CN106362732A - Denitration and demercuration catalyst - Google Patents

Denitration and demercuration catalyst Download PDF

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Publication number
CN106362732A
CN106362732A CN201610750324.6A CN201610750324A CN106362732A CN 106362732 A CN106362732 A CN 106362732A CN 201610750324 A CN201610750324 A CN 201610750324A CN 106362732 A CN106362732 A CN 106362732A
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catalyst
denitration demercuration
demercuration catalyst
denitration
base material
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CN106362732B (en
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赵艳军
杨公平
杨霞
任骞
牟婧
牟海波
韩永波
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Shandong Hairun Environment Protection Technology Co Ltd
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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
    • 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
    • B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
    • 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
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • B01D2255/402—Perovskites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/65—Catalysts not containing noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a denitration and demercuration catalyst and belongs to the field of environment-friendly catalysts. Components of the catalyst form a Mo-V-W/TiO2-Al2O3 system, the functions of denitration and demercuration are achieved at the same time under the effect of the active components Mo, V and W and the carrier TiO2-Al2O3, the structure of tail gas filtering and exhausting equipment can be effectively simplified, and environmental protection cost is reduced. In addition, the catalyst has high dust interference resisting capacity, and still can exert maximum filtering performance on the basis that no frequent halt is needed for removal of accumulated dust, and the catalyst is uniform in aging speed, high in filtering-out capacity and long in service life.

