CN109603922A - A kind of composite titanium dioxide and preparation method thereof for high-ratio surface denitrating catalyst - Google Patents

A kind of composite titanium dioxide and preparation method thereof for high-ratio surface denitrating catalyst Download PDF

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Publication number
CN109603922A
CN109603922A CN201811445470.3A CN201811445470A CN109603922A CN 109603922 A CN109603922 A CN 109603922A CN 201811445470 A CN201811445470 A CN 201811445470A CN 109603922 A CN109603922 A CN 109603922A
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Prior art keywords
parts
titanium dioxide
preparation
catalyst
denitrating catalyst
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Pending
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CN201811445470.3A
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Chinese (zh)
Inventor
肖雨亭
周凤翔
陆金丰
徐光辉
白伟
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Jiangsu Longyuan Catalyst Co Ltd
Guoneng Longyuan Environmental Engineering Co Ltd
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Jiangsu Longyuan Catalyst Co Ltd
Beijing Guodian Longyuan Environmental Engineering Co Ltd
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Priority to CN201811445470.3A priority Critical patent/CN109603922A/en
Publication of CN109603922A publication Critical patent/CN109603922A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts 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
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/30Tungsten
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8621Removing nitrogen compounds
    • B01D53/8625Nitrogen oxides
    • B01D53/8628Processes characterised by a specific catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • B01J35/613
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027Powdering
    • B01J37/0036Grinding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases

Abstract

A kind of composite titanium dioxide and preparation method thereof for high-ratio surface denitrating catalyst, is made of following substance percentage by weight: 100 parts of titanium dioxides, 9-21 parts of activated diatomaceous earths, 4-11 parts of sepiolite powders, 2.8-5.6 parts of zirconium oxides, 0.8-7.9 parts of ammonium paratungstates, 0.5-5.8 parts of cerium oxide, 0.6-2.8 parts of bridging silsesquioxanes, 0.1-0.28 parts of hyper-dispersants.The catalyst pug that the composite titanium dioxide that the present invention is prepared is prepared has the characteristics that plasticity is high, water retention property is good, extrusion is smooth, and the specific surface area of catalyst being prepared is higher than conventional catalyst.

