CN106345454B - Denitration takes off dioxin catalyst - Google Patents
Denitration takes off dioxin catalyst Download PDFInfo
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- CN106345454B CN106345454B CN201610750671.9A CN201610750671A CN106345454B CN 106345454 B CN106345454 B CN 106345454B CN 201610750671 A CN201610750671 A CN 201610750671A CN 106345454 B CN106345454 B CN 106345454B
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- 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
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- 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
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- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- 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
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Abstract
The present invention relates to a kind of denitrations to take off dioxin catalyst, belongs to environmental protection catalyst field.The present invention forms Mo-V-W/TiO between each component of catalyst with aluminium oxide and nano TiO 2 carrying body2‑Al2O3System, in active component Mo, V, W and carrier TiO2‑Al2O3Under the action of realize denitration function, while by magnesium-yttrium-transition metal composition V-W-Ti-Mo system, dioxin can be resolved into HCl, CO very well2、H2O can effectively simplify the structure of tail gas filtering exhaust apparatus, reduce environmentally friendly cost to have both de- dioxin, denitration in one.In addition, the present invention has high antidusting interference performance, on the basis of without frequent shutdown cleaning dust stratification, remains to play maximum strainability, enable the aging speed of catalyst uniform, filter out ability by force and long service life.
Description
Technical field
The present invention relates to a kind of denitrations to take off dioxin catalyst and preparation method thereof, belongs to the catalyst of filtering polluted gas
Field.
Background technique
With China's expanding economy, the quantity of China's coal energy-output ratio and motor vehicle is increased considerably, and causes sky
Various pollutants content is also rising rapidly in gas.By the effort of decades, China is dirty in control dust and sulfur dioxide
Dye aspect has obtained certain success, but control is not yet received in the pollution of dioxin and nitrogen oxides.Therefore, how effectively
Control dioxin nitrogen oxides discharge become current environment protection field focus.
Traditional catalyst can only unidirectionally filter out dioxin or nitrogen oxides, when causing to filter mixed flue gas,
Required equipment construction is complicated, increases production cost.Also, traditional catalyst relies on honeycombed catalyst to be filtered operation,
The structure of this catalyst is simple, however once has large particle to enter catalytic inner, and whole honeycomb hole will be blocked,
It can not carry out normal filtration reaction.Catalyst operation in high pollution environment, dust accumulation be it is inevitable, how be not necessarily to frequent shutdown
It clears up on the basis of dust stratification, remains to that it is enabled to play maximum strainability, be the problem that those skilled in the art need to solve.
The invention proposes a kind of denitrations to take off dioxin catalyst, can filter out dioxin and nitrogen oxides simultaneously, obtained
Catalyst price is low, and carefully, activity is also higher for chemical and thermal stability, and anti-toxicity can be high.In addition, the present invention has height
Antidusting interference performance remains to play maximum strainability, enables catalyst on the basis of without frequent shutdown cleaning dust stratification
Aging speed is uniform, filters out ability by force and long service life.
Summary of the invention
To solve the problems, such as encountering in actual use for high temperature catalyst, the present invention provides a kind of denitrations de- two to dislike
English catalyst can filter out dioxin and nitrogen oxides simultaneously, and obtained catalyst price is low, and chemical and thermal stability is carefully, living
Property it is also higher, and anti-toxicity can be high.In addition, the present invention has high antidusting interference performance, without frequent shutdown cleaning product
It on the basis of ash, remains to play maximum strainability, enables the aging speed of catalyst uniform, filter out ability by force and service life
It is long.
The present invention is achieved by the following technical solutions:
A kind of de- dioxin catalyst of denitration, it is characterised in that be made by following raw materials, the number is parts by weight:
60-70 parts of substrate；
1-3 parts of active constituent；
20-30 parts of auxiliary agent；
2-8 parts of binder；
3-5 parts of plasticizer；
Wherein the substrate includes titanium dioxide, silicon powder and gama-alumina.
Titanium dioxide, silicon powder and gama-alumina are 5:2:3 in mass ratio in the substrate.
The active constituent includes vanadic anhydride, ammonium metatungstate, cerous nitrate and lanthanum nitrate；Above-mentioned vanadic anhydride, partially
The mass ratio of ammonium tungstate, cerous nitrate and lanthanum nitrate is 6:3:1:1.
The auxiliary agent includes yttrium oxide, tungstic acid and molybdenum trioxide；Above-mentioned yttrium oxide, tungstic acid and molybdenum trioxide
Mass ratio is 1:3:3.
The binder includes Suzhou soil, bentonite and calcium carbonate；The mass ratio of above-mentioned Suzhou soil, bentonite and calcium carbonate
For 2:2:1.
