CN106391071A - Preparation method of catalyst with active carbon carrier - Google Patents

Preparation method of catalyst with active carbon carrier Download PDF

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Publication number
CN106391071A
CN106391071A CN201610780845.6A CN201610780845A CN106391071A CN 106391071 A CN106391071 A CN 106391071A CN 201610780845 A CN201610780845 A CN 201610780845A CN 106391071 A CN106391071 A CN 106391071A
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China
Prior art keywords
preparation
parts
carrier
acid
activated carbon
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CN201610780845.6A
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Chinese (zh)
Inventor
史和生
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Nanjing Wo Yu Chemical Co Ltd
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Nanjing Wo Yu Chemical Co Ltd
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Priority to CN201610780845.6A priority Critical patent/CN106391071A/en
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • 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
    • B01D2258/0291—Flue gases from waste incineration plants

Abstract

The invention discloses a catalyst with an active carbon carrier. The catalyst comprises the following raw materials: active carbon, MoO2, Cr2O3, MnO2, SnO2, ZrO2, a lubricant, and heteropolyacid. The preparation method comprises the following steps: impregnating active carbon in an electrolyte solution, carrying out aging, then transferring active carbon to a hydrothermal reactor, carrying out reactions to obtain the carrier; evenly mixing MoO2, Cr2O3, MnO2, SnO2, ZrO2, and heteropolyacid, adding the mixture into the carrier, and carrying out impregnation to obtain the catalyst. The provided denitration catalyst has a low light-off temperature, and has the advantages of high thermal stability and hydrothermal stability, wide active temperature window, high denitration efficiency, and long service life; moreover, the preparation method is simple, the operability is strong, and the production cost is reduced.

