CN103272580B - A kind of half-dried mixing preparation method of titanium tungsten composite oxide powder - Google Patents
A kind of half-dried mixing preparation method of titanium tungsten composite oxide powder Download PDFInfo
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- CN103272580B CN103272580B CN201310164657.7A CN201310164657A CN103272580B CN 103272580 B CN103272580 B CN 103272580B CN 201310164657 A CN201310164657 A CN 201310164657A CN 103272580 B CN103272580 B CN 103272580B
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Abstract
The invention belongs to field of environment protection, specially contain TiO2And WO3Synthetic method of a double-component composite oxide.The synthetic method includes：Appropriate metatitanic acid solid is taken, and it is fine particle metatitanic acid solid to be broken up using the dT of intensive mixer half；In a heated condition, ammonium paratungstate is dissolved in monoethanolamine or hydrogen peroxide nitric acid mixed solution simultaneously；Then secondary tungsten acid ammonium solution and surfactant are added directly into metatitanic acid fine particle, the pH value of material is adjusted with ammoniacal liquor；Carry out mixing with after draining for a period of time using intensive mixer, directly calcined 3~8 hours in rotary kiln, calcined product wears into powder by ball mill or Ultrafine Grinding, you can synthesis TiO2‑WO3Composite oxide powder.Obtained TiO2‑WO3The crystal formation of composite oxides is anatase structured, even particle size, the suitable (80~150m of specific surface area2/g).In the present invention, half-dried mixed head product can be calcined directly, with product composition is controllable, excellent performance, the features such as operating process is simple, it is easy to accomplish large-scale industrial production, and pollutant ammonia excluded by gas phase it is easily controllable.
Description
Technical field
It is specially a kind of for SCR denitration carrier the invention belongs to field of environment protection
The half-dried mixing preparation method of TiO2-WO3 composite oxide powders.
Background technology
Nitrogen oxides (including NO, NO2, abbreviation NOx) is one of coal-burning power plant's major pollutants discharged, and it is to environment
Pollution is increasingly valued by the people, because it can not only cause acid rain and greenhouse effects, can also be with hydrocarbons and smelly
Oxygen acts on forming chemical fumes, while causing the destruction of ozone layer.The main method for being presently used for removing nitrogen oxides is selection
Property catalytic reduction technique (SCR), and the core of the technology is exactly catalyst, the performance of catalyst directly influences SCR system
Denitration performance.
The SCR catalyst commonly used on our times is all to be supported on oxide or composite oxide carrier with active material
On be prepared.Show through numerous studies, using anatase type tio2 as carrier, used as co-catalyst, V2O5 is used as activity for WO3
The V2O5/TiO2-WO3 systems of component, show optimal denitration efficiency and selectivity.
In the V2O5/TiO2-WO3 catalyst that coal-burning power plant uses, TiO2-WO3 oxides as active component load
Body, accounts for the 80%~90% of catalyst total amount；.It follows that titanium dioxide account for total catalyst weight with the content of tungsten oxide
The overwhelming majority, developing high performance titanium tungsten composite oxide powder has important economic benefit and realistic meaning.
Complex procedures and the serious problem of ammonia pollution in TiO2-WO3 oxides are prepared for current wet method, the present invention is provided
The preparation method that can be directly calcined after a kind of half dry-mixing, with product component control accuracy is high, high specific surface area
And stable homogeneous, the features such as operating process is simple, it is easy to accomplish large-scale industrial production, and pollutant ammonia excluded by gas phase it is easy
In control.
The content of the invention
Present invention aim at a kind of TiO2-WO3 oxide composites for SCR denitration carrier of synthesis,
The TiO2-WO3 oxide composites for SCR denitration carrier, specific surface area is 80-150m2/g；Granularity is
3-15 μm, the mass fraction of tungstic acid is 3%-15%, the preparation method of the TiO2-WO3 oxide composites, including
Following steps：
(1) metatitanic acid solid is broken up in intensive mixer, obtains metatitanic acid fine particle, intensive mixer be with
The tilting intensive mixer of pumped vacuum systems and heating system, intensive mixer rotating speed is 500~700 turns/min, is strongly stirred
Mixed process temperature of charge is mixed for 50~70 DEG C；
(2) in ammonium paratungstate being dissolved in into monoethanolamine or hydrogen peroxide-nitric acid mixed solution, secondary tungsten acid ammonium solution is obtained；
(3) secondary tungsten acid ammonium solution is added in metatitanic acid fine particle, continues strong stirring mixing；
(4) surfactant is added in the metatitanic acid fine particle mixture that step (3) is obtained, continues strong stirring
Mixing；
(5) solution ph is adjusted with ammoniacal liquor, continues strong stirring mixing and draining；
(6) strong stirring mixes carries out temperature programming calcining with the material obtained after draining；
(7) calcination product is ground, obtains satisfactory material.
Preferably, raw material metatitanic acid moisture is 40%~50%.