The plasticizer includes hydroxymethyl cellulose and diatom ooze；The mass ratio of above-mentioned hydroxymethyl cellulose and diatom ooze is
3:2。
It further include squeezing out lubricant, the applied amount for squeezing out lubricant is 1.5-3 parts；The extrusion lubricant includes methyl silicon
The mass ratio of oil and high oleic sunflower oil, methyl-silicone oil and high oleic sunflower oil is 3:1.
Denitration of the present invention takes off dioxin catalyst, including following preparation step:
(1) substrate is cooled to 30-60 DEG C, obtains pretreating substrates in 80-120 DEG C of vacuum oven 6-8h；
(2) active constituent and auxiliary agent are weighed, mixing kettle is added, 20-25L deionized water is gradually added into mixing kettle, and open
Stirring is opened, after stirring 2-3h with the speed of 100-200r/min, pretreating substrates in step (1) are added, continues to stir 2-3h；
(3) by the obtained object of step (2), it is put into Muffle furnace, calcines 4-6h at 500-700 DEG C；
(4) the obtained object of step (3) is added binder, plasticizer and squeezes out lubricant and be kneaded, until by material
It is kneaded uniform；
(5) it will be kneaded the material come out, after curing 24-48h, is added in filtering pre-extruded and squeezes out, be filtered to remove material
Middle impurity；
(6) it by the material after filtering pre-extruded, is formed by mold integral extrusion, and according to the length of regulation, it will be above-mentioned
Finished product carries out being cut into segmented body, carries out hemispherical concave machining at the both ends of each segmented body, enables each segmented body
Both ends formed indent hemisphere face；
(7) it is embedded in cross-linked spheres catalyst between two adjacent segmented bodies, obtains finished product.
The preparation method of cross-linked spheres catalyst described in step (7) is the foaming metal processing for being 1-3mm by aperture
At spherical shape, with electrophoretic deposition in the hole of foaming metal one layer function promoter material of plating, the thickness of the function additive material
Degree is less than 0.5mm.
The function additive material is made by following raw materials, and the number is parts by weight:
20-30 parts of gama-alumina；
1-3 parts of vanadic anhydride；
10-15 parts of tungstic acid；
10-12 parts of molybdenum trioxide；
Barium carbonate or 2-8 parts of calcium carbonate；
3-5 parts of diatom ooze；
1-3 parts of Tween-60；
2-3 parts of neopelex；
4-7 parts of polytetrafluorethylepowder powder.
The present invention has the beneficial effects that
1, aluminium oxide and nano TiO 2 carrying body itself specific surface area with higher, adds pore creating material on this basis
Silicon powder can enable substrate have suitable pore structure and water absorption rate, the surface area of carrier can be improved, be conducive to catalyst activity
Ingredient dispersion, to improve activity and the service life of catalyst.
2, Mo-V-W/TiO is formed between each component of catalyst2-Al2O3System, in active component Mo, V, W and load
Body TiO2-Al2O3Under the action of realize denitration function, while by magnesium-yttrium-transition metal composition V-W-Ti-Mo system, can be very
It is good that dioxin is resolved into HCl, CO2、H2O can effectively simplify tail gas filtering discharge to have both de- dioxin, denitration in one
The structure of equipment reduces environmentally friendly cost.
3, rare earth oxide is added can be improved the heat resistance of catalyst, plays stable lattice structure and prevents volume contraction
Double action.
4, cross-linked spheres catalyst is embedded between two adjacent honeycomb segmented bodies, cross-linked spheres catalyst is in synchronization
It can play the role of high heat transfer and multi-pass pipe while filtering.Out of stock de- dioxin catalyst is required in higher temperature
There could be high reaction activity under the conditions of degree, however, temperature when flue gas just gives off is not able to maintain too long, as flue gas exists
It is moved in catalyst, temperature gradually lowers.And foam metal has high heat conduction efficiency, can fully absorb flue gas discharge
The heat carried when beginning enables catalyst front-end and back-end thermally equivalent, is conducive to the conversion ratio for improving out of stock de- dioxin.
Further, since catalyst operation in high dirt environment, once a honeycomb hole of segmented body is blocked, flue gas can also
To enter in next adjacent sectional body from the multi-pass pipeline for crossing cross-linked spheres catalyst, the blocking rate of filter opening is enabled to be greatly lowered.And
And the motion profile of flue gas in the catalyst itself is also uneven, cross-linked spheres catalyst can also play evenly dispersed flue gas
Effect can remain to that it is enabled to play maximum strainability, extend 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 de- dioxin catalyst of denitration, is made, the number is parts by weight by following raw materials:
60-70 parts of substrate；
1-3 parts of active constituent；
20-30 parts of auxiliary agent；
2-8 parts of binder；
3-5 parts of plasticizer；
Wherein the substrate includes titanium dioxide, silicon powder and gama-alumina.