Description

Denitration demercuration catalyst
Technical field
The present invention relates to a kind of denitration demercuration catalyst and preparation method thereof, belong to the catalyst neck of filtering dusty gass Domain.
Background technology
With China's expanding economy, the quantity of China's coal energy-output ratio and motor vehicles increases considerably, and causes sky In gas, various pollutant loads also rise rapid.Through the effort of decades, China is controlling dust and sulfur dioxide dirty Dye aspect has obtained certain success, but the pollution of hydrargyrum and nitrogen oxides is not yet controlled.Therefore, how effectively to control The discharge of hydrargyrum processed and nitrogen oxides becomes the focus of current field of Environment Protection.
Traditional catalyst, hydrargyrum or nitrogen oxides can only be carried out unidirectional filter, lead to filter mixed flue gas when, required Equipment construction is complicated, increases production cost.And, traditional catalyst relies on honeycombed catalyst to carry out filtration operation, this The structure of catalyst is simple, but once there being bulky grain thing to enter catalytic inner, whole piece honeycomb bar hole will occur to block it is impossible to Carry out normal filtration reaction.Catalyst operation in high pollution environment, laying dust is unavoidable, how to clear up without frequent shutdown On the basis of dust stratification, remain to make it play maximum strainability, be the difficult problem that those skilled in the art need to solve.
The present invention proposes a kind of denitration demercuration catalyst, can filter hydrargyrum and nitrogen oxides, obtained catalyst valency simultaneously Lattice are low, and chemically and thermally carefully, activity is also higher for stability, and anti-poisoning performance is high.Additionally, the present invention possesses high antidusting interference Ability, on the basis of without frequent shutdown cleaning dust stratification, remains to play maximum strainability, makes the aging speed of catalyst Homogeneous, the ability that filters is strong and long service life.
Content of the invention
For solve the problems, such as high temperature catalyst actually used during run into, the invention provides a kind of denitration demercuration is urged Agent, can filter hydrargyrum and nitrogen oxides simultaneously, and obtained catalyst price is low, and chemically and thermally carefully, activity is also higher for stability, And anti-poisoning performance is high.Additionally, the present invention possesses high antidusting interference performance, on the basis clearing up dust stratification without frequent shutdown On, remain to play maximum strainability, make the aging speed of catalyst homogeneous, the ability that filters is strong and long service life.
The present invention is achieved by the following technical solutions:
It is characterised in that including base material and active component, the addition of described base material is 60-70 to a kind of denitration demercuration catalyst Part；The addition of active component is 0.3-3 part；Base material includes titanium dioxide, silica flour and gama-alumina；Dioxy in described base material Changing titanium, silica flour and gama-alumina is 5:2:3 in mass ratio；Active component is vanadic anhydride.
Also include auxiliary agent, the addition of described auxiliary agent is 20-30 part；Auxiliary agent includes Tungstic anhydride. and molybdenum trioxide；Tungstic anhydride. Mass ratio with molybdenum trioxide is 1:1.
Also include lubricating binding agent, the addition of described lubrication binding agent is 2-8 part；Lubrication binding agent include bentonite and Methyl-silicone oil；The mass ratio of bentonite and methyl-silicone oil is 2:1.
Also include plasticizer, the addition of described plasticizer is 3-5 part；Plasticizer includes hydroxymethyl cellulose and diatom Mud；The mass ratio of above-mentioned hydroxymethyl cellulose and diatom ooze is 3:2.
A kind of denitration demercuration catalyst of the present invention, including following preparation process:
1) by base material in 80-120 DEG C of vacuum oven 6-8h, it is cooled to 30-60 DEG C, obtain pretreating substrates；
2) weigh active component and auxiliary agent, add mixing kettle, 20-25l deionized water is gradually added into mixing kettle, and open and stir Mix, after the speed stirring 2-3h of 100-200r/min, add pretreating substrates in step (1), continue stirring 2-3h；
3) by the prepared thing of step (2), put into Muffle furnace, calcine 4-6h at 500-700 DEG C；
4) the prepared thing of step (3) is added lubrication binding agent and plasticizer to be kneaded, until by material mixing uniformly；
5) material out by mixing, after ripening 24-48h, is added in filtration pre-extruded and extrudes, be filtered to remove miscellaneous in material Matter；
6) material after pre-extruded will be filtered, by mould integral extrusion molding, and the length according to regulation, above-mentioned finished product is entered Row cuts into segmented body, carries out hemispherical concave machining at the two ends of each segmented body, makes the two ends of each segmented body Form the hemisphere face of indent；
7) cross-linked spheres catalyst, i.e. finished product are embedded between two adjacent segmented body.
The preparation method of the cross-linked spheres catalyst described in step 7) is that the foaming metal for 1-3mm is processed into by aperture Spherical, with electrophoretic deposition foaming metal in the hole plating one layer function promoter material, the thickness of described function additive material Less than 0.5mm.
Described foaming metal is nickel foam.
Described function additive material is obtained by following raw materials, and described number is weight portion:
Gama-alumina 20-30 part；
Vanadic anhydride 1-3 part；
Tungstic anhydride. 10-15 part；
Molybdenum trioxide 10-12 part；
Brium carbonate or Calcium Carbonate 2-8 part；
Diatom ooze 3-5 part；
Tween-60 1-3 part；
Dodecylbenzene sodium sulfonate 2-3 part；
Polytetrafluorethylepowder powder 4-7 part.
The present invention is had the beneficial effect that
1st, aluminium oxide and nano TiO 2 carrying body have higher specific surface area in itself, add pore creating material silicon on this basis Powder, can make base material have suitable pore structure and water absorption rate, can improve the surface area of carrier, be conducive to catalyst activity to become Dispersion, to improve activity and the life-span of catalyst.