Description

A kind of composite titanium dioxide and preparation method thereof for high-ratio surface denitrating catalyst
Technical field
The present invention relates to denitrating catalyst preparation technical fields more particularly to a kind of for high-ratio surface denitrating catalyst Composite titanium dioxide and preparation method thereof.
Background technique
Nitrogen oxide NOx (NO, NO2And N2O) be global atmosphere pollution one of major pollutants, cause photochemical fog, The environmental problems such as acid rain, depletion of the ozone layer seriously affect the living environment and quality of life of people, attract wide attention, control The discharge amount of NOx processed has great significance for improving air quality, construction Eco-friendly society.In numerous denitration sides In method, selective catalytic reduction (SCR) is efficient with it, mature, stable denitration performance gradually occupies industrial denitration field and leads Head status, currently, most common SCR denitration is medium temperature (300-420 DEG C), 18 hole homogeneous catalysis, still, some Gas fired-boiler, or after dust-removal and desulfurizing, dustiness and the relatively low boiler of sulfur content, are urged using conventional 18 holes in flue gas Agent can have the problems such as catalyst usage amount is big, and catalytic inner flow velocity is high, and denitration efficiency is low, therefore, 30 holes, 40 holes, 50 The high-ratio surface denitrating catalyst of the even higher hole count in hole comes into being.
Chinese patent CN201610891414.7 discloses a kind of for NH in denitrating flue gas4HSO4The vanadium base of decomposition is compound The preparation method of titanium dioxide catalyst, the load and vanadium base of preparation, vanadium including composite titanium dioxide on composite titanium dioxide are compound The roasting of titanium dioxide;It is compound that vanadium base has been prepared by loading a certain amount of vanadic anhydride on composite titanium dioxide in the present invention Titanium dioxide catalyst reduces the decomposition temperature of ammonium hydrogen sulfate;The preparation method simple process, strong operability, are applicable to Heavy industrialization.
Chinese patent CN201010513687.0 discloses a kind of for removing the catalyst of NOx comprising major catalyst, Carrier and glass fibre, the major catalyst are the vanadic anhydride (V2O5) for accounting for weight percentage and being 0.05~3%, institute Stating carrier is the composite titanium dioxide for accounting for weight percentage and being 85%~97%, and the glass fibre accounts for weight percentage and is 3%~7%;Its manufacturing method is that raw material is mediated, filters aging, extrusion forming, drying, roasting reinforcing, cutting finished product, end Face hardening, detection packaging and exhaust-gas treatment manufacture high value added product and waste water recycling and the grinding reuse of dust waste etc. Auxiliary process.Catalyst of the invention realizes green zero-emission in preparation, can be used for removing NOx and takes off suitable for SCR Nitre technique, while the activity of catalyst has obtained stabilization with the service life, is an important breakthrough of catalyst industry.
But directly prepare that high there is pug viscosity than table catalyst using conventional titanium white powder and common process at present Not enough, the problems such as water retention property is bad, and plasticity is bad results in the catalyst mud embryo appearance that catalyst extruded velocity is slow and squeezes out The problems such as easy to crack, yield rate is extremely low, and therefore, developing a kind of dedicated composite titanium dioxide of high-ratio surface denitrating catalyst is extremely It is necessary.
Summary of the invention