Each ingredient and dosage in specific embodiment see the table below:
| Ingredient | Embodiment one | Embodiment two | Embodiment three |
| Substrate | 60 parts | 65 parts | 70 parts |
| Active constituent | 1 part | 1.2 part | 3 parts |
| Auxiliary agent | 20 parts | 25 parts | 30 parts |
| Binder | 2 parts | 25 parts | 8 parts |
| Plasticizer | 3 parts | 3.7 part | 5 parts |
| Squeeze out lubricant | 1.5 part | 2 parts | 3 parts |
Titanium dioxide, silicon powder and gama-alumina are 5:2:3 in mass ratio in the substrate.
The active constituent includes vanadic anhydride, ammonium metatungstate, cerous nitrate and lanthanum nitrate；Above-mentioned vanadic anhydride, partially
The mass ratio of ammonium tungstate, cerous nitrate and lanthanum nitrate is 6:3:1:1.
The auxiliary agent includes yttrium oxide, tungstic acid and molybdenum trioxide；Above-mentioned yttrium oxide, tungstic acid and molybdenum trioxide
Mass ratio is 1:3:3.
The binder includes Suzhou soil, bentonite and calcium carbonate；The mass ratio of above-mentioned Suzhou soil, bentonite and calcium carbonate
For 2:2:1.
The plasticizer includes hydroxymethyl cellulose and diatom ooze；The mass ratio of above-mentioned hydroxymethyl cellulose and diatom ooze is
3:2。
It further include squeezing out lubricant, the applied amount for squeezing out lubricant is 1.5-3 parts；The extrusion lubricant includes methyl silicon
The mass ratio of oil and high oleic sunflower oil, methyl-silicone oil and high oleic sunflower oil is 3:1.
Denitration of the present invention takes off dioxin catalyst, including following preparation step:
(1) substrate is cooled to 30-60 DEG C, obtains pretreating substrates in 80-120 DEG C of vacuum oven 6-8h；
(2) active constituent and auxiliary agent are weighed, mixing kettle is added, 20-25L deionized water is gradually added into mixing kettle, and open
Stirring is opened, after stirring 2-3h with the speed of 100-200r/min, pretreating substrates in step (1) are added, continues to stir 2-3h；
(3) by the obtained object of step (2), it is put into Muffle furnace, calcines 4-6h at 500-700 DEG C；
(4) the obtained object of step (3) is added binder, plasticizer and squeezes out lubricant and be kneaded, until by material
It is kneaded uniform；
(5) it will be kneaded the material come out, after curing 24-48h, is added in filtering pre-extruded and squeezes out, be filtered to remove material
Middle impurity；
(6) it by the material after filtering pre-extruded, is formed by mold integral extrusion, and according to the length of regulation, it will be above-mentioned
Finished product carries out being cut into segmented body, carries out hemispherical concave machining at the both ends of each segmented body, enables each segmented body
Both ends formed indent hemisphere face；
(7) it is embedded in cross-linked spheres catalyst between two adjacent segmented bodies, obtains finished product.
The preparation method of cross-linked spheres catalyst described in step (7) is the foaming metal processing for being 1-3mm by aperture
At spherical shape, with electrophoretic deposition in the hole of foaming metal one layer function promoter material of plating, the thickness of the function additive material
Degree is less than 0.5mm.The foaming metal is nickel foam.
The function additive material is made by following raw materials, and the number is parts by weight:
20-30 parts of gama-alumina；
1-3 parts of vanadic anhydride；
10-15 parts of tungstic acid；
10-12 parts of molybdenum trioxide；
Barium carbonate or 2-8 parts of calcium carbonate；
3-5 parts of diatom ooze；
1-3 parts of Tween-60；
2-3 parts of neopelex；
4-7 parts of polytetrafluorethylepowder powder.
Function additive material each ingredient in a particular embodiment and dosage see the table below:
| Ingredient | Embodiment one | Embodiment two | Embodiment three |
| Gama-alumina | 20 parts | 25 parts | 30 parts |
| Vanadic anhydride | 1 part | 1.5 part | 3 parts |
| Tungstic acid | 10 parts | 13 parts | 15 parts |
| Molybdenum trioxide | 10 parts | 11 parts | 12 parts |
| Barium 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 |
| Neopelex | 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 (%) | Dioxin removal efficiency (%) |
| Embodiment one | 96.3 | 99.3 |
| Embodiment two | 97 | 99.4 |
| Embodiment three | 97.1 | 99.7 |
Above-mentioned the results show, service performance of the invention is good, can effectively remove nitre and dioxin in flue gas, fits
Preferably in the industry cycle advisor is universal.