2nd, form mo-v-w/tio between each group of catalyst is divided2-al2o3System, in active component mo, v, w and load Body tio2-al2o3In the presence of realize the function of denitration demercuration simultaneously, can effectively simplify the structure of tail gas filtering exhaust apparatus, fall Low environmental protection cost.
3rd, add rare earth oxide can improve the thermostability of catalyst, play stable lattice structure and prevent volume contraction Dual function.
4th, embed cross-linked spheres catalyst between two adjacent cellular segmented body, cross-linked spheres catalyst is in synchronization The effect of high heat transfer and many siphunculus can be played while filtration.Out of stock demercuration catalyst is required in higher temperature strip Just can have high reaction activity, however, temperature when flue gas just gives off can not keep too long, with flue gas in catalysis under part Move in agent, temperature gradually lowers.And foam metal all has high heat conduction efficiency, at the beginning of flue gas discharge can be fully absorbed When the heat that carries, make catalyst front-end and back-end thermally equivalent, be conducive to improving the conversion ratio of out of stock demercuration.
Further, since catalyst operation in high dirt environment, once segmented body honeycomb hole is blocked, flue gas also may be used To enter in next adjacent sectional body from the many siphunculus road crossing cross-linked spheres catalyst, the blocking rate of filter opening is made to be greatly lowered.And And, flue gas movement locus in the catalyst itself are also uneven, and cross-linked spheres catalyst can also play dispersed flue gas Effect, can remain to make it play maximum strainability, extends catalyst on the basis of without frequent shutdown cleaning dust stratification Whole service life.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described, and specific embodiment does not limit the present invention.
A kind of denitration demercuration catalyst, including base material and active component, the addition of described base material is 60-70 part；Activity The addition of composition is 0.3-3 part；Base material includes titanium dioxide, silica flour and gama-alumina；Titanium dioxide, silicon in described base material Powder and gama-alumina are 5:2:3 in mass ratio；Active component is vanadic anhydride.
Also include auxiliary agent, the addition of described auxiliary agent is 20-30 part；Auxiliary agent includes Tungstic anhydride. and molybdenum trioxide；Tungstic anhydride. Mass ratio with molybdenum trioxide is 1:1.
Also include lubricating binding agent, the addition of described lubrication binding agent is 2-8 part；Lubrication binding agent include bentonite and Methyl-silicone oil；The mass ratio of bentonite and methyl-silicone oil is 2:1.
Also include plasticizer, the addition of described plasticizer is 3-5 part；Plasticizer includes hydroxymethyl cellulose and diatom Mud；The mass ratio of above-mentioned hydroxymethyl cellulose and diatom ooze is 3:2.
Each composition in a particular embodiment and consumption see table:
Composition Embodiment one Embodiment two Embodiment three
Base material 60 parts 65 parts 70 parts
Vanadic anhydride 0.3 part 1 part 3 parts
Auxiliary agent 20 parts 25 parts 30 parts
Lubrication binding agent 2 parts 6 parts 8 parts
Plasticizer 3 parts 4 parts 5 parts
A kind of denitration demercuration catalyst of the present invention, including following preparation process:
1) by base material in 80-120 DEG C of vacuum oven 6-8h, it is cooled to 30-60 DEG C, obtain pretreating substrates；
2) weigh active component and auxiliary agent, add mixing kettle, 20-25l deionized water is gradually added into mixing kettle, and open and stir Mix, after the speed stirring 2-3h of 100-200r/min, add pretreating substrates in step (1), continue stirring 2-3h；
3) by the prepared thing of step (2), put into Muffle furnace, calcine 4-6h at 500-700 DEG C；
4) the prepared thing of step (3) is added lubrication binding agent and plasticizer to be kneaded, until by material mixing uniformly；
5) material out by mixing, after ripening 24-48h, is added in filtration pre-extruded and extrudes, be filtered to remove miscellaneous in material Matter；
6) material after pre-extruded will be filtered, by mould integral extrusion molding, and the length according to regulation, above-mentioned finished product is entered Row cuts into segmented body, carries out hemispherical concave machining at the two ends of each segmented body, makes the two ends of each segmented body Form the hemisphere face of indent；
7) cross-linked spheres catalyst, i.e. finished product are embedded between two adjacent segmented body.
The preparation method of the cross-linked spheres catalyst described in step 7) is that the foaming metal for 1-3mm is processed into by aperture Spherical, with electrophoretic deposition foaming metal in the hole plating one layer function promoter material, the thickness of described function additive material Less than 0.5mm.
Described foaming metal is nickel foam.
Described function additive material is obtained by following raw materials, and described number is weight portion:
Gama-alumina 20-30 part；
Vanadic anhydride 1-3 part；
Tungstic anhydride. 10-15 part；
Molybdenum trioxide 10-12 part；
Brium carbonate or Calcium Carbonate 2-8 part；
Diatom ooze 3-5 part；
Tween-60 1-3 part；
Dodecylbenzene sodium sulfonate 2-3 part；
Polytetrafluorethylepowder powder 4-7 part.
Function additive material each composition in a particular embodiment and consumption see table:
Composition Embodiment one Embodiment two Embodiment three
Gama-alumina 20 parts 25 parts 30 parts
Vanadic anhydride 1 part 1.5 part 3 parts
Tungstic anhydride. 10 parts 13 parts 15 parts
Molybdenum trioxide 10 parts 11 parts 12 parts
Brium carbonate or Calcium Carbonate 2 parts 5 parts 8 parts
Diatom ooze 3 parts 4 parts 5 parts
Tween-60 1 part 1.5 part 3 parts
Dodecylbenzene sodium sulfonate 2 parts 2.5 part 3 parts
Polytetrafluorethylepowder powder 4 parts 5 parts 7 parts
The experimental result of above-described embodiment is as follows:
Laboratory sample Out of stock rate (%) Mercury removal rate (%)
Embodiment one 98 98
Embodiment two 98.1 97.5
Embodiment three 97.6 97.9
Above-mentioned the results show, the serviceability of the present invention is good, can effectively remove nitre and the hydrargyrum in flue gas, suitably in the industry cycle Advisor popularizes.