Description

A kind of preparation method of the catalyst with activated carbon as carrier
Technical field
The invention belongs to catalyst field, the preparation side of more particularly, to a kind of denitrating catalyst with activated carbon as carrier Method.
Background technology
Nitrogen oxides are very serious to the pollution of environment, and nitrogen oxides are the basis of nitric acid type acid rain, are to form light again One of chemical fumes, the main matter damaging the ozone layer；Nitrogen oxides also have very strong toxicity, can cause pole to health Macrolesion.In recent years, with economic fast development, the discharge capacity of nitrogen oxides pollution thing increases sharply, severe contamination life State environment, it has also become the environmental problem of global concern.
By the discharge capacity of its nitrogen oxides being controlled in thermal power plant and industrial furnace De-NO_x, its The denitration of middle selective catalytic reduction (SCR) is one of most widely used, gas denitrifying technology that technology is the most ripe in the world, Its technological core is to employ denitrating catalyst, has the advantages that reaction temperature is relatively low, purifying rate is high, reliable.Flat board Formula catalyst is a very important class in this kind of catalyst, has the higher market share.
The mechanical performance of denitrating catalyst is used for the life-span and has a significant impact, and the flying dust in flue gas constantly washes away catalyst Surface may result in catalyst large area to peel off and cave in, thus greatly shortening catalyst life.Additionally, China will welcome big rule The inactivation denitrating catalyst regeneration market of mould, the regeneration of inactivation denitrating catalyst is not only advantageous to environmental conservation, saves material, Realize the cycling and reutilization of resource, and reduce denitration cost, avoid causing the two of the serious waste of resource and environment simultaneously Secondary pollution, State Council exists《With regard to accelerating development the suggestion of energy-conserving and environment-protective industry》In, clearly propose denitration to be greatly developed and urge Agent regeneration techniques.If catalytic mechanical performance is not good, the phenomenons such as serious peeling are occurred to will be unable to carry out in use Regeneration, this partial catalyst must be processed as danger wastes, and processing cost is high and environmental pollution is serious.
Content of the invention
It is an object of the invention to provide a kind of denitration efficiency height and the strong denitration catalyst with activated carbon as carrier of stability The preparation method of agent.
Technical scheme：The denitrating catalyst with activated carbon as carrier for the present invention, includes the following raw material by weight：Activity Charcoal 200-250 part, MoO210-30 part, Cr2O35-20 part, MnO220-30 part, SnO22-12 part, ZrO29-27 part, lubrication Agent 17-35 part and heteropoly acid 6-15 part.Preferably, the parts by weight of lubricant can be 25-32 part, and it at least includes polyureas lubrication One of fat, epoxy resin, polyacrylate, fatty acid amide, Oleic acid, carboxylic acid, esters of silicon acis or fluorocarbon oil；The weight of heteropoly acid Number can be 10-15 part, and it may include 12- tungstophosphoric acid, 12- tungstosilicic acid or 12- molybdenum silicic acid；The parts by weight of activated carbon are 225- 245 parts；MoO2Parts by weight be 15-25 part.
The method of the denitrating catalyst with activated carbon as carrier for the present invention preparation comprises the steps：
(1) activated carbon is added in electrolyte solution and impregnates, after ageing 15-35h, mixed liquor is transferred in water heating kettle, React 12-15h again under the conditions of 120-160 DEG C, through filtering, washing, be dried, after roasting, that is, absorbent charcoal carrier be obtained；
(2) weigh MoO by weight2、Cr2O3、MnO2、SnO2、ZrO2, lubricant and heteropoly acid, by MoO2、Cr2O3、 MnO2、SnO2、ZrO2And after heteropoly acid mixes, add above-mentioned prepared carrier, dipping, prepared denitrating catalyst slurry, this is starched Material is mixed with lubricant, drying, after roasting, that is, denitrating catalyst is obtained.
The above-mentioned catalyst with activated carbon as carrier is in the application in denitration also within protection scope of the present invention.
Beneficial effect：Compared with prior art, the remarkable advantage of the present invention is：This denitrating catalyst has relatively low rising and lives Temperature, its heat stability and hydrothermal stability are strong, active temperature windows width, denitration efficiency are high, and catalyst life is long；Meanwhile, The preparation method of the present invention is simple, workable, reduces production cost.
Specific embodiment
With reference to embodiment, technical scheme is described further.
Embodiment 1
Raw material：225 parts of activated carbon, MoO215 parts, Cr2O315 parts, MnO225 parts, SnO28 parts, ZrO220 parts, polyureas 32 parts of grease and 10 parts of 12- tungstophosphoric acid.
Preparation method：(1) activated carbon is added in electrolyte solution and impregnate, after ageing 20h, mixed liquor is transferred to hydro-thermal In kettle, then react 13h under the conditions of 130 DEG C, through filtering, washing, be dried, after roasting, that is, absorbent charcoal carrier be obtained；
(2) weigh MoO by weight2、Cr2O3、MnO2、SnO2、ZrO2, polyurea grease and 12- tungstophosphoric acid, will MoO2、Cr2O3、MnO2、SnO2、ZrO2And after 12- tungstophosphoric acid mixes, add above-mentioned prepared carrier, dipping, prepared denitration catalyst Agent slurry, this slurry is mixed with lubricant, is coated on rustless steel steel mesh, 4h is dried at 100 DEG C, 450 DEG C of air atmospheres Lower roasting 9h, that is, be obtained denitrating catalyst.
Embodiment 2
Raw material：235 parts of activated carbon, MoO225 parts, Cr2O310 parts, MnO222 parts, SnO210 parts, ZrO215 parts, profit 25 parts of lubrication prescription and 15 parts of 12- tungstosilicic acid, wherein, lubricant is epoxy resin and polyacrylate.
Preparation method：(1) activated carbon is added in electrolyte solution and impregnate, after ageing 30h, mixed liquor is transferred to hydro-thermal In kettle, then react 14h under the conditions of 140 DEG C, through filtering, washing, be dried, after roasting, that is, absorbent charcoal carrier be obtained；
(2) weigh MoO by weight2、Cr2O3、MnO2、SnO2、ZrO2, lubricant and 12- tungstosilicic acid, by MoO2、 Cr2O3、MnO2、SnO2、ZrO2And after 12- tungstosilicic acid mixes, add above-mentioned prepared carrier, dipping, prepared denitrating catalyst slurry Material, this slurry is mixed with lubricant, is coated on rustless steel steel mesh, 3h is dried at 110 DEG C, roasts under 430 DEG C of air atmospheres Burn 12h, that is, denitrating catalyst is obtained.
Embodiment 3
Raw material：245 parts of activated carbon, MoO230 parts, Cr2O35 parts, MnO230 parts, SnO22 parts, ZrO227 parts, lubrication 17 parts of agent and 15 parts of 12- molybdenum silicic acid, wherein, lubricant is fatty acid amide and Oleic acid.
Preparation method：(1) activated carbon is added in electrolyte solution and impregnate, after ageing 15h, mixed liquor is transferred to hydro-thermal In kettle, then react 12h under the conditions of 120 DEG C, through filtering, washing, be dried, after roasting, that is, absorbent charcoal carrier be obtained；
(2) by MoO2、Cr2O3、MnO2、SnO2、ZrO2And after 12- molybdenum silicic acid mixes, add above-mentioned prepared carrier, leaching Stain, prepared denitrating catalyst slurry, this slurry is mixed with lubricant, is coated on rustless steel steel mesh, at 95 DEG C, 6h is dried, Roasting 10h under 410 DEG C of air atmospheres, that is, be obtained denitrating catalyst.
Embodiment 4
Raw material：240 parts of activated carbon, MoO210 parts, Cr2O320 parts, MnO220 parts, SnO212 parts, ZrO29 parts, lubrication 35 parts of agent and 6 parts of 12- molybdenum silicic acid, wherein, lubricant is carboxylic acid, esters of silicon acis and fluorocarbon oil.
Preparation method：(1) activated carbon is added in electrolyte solution and impregnate, after ageing 35h, mixed liquor is transferred to hydro-thermal In kettle, then react 15h under the conditions of 160 DEG C, through filtering, washing, be dried, after roasting, that is, absorbent charcoal carrier be obtained；
(2) by MoO2、Cr2O3、MnO2、SnO2、ZrO2And after 12- molybdenum silicic acid mixes, add above-mentioned prepared carrier, leaching Stain, prepared denitrating catalyst slurry, this slurry is mixed with lubricant, is coated on rustless steel steel mesh, at 95 DEG C, 6h is dried, Roasting 10h under 410 DEG C of air atmospheres, that is, be obtained denitrating catalyst.
The denitrating catalyst of embodiment 1-4 preparation is put in fixed-bed micro-reactor and is evaluated, in this reactor Temperature be 400 DEG C, simulated flue gas consist of NO concentration be 450ppm, NH3Concentration is 450ppm, O2Content is 5%, vapor Content is 5%, and remaining is N2, gas volume air speed 30000h-1, and entrance NO concentration detected by flue gas analyzer.Obtain Experimental result as shown in table 1.
The denitration efficiency synopsis of the denitrating catalyst that 1-4 is obtained implemented by table 1
As shown in Table 1, not only denitration efficiency is high for the denitrating catalyst that embodiment 1-4 is obtained, and it has relatively low rising and lives Temperature, heat-flash stability and hydrothermal stability are strong, its active temperature windows width, life-span length simultaneously.