Height is directly prepared the purpose of the present invention is to solve conventional titanium white powder and common process to exist than table catalyst Pug viscosity not enough, the problems such as water retention property is bad, and plasticity is bad, result in that catalyst extruded velocity is slow and what is squeezed out urges Agent mud embryo is easy the problems such as cracking, provides a kind of composite titanium dioxide dedicated for preparing high-specific surface area denitrating catalyst Preparation process, the catalyst pug that the composite titanium dioxide being prepared is prepared has that plasticity is high, water retention property is good, squeezes out Smooth feature, the specific surface area of catalyst being prepared are higher than conventional catalyst.
The invention adopts the following technical scheme:
Composite titanium dioxide for high-ratio surface denitrating catalyst of the invention is made of by weight following substance: 100 parts of titanium dioxides, 9-21 parts of activated diatomaceous earths, 4-11 parts of sepiolite powders, 2.8-5.6 parts of zirconium oxides, 0.8-7.9 parts of para-tungstic acids Ammonium, 0.5-5.8 part cerium oxide, 0.6-2.8 parts of bridging silsesquioxanes, 0.1-0.28 parts of hyper-dispersants.
One of as a preferred technical scheme: composite titanium dioxide of the invention is made of by weight following substance: 100 Part titanium dioxide, 12 parts of activated diatomaceous earths, 8 parts of sepiolite powders, 4 parts of zirconium oxides, 0.8 part of ammonium paratungstate, 0.8 part of cerium oxide, 1 part of bridge Join silsesquioxane, 0.1 part of hyper-dispersant.
The bridging silsesquioxane is KH560-660 and/or KH560-540.
The hyper-dispersant is end mercaptoacetylamide polymethyl acrylate.
The preparation method of composite titanium dioxide for high-ratio surface denitrating catalyst of the invention, it is characterised in that: described Specific step is as follows for method:
(1) titanium dioxide, activated diatomaceous earth, zirconium oxide, ammonium paratungstate, cerium oxide, bridging silsesquioxane, demineralized water are mixed It closes, suspension is made, suspension mass concentration is 25%-35%, stirs 0.5-2h at 30-80 DEG C;
(2) suspension in step (1) is placed in ball mill, carries out wet ball grinding after hyper-dispersant is added, ball milling is complete At rear washing and drying;
(3) it can be obtained after being sufficiently mixed composite powder obtained in step (2) and sepiolite powder in blender To the composite titanium dioxide for being used to prepare high-ratio surface denitrating catalyst.
In step (1), 1h preferably is stirred at 50 DEG C.
In step (1), preferably suspension mass concentration is 30%.
In step (2), ball milling granularity is 2000-5000 mesh.
In step (3), sepiolite powder granularity is 800-1500 mesh.
In step (3), mixing time 1-2h.
The beneficial effects of the present invention are:
(1) present invention improves the modeling of pug by increasing Component Vectors ingredient activated diatomaceous earth and Activated Sepiolite powder Property, improve the mobility and water-retaining property of pug by adjusting the grain composition of different carriers component powders.
(2) present invention improves powder property by addition part of the metal oxide active constituent zirconium oxide and cerium oxide, The denitration activity of product is improved simultaneously.
(3) present invention uses bridging silsesquioxane to improve powder characteristics as surfactant, and powder is prepared Pug have preferably viscosity, while the organic long-chain being embedded after calcining can catalytic inner formed large number of orifices Road improves the specific surface area of catalyst.
(4) the catalyst pug that the composite titanium dioxide that the present invention is prepared is prepared has plasticity height, water retention property Well, smooth feature is squeezed out, the specific surface area of catalyst being prepared is higher than conventional catalyst.
Specific embodiment
The embodiment recorded herein is specific specific embodiment of the invention, for illustrating design of the invention, Be it is explanatory and illustrative, should not be construed as the limitation to embodiment of the present invention and the scope of the invention.Except what is recorded herein Outside embodiment, those skilled in the art can also based on the claim of this application book and specification disclosure of that using aobvious and The other technical solutions being clear to, these technical solutions include using any obvious to making for the embodiment recorded herein The technical solution of substitutions and modifications.