Claims (1)
1. a kind of denitration takes off dioxin catalyst, it is characterised in that be made by following raw materials, the number is parts by weight:
Wherein the substrate includes titanium dioxide, silicon powder and gama-alumina；
Titanium dioxide, silicon powder and gama-alumina are 5:2:3 in mass ratio in the substrate；
The active constituent includes vanadic anhydride, ammonium metatungstate, cerous nitrate and lanthanum nitrate；Above-mentioned vanadic anhydride, metatungstic acid
The mass ratio of ammonium, cerous nitrate and lanthanum nitrate is 6:3:1:1；
The auxiliary agent includes yttrium oxide, tungstic acid and molybdenum trioxide；The quality of above-mentioned yttrium oxide, tungstic acid and molybdenum trioxide
Than for 1:3:3；
The binder includes Suzhou soil, bentonite and calcium carbonate；The mass ratio of above-mentioned Suzhou soil, bentonite and calcium carbonate is 2:
2:1；
The plasticizer includes hydroxymethyl cellulose and diatom ooze；The mass ratio of above-mentioned hydroxymethyl cellulose and diatom ooze is 3:2；
It further include squeezing out lubricant, the applied amount for squeezing out lubricant is 1.5-3 parts；The extrusion lubricant include methyl-silicone oil and
The mass ratio of high oleic sunflower oil, methyl-silicone oil and high oleic sunflower oil is 3:1；
Including following preparation step:
1) substrate is cooled to 30-60 DEG C in 80-120 DEG C of vacuum oven 6-8h, obtains pretreating substrates；
2) active constituent and auxiliary agent are weighed, mixing kettle is added, 20-25L deionized water is gradually added into mixing kettle, and open and stir
It mixes, after stirring 2-3h with the speed of 100-200r/min, pretreating substrates in step 1) is added, continue to stir 2-3h；
3) by the obtained object of step 2), it is put into Muffle furnace, calcines 4-6h at 500-700 DEG C；
4) the obtained object of step 3) is added binder, plasticizer and squeezes out lubricant and be kneaded, until material is kneaded equal
It is even；
5) it will be kneaded the material come out, after curing 24-48h, is added in filtering pre-extruded and squeezes out, be filtered to remove miscellaneous in material
Matter；
6) material after pre-extruded will be filtered, formed by mold integral extrusion, and according to the length of regulation, by above-mentioned finished product into
Row is cut into segmented body, carries out hemispherical concave machining at the both ends of each segmented body, enables the both ends of each segmented body
Form the hemisphere face of indent；
7) it is embedded in cross-linked spheres catalyst between two adjacent segmented bodies, obtains finished product；
The preparation method of cross-linked spheres catalyst described in step 7) is the foaming metal processing balling-up for being 1-3mm by aperture
Shape, with electrophoretic deposition, one layer function promoter material of plating, the thickness of the function additive material are small in the hole of foaming metal
In 0.5mm；
The foaming metal is nickel foam；
The function additive material is made by following raw materials, and the number is parts by weight:
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| CN107890777A (en) * | 2017-11-28 | 2018-04-10 | 辽宁鑫隆科技有限公司 | A kind of catalytic-reduction denitrified method of dry method |
| CN109482049B (en) * | 2019-01-02 | 2021-07-23 | 武汉科林化工集团有限公司 | Dry desulfurization, denitrification and purification integrated process for coke oven flue gas |
| CN111672504B (en) * | 2020-06-03 | 2024-03-19 | 北京海顺德钛催化剂有限公司 | Catalyst for moving bed and/or fluidized bed denitration device and preparation method and application thereof |
| CN111530449B (en) * | 2020-06-09 | 2021-08-10 | 江苏龙净科杰环保技术有限公司 | Wall-flow dedusting low-temperature denitration honeycomb catalyst for flue gas and preparation process 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 |
| CN114377683B (en) * | 2022-01-25 | 2023-11-14 | 大唐南京环保科技有限责任公司 | Arsenic poisoning-resistant denitration catalyst and preparation method thereof |
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| 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 |
| CN104226301A (en) * | 2014-09-16 | 2014-12-24 | 东营信拓汽车消声器有限公司 | Preparation method of rare-earth-based composite multi-component denitrification and dioxin removal catalyst |
| CN104841489A (en) * | 2015-05-29 | 2015-08-19 | 山东爱亿普环保科技有限公司 | Rare-earth-based composite multi-component denitration and dioxin-removing 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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