Claims (8)

1. it is characterised in that including base material and active component, the addition of described base material is 60-70 to a kind of denitration demercuration catalyst Part；The addition of active component is 0.3-3 part；Base material includes titanium dioxide, silica flour and gama-alumina；Dioxy in described base material Changing titanium, silica flour and gama-alumina is 5:2:3 in mass ratio；Active component is vanadic anhydride.
2. as claimed in claim 1 a kind of denitration demercuration catalyst it is characterised in that: also include auxiliary agent, the adding of described auxiliary agent Dosage is 20-30 part；Auxiliary agent includes Tungstic anhydride. and molybdenum trioxide；The mass ratio of Tungstic anhydride. and molybdenum trioxide is 1:1.
3. as claimed in claim 2 a kind of denitration demercuration catalyst it is characterised in that: also include lubricate binding agent, described profit The addition of sliding binding agent is 2-8 part；Lubrication binding agent includes bentonite and methyl-silicone oil；Bentonite and the quality of methyl-silicone oil Than for 2:1.
4. as claimed in claim 3 a kind of denitration demercuration catalyst it is characterised in that: also include plasticizer, described plasticizer Addition be 3-5 part；Plasticizer includes hydroxymethyl cellulose and diatom ooze；Above-mentioned hydroxymethyl cellulose and the quality of diatom ooze Than for 3:2.
5. as claimed in claim 4 a kind of denitration demercuration catalyst it is characterised in that include following preparation process:
1) by base material in 80-120 DEG C of vacuum oven 6-8h, it is cooled to 30-60 DEG C, obtain pretreating substrates；
2) weigh active component and auxiliary agent, add mixing kettle, 20-25l deionized water is gradually added into mixing kettle, and open and stir Mix, after the speed stirring 2-3h of 100-200r/min, add pretreating substrates in step (1), continue stirring 2-3h；
3) by the prepared thing of step (2), put into Muffle furnace, calcine 4-6h at 500-700 DEG C；
4) the prepared thing of step (3) is added lubrication binding agent and plasticizer to be kneaded, until by material mixing uniformly；
5) material out by mixing, after ripening 24-48h, is added in filtration pre-extruded and extrudes, be filtered to remove miscellaneous in material Matter；
6) material after pre-extruded will be filtered, by mould integral extrusion molding, and the length according to regulation, above-mentioned finished product is entered Row cuts into segmented body, carries out hemispherical concave machining at the two ends of each segmented body, makes the two ends of each segmented body Form the hemisphere face of indent；
7) cross-linked spheres catalyst, i.e. finished product are embedded between two adjacent segmented body.
6. as claimed in claim 5 a kind of denitration demercuration catalyst it is characterised in that: the cross-linked spheres described in step 7) are urged The preparation method of agent is the foaming metal processing globulate by aperture for 1-3mm, with electrophoretic deposition in the hole of foaming metal Interior plating one layer function promoter material, the thickness of described function additive material is less than 0.5mm.
7. as claimed in claim 6 a kind of denitration demercuration catalyst it is characterised in that: described foaming metal be nickel foam.
8. as claimed in claim 7 a kind of denitration demercuration catalyst it is characterised in that: described function additive material is by following former Material is obtained, and described number is weight portion:
Gama-alumina 20-30 part；
Vanadic anhydride 1-3 part；
Tungstic anhydride. 10-15 part；
Molybdenum trioxide 10-12 part；
Brium carbonate or Calcium Carbonate 2-8 part；
Diatom ooze 3-5 part；
Tween-60 1-3 part；
Dodecylbenzene sodium sulfonate 2-3 part；
Polytetrafluorethylepowder powder 4-7 part.
CN201610750324.6A 2016-08-30 2016-08-30 Denitration demercuration catalyst Active CN106362732B (en)

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CN110548501A (en) * 2019-07-26 2019-12-10 天津浩创节能环保设备有限公司 denitration and demercuration catalyst and preparation method thereof
CN113750981A (en) * 2021-09-26 2021-12-07 北京市科学技术研究院城市安全与环境科学研究所 Catalyst for synergistically purifying various pollutants and preparation method thereof

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CN103990487A (en) * 2014-06-10 2014-08-20 李灏呈 Denitration and demercuration catalyst and preparation method thereof
CN104226372A (en) * 2014-10-08 2014-12-24 镇江市亚东高压电器厂 Flat-plate-type denitration catalyst and preparation method thereof
CN105107517A (en) * 2015-07-21 2015-12-02 安徽省元琛环保科技有限公司 Preparation method of dioxin removal and denitration catalyst and product thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080166282A1 (en) * 2007-01-09 2008-07-10 Golden Stephen J Ammonia SCR catalyst and method of using the catalyst
CN102166516A (en) * 2011-03-10 2011-08-31 青岛华拓电力环保有限公司 Catalytic agent for denitrating smoke and preparation technology thereof
CN103962124A (en) * 2013-02-04 2014-08-06 上海达源环境科技工程有限公司 Flue gas denitration catalyst
CN103537273A (en) * 2013-09-30 2014-01-29 华中科技大学 Denitration catalyst for collaborative mercury removal and preparation method thereof
CN103752347A (en) * 2014-01-26 2014-04-30 南京宇行环保科技有限公司 Preparation method of honeycomb denitration catalyst
CN103990487A (en) * 2014-06-10 2014-08-20 李灏呈 Denitration and demercuration catalyst and preparation method thereof
CN104226372A (en) * 2014-10-08 2014-12-24 镇江市亚东高压电器厂 Flat-plate-type denitration catalyst and preparation method thereof
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110548501A (en) * 2019-07-26 2019-12-10 天津浩创节能环保设备有限公司 denitration and demercuration catalyst and preparation method thereof
CN113750981A (en) * 2021-09-26 2021-12-07 北京市科学技术研究院城市安全与环境科学研究所 Catalyst for synergistically purifying various pollutants and preparation method thereof

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