Embodiment 1
By 500kg titanium dioxide, 60kg activated diatomaceous earth, 20kg zirconium oxide, 4kg cerium oxide, secondary tungsten acid ammonium solution (WO3It accounts for Total mass ratio 5%), the mixing of 5kg bridging silsesquioxane KH560-660 and 1300L demineralized water, then 50 DEG C of stirring 1h turn It moves in ball mill, the end 0.5kg mercaptoacetylamide polymethyl acrylate is added and carries out wet ball-milling, grind size is 5000 mesh. It is washed after grinding and dry.The powder and 40kg Activated Sepiolite powder (1000 mesh) obtained after the completion of will be dry is in blender The high-specific surface area denitrating catalyst specific complex titanium dioxide is obtained after middle stirring 1.5h.
Embodiment 2
By 500kg titanium dioxide, 80kg activated diatomaceous earth, 10kg zirconium oxide, 2.5kg cerium oxide, secondary tungsten acid ammonium solution (WO3 Account for total mass ratio 5%), 6kg bridging silsesquioxane KH560-660 and 1400L demineralized water mixing, 50 DEG C of stirring 1h, then It is transferred in ball mill, 0.5kg hyper-dispersant is added and carries out wet ball-milling, grind size is 4000 mesh.It is washed after grinding And it is dry.The powder obtained after the completion of will be dry obtains after stirring 2h in blender with 40kg Activated Sepiolite powder (800 mesh) The high-specific surface area denitrating catalyst specific complex titanium dioxide.
Embodiment 3
By 500kg titanium dioxide, 90kg activated diatomaceous earth, 12kg zirconium oxide, 10kg cerium oxide, secondary tungsten acid ammonium solution (WO3It accounts for Total mass ratio 5%), the mixing of 8kg bridging silsesquioxane KH560-660 and 1400L demineralized water, then 50 DEG C of stirring 1h turn It moves in ball mill, 0.5kg hyper-dispersant is added and carries out wet ball-milling, grind size is 5000 mesh.It is washed simultaneously after grinding It is dry.The powder and 40kg Activated Sepiolite powder (800 mesh) obtained after the completion of will be dry obtains institute after stirring 2h in blender State high-specific surface area denitrating catalyst specific complex titanium dioxide.
Embodiment 4
By 500kg titanium dioxide, 80kg activated diatomaceous earth, 12kg zirconium oxide, 10kg cerium oxide, secondary tungsten acid ammonium solution (WO3It accounts for Total mass ratio 5%), the mixing of 8kg bridging silsesquioxane KH560-660 and 1400L demineralized water, then 50 DEG C of stirring 1h turn It moves in ball mill, 0.5kg hyper-dispersant is added and carries out wet ball-milling, grind size is 3000 mesh.It is washed simultaneously after grinding It is dry.The powder obtained after the completion of will be dry obtains after stirring 1.5h in blender with 40kg Activated Sepiolite powder (1000 mesh) The high-specific surface area denitrating catalyst specific complex titanium dioxide.
The pug that moisture is 28% is prepared using above-described embodiment respectively, at room temperature by the same quality of same shape The naked leakage of pug sample surveys its weight-loss ratio every 4h, the results are shown in Table 1 in outdoor:
Table 1
Sample 4 hours 8 hours 12 hours 16 hours 20 hours
Embodiment 1 0.3% 0.5% 0.9% 1.2% 1.5%
Embodiment 2 0.6% 0.9% 1.3% 1.6% 2.0%
Embodiment 3 0.6% 0.8% 1.2% 1.6% 1.9%
Embodiment 4 0.5% 0.7% 1.0% 1.3% 1.7%
Conventional titanium dioxide 1.2% 2.1% 3.3% 4.5% 6.1%
It can significantly see that the pug water retention property of embodiment powder preparation is better than conventional pug.
The extrusion for carrying out catalyst mud embryo using above-mentioned pug respectively, records the ratio of extruded velocity and last finished catalyst Surface area and denitration efficiency (standard laboratory conditions: temperature: 380 DEG C;NOx:500ppm;SO2:≤100ppm;O2: 5%;H2O: 10%;NH3/ NOx:1/1;Lv:6m/s.):
Table 2
This it appears that using this method prepare composite titanium dioxide made from plasticity of slurry it is more preferable, in extrusioning catalyst When extruded velocity faster, the specific surface area of catalyst being prepared is higher, and denitration efficiency is also higher.

