titanium dioxide 36, tungsten trioxide 6, silicon powder 4, ammonia water 10, distilled water 17, ammonium metavanadate water solution 10, lubricant 3, plasticizer 3, binder 5, wood pulp 3 and glass fiber 5.
Wherein the lubricant is glycerol or triethanolamine, the plasticizer is terephthalic acid or dioctyl phthalate, and the adhesive is polyvinyl alcohol.
A preparation process of an SCR denitration catalyst mainly comprises the following steps:
(1) putting anatase type titanium dioxide, tungsten trioxide and silicon powder into a planetary ball mill for ball milling for 15 minutes, introducing high-temperature steam at 100 ℃ into the planetary ball mill, and performing ball milling and activation to prepare a carrier;
(2) sequentially adding a lubricant, distilled water, ammonia water, an ammonium metavanadate water solution, a plasticizer, a binder, wood pulp and glass fiber into the carrier, feeding the mixture into a stirrer, adding the distilled water while stirring, and uniformly stirring to prepare slurry;
(3) introducing oxygen at 350 ℃ and calcining for 1 hour, and then calcining for 3 hours at 450 ℃ in a nitrogen atmosphere to obtain the SCR denitration catalyst.
Wherein, in the step (2), firstly, adding the lubricant, and continuing stirring at the stirring speed of 500r/min for 10 min; then adding distilled water, and adjusting the water content to 36%; then adding ammonia water to adjust the pH value to 8, wherein the system temperature is 50 ℃; and finally, sequentially adding an ammonium metavanadate aqueous solution, a plasticizer, a binder, wood pulp and glass fiber, continuously stirring at the stirring speed of 90r/min for 8min, adjusting the water content to 40% and controlling the system temperature to 50 ℃.
Wherein, in the step (2), the water content of the prepared slurry is below 20 percent.
And (3) introducing oxygen at 380 ℃ to calcine for 1 hour, and then calcining for 3 hours at 475 ℃ in a nitrogen atmosphere to obtain the SCR denitration catalyst.
In the step (1), in the ball milling process, the ball milling balls used in the ball milling tank are corundum balls.
Example 3
The SCR denitration catalyst comprises the following components in percentage by weight: the composite material comprises 38 parts of anatase titanium dioxide, 5 parts of tungsten trioxide, 3 parts of silicon powder, 10 parts of ammonia water, 18 parts of distilled water, 12 parts of an ammonium metavanadate aqueous solution, 3 parts of a lubricant, 3 parts of a plasticizer, 5 parts of a binder, 1 part of wood pulp and 5 parts of glass fiber.
Wherein the lubricant is glycerol or triethanolamine, the plasticizer is terephthalic acid or dioctyl phthalate, and the adhesive is polyvinyl alcohol.
A preparation process of an SCR denitration catalyst mainly comprises the following steps:
(1) putting anatase type titanium dioxide, tungsten trioxide and silicon powder into a planetary ball mill for ball milling for 15 minutes, introducing high-temperature steam at 100 ℃ into the planetary ball mill, and performing ball milling and activation to prepare a carrier;
(2) sequentially adding a lubricant, distilled water, ammonia water, an ammonium metavanadate water solution, a plasticizer, a binder, wood pulp and glass fiber into the carrier, feeding the mixture into a stirrer, adding the distilled water while stirring, and uniformly stirring to prepare slurry;
(3) introducing oxygen at 350 ℃ and calcining for 1 hour, and then calcining for 3 hours at 450 ℃ in a nitrogen atmosphere to obtain the SCR denitration catalyst.
Wherein, in the step (2), firstly, adding the lubricant, and continuing stirring at the stirring speed of 500r/min for 10 min; then adding distilled water, and adjusting the water content to 36%; then adding ammonia water to adjust the pH value to 8, wherein the system temperature is 50 ℃; and finally, sequentially adding an ammonium metavanadate aqueous solution, a plasticizer, a binder, wood pulp and glass fiber, continuously stirring at the stirring speed of 90r/min for 8min, adjusting the water content to 40% and controlling the system temperature to 55 ℃.
Wherein, in the step (2), the water content of the prepared slurry is below 20 percent.