Preferably, the mass ratio of the quality of ammonium paratungstate and monoethanolamine is 3: 1.5~1, the quality of ammonium paratungstate with it is double
The volume ratio of oxygen water-nitric acid mixed solution is 1: 1~1.5.
Preferably, hydrogen peroxide and the mass ratio of nitric acid are 10: 0.5~1 in hydrogen peroxide-nitric acid mixed solution.
Preferably, the ammonia concn of regulation pH is 20%~25%, and regulation pH value is 7~11.
Preferably, it is 30%~40% that strong stirring mixes and material moisture is obtained after draining.
Preferably, the speed of temperature programming be 5~15 DEG C/min, calcining heat be 400~600 DEG C, calcination time be 3~
8 hours.
Preferably, the Ginding process for using is ball-milling method or Ultrafine Grinding polishing.
Compared with prior art, have the following advantages：
(1) preparation method of the invention, can Simplified flowsheet, reduction without metatitanic acid solid is made into slurries without drying
Energy consumption, and properties of product stable homogeneous.
(2) preparation method of the invention can reduce the control difficulty to pollutant.
(3) preparation method of the invention reduces the loss of raw material ammonium paratungstate and metatitanic acid, and component control accuracy is high, into
This is low.
Specific embodiment
Come to be further described the present invention (agents useful for same is for chemistry is pure in embodiment) by the following examples, need
It should be noted that the following examples are used only as example, present invention is not limited thereto.
Embodiment 1：Tungstic acid content is the preparation of the TiO2-WO3 oxide composites of 10wt%.
Step 1：By 300kg metatitanic acid solids in intensive mixer with 600 turns/min rotating speed mixing 0.5h, by metatitanic acid
Solid breaks up the fine particle less than 0.5mm as diameter.
Step 2：18.7kg ammonium paratungstates are dissolved in 6.2kg monoethanolamines, the solution of ammonium paratungstate is obtained.
Step 3：Secondary tungsten acid ammonium solution is added in metatitanic acid fine particle, continues strong stirring mixing 0.5h.
Step 4：3kg surfactants are added in the metatitanic acid fine particle mixture obtained in step 3, continue strong
Power stirring mixing 0.5h.
Step 5：Solution ph to 8.3 is adjusted with ammoniacal liquor, continuing strong stirring mixing 0.5h, draining 0.5h to moisture is
40% solid.
Step 6：The product that step 5 is obtained is raised to 550 DEG C of calcining 4h with 10 DEG C/min heating rates.
Step 7：Calcination product is carried out into Ultrafine Grinding to be ground, the TiO2-WO3 that granularity (D90) is 6 μm is obtained and is combined
Oxide powder.
Embodiment 2：Tungstic acid content is the preparation of the TiO2-WO3 oxide composites of 5wt%.
Step 1：By 300kg metatitanic acid solids in intensive mixer with 600 turns/min rotating speed mixing 0.5h, by metatitanic acid
Solid breaks up the fine particle less than 0.5mm as diameter.
Step 2：8.9kg ammonium paratungstates are dissolved in 3kg monoethanolamines, the solution of ammonium paratungstate is obtained.
Step 3：Secondary tungsten acid ammonium solution is added in metatitanic acid fine particle, continues strong stirring mixing 0.5h.
Step 4：3kg surfactants are added in the metatitanic acid fine particle mixture that step 3 is obtained, continue strength
Stirring mixing 0.5h.
Step 5：Solution ph to 8.5 is adjusted with ammoniacal liquor, continuing strong stirring mixing 0.5h, draining 0.5h to moisture is
35% solid.
Step 6：The product that step 5 is obtained is raised to 550 DEG C of calcining 4h with 10 DEG C/min heating rates.
Step 7：Calcination product is carried out to utilize ball mill grinding, the TiO2-WO3 that granularity (D90) is 3 μm is obtained and is combined
Oxide powder.
Embodiment 3：Tungstic acid content is the preparation of the TiO2-WO3 oxide composites of 8wt%.
Step 1：By 300kg metatitanic acid solids in intensive mixer with 600 turns/min rotating speed mixing 0.5h, by metatitanic acid
Solid breaks up the fine particle less than 0.5mm as diameter.
Step 2：14.7kg ammonium paratungstates are dissolved in 14.7kg hydrogen peroxide-nitric acid mixed solution, ammonium paratungstate is obtained molten
Liquid.
Step 3：Secondary tungsten acid ammonium solution is added in metatitanic acid fine particle, continues strong stirring mixing 0.5h.
Step 4：3kg surfactants are added in the metatitanic acid fine particle mixture that step 3 is obtained, continue strength
Stirring mixing 0.5h.
Step 5：Solution ph to 8.5 is adjusted with ammoniacal liquor, continuing strong stirring mixing 0.5h, draining 0.5h to moisture is
39% solid.
Step 6：The product that step 5 is obtained is raised to 550 DEG C of calcining 4h with 10 DEG C/min heating rates.
Step 7：Calcination product is carried out to utilize ball mill grinding, the TiO2-WO3 that granularity (D90) is 5 μm is obtained and is combined
Oxide powder.