Claims (10)

1. a kind of composite titanium dioxide for high-ratio surface denitrating catalyst, it is characterised in that: the composite titanium dioxide be by Following substance forms by weight: 100 parts of titanium dioxides, 9-21 parts of activated diatomaceous earths, 4-11 parts of sepiolite powders, 2.8-5.6 parts of oxygen Change zirconium, 0.8-7.9 parts of ammonium paratungstates, 0.5-5.8 parts of cerium oxide, 0.6-2.8 parts of bridging silsesquioxanes, 0.1-0.28 parts of oversubscription Powder.
2. being used for the composite titanium dioxide of high-ratio surface denitrating catalyst as described in claim 1, it is characterised in that: described answers It closes titanium dioxide to be made of by weight following substance: 100 parts of titanium dioxides, 12 parts of activated diatomaceous earths, 8 parts of sepiolite powders, 4 parts of oxygen Change zirconium, 0.8 part of ammonium paratungstate, 0.8 part of cerium oxide, 1 part of bridging silsesquioxane, 0.1 part of hyper-dispersant.
3. being used for the composite titanium dioxide of high-ratio surface denitrating catalyst as described in claim 1, it is characterised in that: the bridge Connection silsesquioxane is KH560-660 and/or KH560-540.
4. being used for the composite titanium dioxide of high-ratio surface denitrating catalyst as described in claim 1, it is characterised in that: described is super Dispersing agent is end mercaptoacetylamide polymethyl acrylate.
5. a kind of side for preparing the composite titanium dioxide according to any one of claims 1-4 for high-ratio surface denitrating catalyst Method, it is characterised in that: specific step is as follows for the method:
(1) titanium dioxide, activated diatomaceous earth, zirconium oxide, ammonium paratungstate, cerium oxide, bridging silsesquioxane, demineralized water are mixed, Suspension is made, suspension mass concentration is 25%-35%, stirs 0.5-2h at 30-80 DEG C;
(2) suspension in step (1) is placed in ball mill, carries out wet ball grinding after hyper-dispersant is added, after the completion of ball milling It washs and dries;
(3) use can be obtained after being sufficiently mixed composite powder obtained in step (2) and sepiolite powder in blender In the composite titanium dioxide for preparing high-ratio surface denitrating catalyst.
6. preparation method as claimed in claim 5, it is characterised in that: in step (1), stir 1h at 50 DEG C.
7. preparation method as claimed in claim 5, it is characterised in that: in step (1), suspension mass concentration is 30%.
8. preparation method as claimed in claim 5, it is characterised in that: in step (2), ball milling granularity is 2000-5000 mesh.
9. preparation method as claimed in claim 5, it is characterised in that: in step (3), sepiolite powder granularity is 800-1500 Mesh.
10. preparation method as claimed in claim 5, it is characterised in that: in step (3), mixing time 1-2h.
CN201811445470.3A 2018-11-29 2018-11-29 A kind of composite titanium dioxide and preparation method thereof for high-ratio surface denitrating catalyst Pending CN109603922A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101444727A (en) * 2008-12-17 2009-06-03 中材高新材料股份有限公司 Integral honeycombed catalyst for SCR flue-gas denitration and preparation method therefor
CN103861581A (en) * 2012-12-14 2014-06-18 上海郎特电力环保科技有限公司 Perovskite-type substance La<1-x>Sr<x>CrO<3>, heat-engine plant denitration composite catalyst, and preparation methods of perovskite-type substance La<1-x>Sr<x>CrO<3> and heat-engine plant denitration composite catalyst
CN104060348A (en) * 2014-06-16 2014-09-24 东华大学 Preparation method of polyacrylonitrile-based nano porous carbon fibers by using polyhedral oligomeric silsesquioxane as pore-foaming agent, and polyacrylonitrile-based nano porous carbon fibers
CN105289676A (en) * 2015-10-27 2016-02-03 展宗城 Foam-like low-temperature SCR catalyst and preparation method thereof
CN105854831A (en) * 2016-06-20 2016-08-17 浙江澄宇环保新材料股份有限公司 Calcium carbonate compound for desulfurization and denitrification
CN106111149A (en) * 2016-06-16 2016-11-16 浙江三龙催化剂有限公司 Boats and ships denitrating catalyst and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101444727A (en) * 2008-12-17 2009-06-03 中材高新材料股份有限公司 Integral honeycombed catalyst for SCR flue-gas denitration and preparation method therefor
CN103861581A (en) * 2012-12-14 2014-06-18 上海郎特电力环保科技有限公司 Perovskite-type substance La<1-x>Sr<x>CrO<3>, heat-engine plant denitration composite catalyst, and preparation methods of perovskite-type substance La<1-x>Sr<x>CrO<3> and heat-engine plant denitration composite catalyst
CN104060348A (en) * 2014-06-16 2014-09-24 东华大学 Preparation method of polyacrylonitrile-based nano porous carbon fibers by using polyhedral oligomeric silsesquioxane as pore-foaming agent, and polyacrylonitrile-based nano porous carbon fibers
CN105289676A (en) * 2015-10-27 2016-02-03 展宗城 Foam-like low-temperature SCR catalyst and preparation method thereof
CN106111149A (en) * 2016-06-16 2016-11-16 浙江三龙催化剂有限公司 Boats and ships denitrating catalyst and preparation method thereof
CN105854831A (en) * 2016-06-20 2016-08-17 浙江澄宇环保新材料股份有限公司 Calcium carbonate compound for desulfurization and denitrification

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