And (3) introducing oxygen at 380 ℃ to calcine for 1 hour, and then calcining for 3 hours at 475 ℃ in a nitrogen atmosphere to obtain the SCR denitration catalyst.
In the step (1), in the ball milling process, the ball milling balls used in the ball milling tank are corundum balls.
Example 4
The SCR denitration catalyst comprises the following components in percentage by weight: the composite material comprises 38 percent of anatase titanium dioxide, 5 percent of tungsten trioxide, 3 percent of silicon powder, 9 percent of ammonia water, 17 percent of distilled water, 11 percent of ammonium metavanadate water solution, 3 percent of lubricant, 3 percent of plasticizer, 5 percent of binder, 1 percent of wood pulp and 5 percent of glass fiber.
Wherein the lubricant is glycerol or triethanolamine, the plasticizer is terephthalic acid or dioctyl phthalate, and the adhesive is polyvinyl alcohol.
A preparation process of an SCR denitration catalyst mainly comprises the following steps:
(1) putting anatase type titanium dioxide, tungsten trioxide and silicon powder into a planetary ball mill for ball milling for 15 minutes, introducing high-temperature steam at 100 ℃ into the planetary ball mill, and performing ball milling and activation to prepare a carrier;
(2) sequentially adding a lubricant, distilled water, ammonia water, an ammonium metavanadate water solution, a plasticizer, a binder, wood pulp and glass fiber into the carrier, feeding the mixture into a stirrer, adding the distilled water while stirring, and uniformly stirring to prepare slurry;
(3) and introducing oxygen at 400 ℃ to calcine for 1 hour, and then calcining for 3 hours at 500 ℃ in a nitrogen atmosphere to obtain the SCR denitration catalyst.
Wherein, in the step (2), firstly, adding the lubricant, and continuing stirring at the stirring speed of 500-600 r/min for 10 min; then adding distilled water, and adjusting the water content to 38%; then adding ammonia water to adjust the pH value to 9, wherein the system temperature is 60 ℃; and finally, sequentially adding an ammonium metavanadate aqueous solution, a plasticizer, a binder, wood pulp and glass fiber, continuously stirring at the stirring speed of 100r/min for 8min, adjusting the water content to 45%, and controlling the system temperature to 55 ℃.
Wherein, in the step (2), the water content of the prepared slurry is below 20 percent.
And (3) introducing oxygen at 380 ℃ to calcine for 1 hour, and then calcining for 3 hours at 475 ℃ in a nitrogen atmosphere to obtain the SCR denitration catalyst.
In the step (1), in the ball milling process, the ball milling balls used in the ball milling tank are corundum balls.
Wherein the specific surface area of the prepared SCR denitration catalyst is 150m2/g。
A preparation process of an SCR denitration catalyst mainly comprises the following steps:
(1) putting anatase type titanium dioxide, tungsten trioxide and silicon powder into a planetary ball mill for ball milling for 15 minutes, introducing high-temperature steam at 100 ℃ into the planetary ball mill, and performing ball milling and activation to prepare a carrier;
(2) sequentially adding a lubricant, distilled water, ammonia water, an ammonium metavanadate water solution, a plasticizer, a binder, wood pulp and glass fiber into the carrier, feeding the mixture into a stirrer, adding the distilled water while stirring, and uniformly stirring to prepare slurry;
(3) introducing oxygen at 350 ℃ and calcining for 1 hour, and then calcining for 3 hours at 450 ℃ in a nitrogen atmosphere to obtain the SCR denitration catalyst.
Wherein, in the step (2), firstly, adding the lubricant, and continuing stirring at the stirring speed of 500r/min for 10 min; then adding distilled water, and adjusting the water content to 36%; then adding ammonia water to adjust the pH value to 8, wherein the system temperature is 50 ℃; and finally, sequentially adding an ammonium metavanadate aqueous solution, a plasticizer, a binder, wood pulp and glass fiber, continuously stirring at the stirring speed of 90r/min for 8min, adjusting the water content to 40% and controlling the system temperature to 50 ℃.
Wherein, in the step (2), the water content of the prepared slurry is below 20 percent.
And (3) introducing oxygen at 380 ℃ to calcine for 1 hour, and then calcining for 3 hours at 475 ℃ in a nitrogen atmosphere to obtain the SCR denitration catalyst.