Brief description of the drawings
Fig. 1 is the XRD spectra of the sample that the WO3 mass fractions prepared by embodiment two are 5%；
Fig. 2 is the content of each component in the sample that the WO3 mass fractions prepared by embodiment two are 5%.
Claims (8)
1. a kind of preparation method of TiO2-WO3 oxide composites for SCR denitration carrier, described for SCR
The TiO2-WO3 oxide composites of denitration catalyst carrier, specific surface area is 80-150m2/g；Granularity is 3-15 μm, three oxygen
The mass fraction for changing tungsten is 3%-15%, it is characterised in that the preparation method of the TiO2-WO3 oxide composites, including
Following steps：
(1) metatitanic acid solid is broken up in intensive mixer, obtains metatitanic acid fine particle, intensive mixer is true with taking out
The tilting intensive mixer that empty set is united with heating system, intensive mixer rotating speed is 500~700 turns/min, and strong stirring is mixed
It is 50~70 DEG C to close process materials temperature；
(2) in ammonium paratungstate being dissolved in into monoethanolamine or hydrogen peroxide-nitric acid mixed solution, secondary tungsten acid ammonium solution is obtained；
(3) secondary tungsten acid ammonium solution is added in metatitanic acid fine particle, continues strong stirring mixing；
(4) surfactant is added in the metatitanic acid fine particle mixture that step (3) is obtained, continues strong stirring and mix
Close；
(5) solution ph is adjusted with ammoniacal liquor, continues strong stirring mixing and draining；
(6) strong stirring mixes carries out temperature programming calcining with the material obtained after draining；
(7) calcination product is ground, obtains satisfactory material.
2. the preparation method of the TiO2-WO3 oxide composites of SCR denitration carrier is used for described in claim 1, its
It is characterised by, raw material metatitanic acid moisture is 40%~50%.
3. the preparation method of the TiO2-WO3 oxide composites of SCR denitration carrier is used for described in claim 1, its
It is characterised by, the quality of ammonium paratungstate is 3: 1.5~1 with the mass ratio of monoethanolamine, quality and the hydrogen peroxide-nitre of ammonium paratungstate
The volume ratio of sour mixed solution is 1: 1~1.5.
4. the preparation method of the TiO2-WO3 oxide composites of SCR denitration carrier is used for described in claim 1, its
It is characterised by, hydrogen peroxide and the mass ratio of nitric acid are 10: 0.5~1 in hydrogen peroxide-nitric acid mixed solution.
5. the preparation method of the TiO2-WO3 oxide composites of SCR denitration carrier is used for described in claim 1, its
It is characterised by, the ammonia concn for adjusting pH is 20%~25%, regulation pH value is 7~11.
6. the preparation method of the TiO2-WO3 oxide composites of SCR denitration carrier is used for described in claim 1, its
It is characterised by, it is 30%~40% that material moisture is obtained after strong stirring mixing and draining.
7. the preparation method of the TiO2-WO3 oxide composites of SCR denitration carrier is used for described in claim 1, its
It is characterised by, the speed of temperature programming is 5~15 DEG C/min, and calcining heat is 400~600 DEG C, and calcination time is 3~8 hours.
8. the preparation method of the TiO2-WO3 oxide composites of SCR denitration carrier is used for described in claim 1, its
It is characterised by, the Ginding process for using is ball-milling method or Ultrafine Grinding polishing.
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| CN103586017B (en) * | 2013-11-22 | 2015-03-25 | 西南化工研究设计院有限公司 | Preparation method of titanium and tungsten powder for flue gas denitration catalyst and product prepared through preparation method |
| CN105727931A (en) * | 2016-03-17 | 2016-07-06 | 辽宁鑫隆科技有限公司 | Preparation method of low-temperature and non-toxic SCR denitration catalyst |
| CN108246309A (en) * | 2017-12-29 | 2018-07-06 | 湖北神雾热能技术有限公司 | A kind of transition metal denitrating catalyst powder and preparation method thereof |
| CN108816216A (en) * | 2018-06-29 | 2018-11-16 | 凯龙高科技股份有限公司 | A kind of high temperature modification SCR catalyst and its preparation method and application |
| CZ2019555A3 (en) * | 2019-08-26 | 2020-06-10 | Unipetrol výzkumně vzdělávací centrum, a.s. | Process for producing mixed titanium oxides |
| US11986801B1 (en) | 2024-02-12 | 2024-05-21 | King Faisal University | Synthesis of a Au-(TiO2-x/WO3-x) semiconductor composite using fluidized bed chemical vapor deposition (FBCVD) |
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| CN102294273B (en) * | 2011-07-19 | 2013-02-13 | 四川华铁钒钛科技股份有限公司 | Preparation method for TiO2-WO3 composite powder used as catalyst carrier |
| CN102896002B (en) * | 2012-10-10 | 2014-10-29 | 浙江海亮环境材料有限公司 | Method for preparing titanium dioxide-tungsten trioxide (TiO2-WO3) composite powder |
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