Claims (8)

1. a kind of method of the denitrating catalyst prepared with activated carbon as carrier is it is characterised in that comprise the steps：
(1) activated carbon is added in electrolyte solution and impregnate, after ageing 15-35h, mixed liquor is transferred in water heating kettle, then React 12-15h under the conditions of 120-160 DEG C, through filtering, washing, be dried, after roasting, that is, absorbent charcoal carrier be obtained；
(2) weigh MoO by weight2、Cr2O3、MnO2、SnO2、ZrO2, lubricant and heteropoly acid, by MoO2、Cr2O3、MnO2、 SnO2、ZrO2And heteropoly acid mix after, add above-mentioned prepared carrier, dipping, prepared denitrating catalyst slurry, by this slurry with Lubricant mixes, drying, after roasting, that is, denitrating catalyst is obtained.
2. preparation method according to claim 1 is it is characterised in that in step (2), described lubricant at least includes polyureas One of grease, epoxy resin, polyacrylate, fatty acid amide, Oleic acid, carboxylic acid, esters of silicon acis or fluorocarbon oil.
3. preparation method according to claim 1 is it is characterised in that in step (2), described heteropoly acid includes 12- tungsten phosphorus Acid, 12- tungstosilicic acid or 12- molybdenum silicic acid.
4. preparation method according to claim 1 is it is characterised in that in step (1) and (2), the mass fraction of each component As follows：
Activated carbon 200-250 part, 50-80 part, 20-40 part, MoO210-30 part, Cr2O35-20 part, MnO220-30 part, SnO22- 12 parts, ZrO29-27 part, lubricant 17-35 part and heteropoly acid 6-15 part.
5. preparation method according to claim 1 is it is characterised in that the parts by weight of described activated carbon are 225-245 part.
6. preparation method according to claim 1 is it is characterised in that described MoO2Parts by weight be 15-25 part.
7. preparation according to claim 5 is with activated carbon -- and the method for the denitrating catalyst as carrier is it is characterised in that institute The parts by weight stating lubricant are 25-32 part.
8. preparation according to claim 5 is with activated carbon -- and the method for the denitrating catalyst as carrier is it is characterised in that institute The parts by weight stating heteropoly acid are 10-15 part.
CN201610780845.6A 2016-08-31 2016-08-31 Preparation method of catalyst with active carbon carrier Withdrawn CN106391071A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101185886A (en) * 2007-11-21 2008-05-28 北京博奇电力科技有限公司 SCR denitration catalyst and preparation method thereof
CN102950008A (en) * 2011-08-29 2013-03-06 中国石油化工股份有限公司 Composite smoke SCR (selective catalytic reduction) denitrification catalyst and preparation method thereof
CN103861628A (en) * 2012-12-14 2014-06-18 上海郎特电力环保科技有限公司 Flue-gas denitration catalyst incapable of being deactivated by basic metallic oxides, preparation method thereof and applications thereof
CN105688974A (en) * 2016-01-11 2016-06-22 大唐南京环保科技有限责任公司 Denitration catalyst with SBA-15/TiO2 serving as carrier and preparing method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101185886A (en) * 2007-11-21 2008-05-28 北京博奇电力科技有限公司 SCR denitration catalyst and preparation method thereof
CN102950008A (en) * 2011-08-29 2013-03-06 中国石油化工股份有限公司 Composite smoke SCR (selective catalytic reduction) denitrification catalyst and preparation method thereof
CN103861628A (en) * 2012-12-14 2014-06-18 上海郎特电力环保科技有限公司 Flue-gas denitration catalyst incapable of being deactivated by basic metallic oxides, preparation method thereof and applications thereof
CN105688974A (en) * 2016-01-11 2016-06-22 大唐南京环保科技有限责任公司 Denitration catalyst with SBA-15/TiO2 serving as carrier and preparing method thereof

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