In the step (1), in the ball milling process, the ball milling balls used in the ball milling tank are corundum balls.
Table 1 is a table comparing the evaluation data of SCR denitration catalysts in examples and the prior art
It can be seen that the catalysts prepared in examples 1, 2, 3 and 4 have better denitration efficiency and SO than the conventional SCR denitration catalyst in the prior art2/SO3The conversion rate was slightly improved.
In the description herein, it will be understood that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used merely to facilitate the description of the present patent application and to simplify the description, and do not indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the present patent application.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present application, "a plurality" means at least two, e.g., two, three, etc., unless explicitly specified otherwise.
In this specification, unless expressly stated or limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can include, for example, fixed connections, removable connections, or integral combinations thereof; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable manner, unless otherwise specifically limited. The specific meanings of the above terms in the present specification can be understood by those of ordinary skill in the art as appropriate.
In this specification, unless explicitly stated or limited otherwise, a first feature may be "on" or "under" a second feature such that the first and second features are in direct contact, or the first and second features are in indirect contact via an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or obliquely above the second feature, or may simply mean that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it should be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that changes, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (8)
1. The SCR denitration catalyst is characterized by comprising the following components in percentage by weight: 35-45 parts of anatase titanium dioxide, 5-6 parts of tungsten trioxide, 3-4 parts of silicon powder, 9-14 parts of ammonia water, 17-35 parts of distilled water, 11-13 parts of an ammonium metavanadate aqueous solution, 3-4 parts of a lubricant, 3-4 parts of a plasticizer, 5-8 parts of a binder, 1-3 parts of wood pulp and 5-7 parts of glass fiber.
2. The SCR denitration catalyst of claim 1, wherein the lubricant is glycerin or triethanolamine, the plasticizer is collaphthalene dicarboxylic acid or dioctyl-phthalate, and the binder is polyvinyl alcohol.
3. The preparation process of the SCR denitration catalyst according to claim 1, which mainly comprises the following steps:
(1) putting anatase type titanium dioxide, tungsten trioxide and silicon powder into a planetary ball mill for ball milling for 15-20 minutes, introducing high-temperature steam at 100-120 ℃ into the planetary ball mill, and performing ball milling and activation to prepare a carrier;
(2) sequentially adding a lubricant, distilled water, ammonia water, an ammonium metavanadate water solution, a plasticizer, a binder, wood pulp and glass fiber into the carrier, feeding the mixture into a stirrer, adding the distilled water while stirring, and uniformly stirring to prepare slurry;
(3) introducing oxygen at 350-400 ℃ and calcining for 1 hour, and then calcining for 3 hours at 450-500 ℃ in nitrogen atmosphere to obtain the SCR denitration catalyst.
4. The SCR denitration catalyst and the preparation process thereof as claimed in claim 3, wherein in the step (2), the lubricant is added first, and the stirring is continued, wherein the stirring speed is 500-600 r/min, and the stirring time is 10-15 min; then adding distilled water, and adjusting the water content to 36-40%; then adding ammonia water to adjust the pH value to 8-9, wherein the system temperature is 50-60 ℃; and finally, sequentially adding an ammonium metavanadate aqueous solution, a plasticizer, a binder, wood pulp and glass fiber, continuously stirring at the stirring speed of 90-110 r/min for 8min, adjusting the water content to 40-45% and the system temperature to 50-55 ℃.
5. The SCR denitration catalyst and the process of claim 4, wherein the water content of the slurry obtained in step (2) is below 20%.
6. The SCR denitration catalyst and the preparation process thereof according to claim 3, wherein in the step (3), oxygen is introduced at 380 ℃ for calcination for 1 hour, and then calcination is performed at 475 ℃ for 3 hours in a nitrogen atmosphere, so as to obtain the SCR denitration catalyst.
7. The SCR denitration catalyst and the process of claim 3, wherein in the step (1), the ball milling balls used in the ball mill pot are corundum balls during the ball milling process.
8. The SCR denitration catalyst and the preparation process thereof as claimed in any one of claims 3 to 7, wherein the specific surface area of the prepared SCR denitration catalyst is 60 to 170m2/g。
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