CN104108751B - A kind of preparation method of anatase crystal titanium dioxide - Google Patents
A kind of preparation method of anatase crystal titanium dioxide Download PDFInfo
- Publication number
- CN104108751B CN104108751B CN201310144882.4A CN201310144882A CN104108751B CN 104108751 B CN104108751 B CN 104108751B CN 201310144882 A CN201310144882 A CN 201310144882A CN 104108751 B CN104108751 B CN 104108751B
- Authority
- CN
- China
- Prior art keywords
- tio
- roasting
- preparation
- metatitanic acid
- steam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000013078 crystal Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004408 titanium dioxide Substances 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 238000010792 warming Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000004899 motility Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The preparation method that the present invention provides a kind of anatase crystal titanium dioxide for SCR denitration.With Production By Sulfuric Acid Process TiO2Wet metatitanic acid in technique is raw material, under certain atmosphere, by the mode of ramped heating schedule substep roasting sample, realizes the control to titanium dioxide specific surface area and crystal particle diameter size by changing roasting condition.It is an advantage of the current invention that raw material is easy to get, preparation method is simple, need not introduce other materials in preparation process.
Description
One, technical field:
The present invention relates to a kind of specific surface area and the preparation method of the controlled anatase crystal titanium dioxide of crystal particle diameter size.
Two, background technology:
Nitrogen oxides (NOx) it is one of the main harmful substance of atmosphere pollution.Since the nineties in 20th century, China is along with the increase of economic sustained and rapid development and energy-consuming, annual NOxDischarge capacity constantly rises.NOxPollutant emission problem caused the great attention of government, current country to require building, extend and newly-built fired power generating unit to be listed denitrating system in construction plan in.
SCR (SelectiveCatalyticReduction, SCR) method has denitration efficiency height, the feature that side effect is less, it has also become home and abroad station and the most ripe mainstream technology of Industrial Stoves denitration.The industrial SCR catalyst obtaining large-scale application at present is mainly load at Detitanium-ore-type TiO2V on carrier2O5-WO3/TiO2And V2O5-MoO3/TiO2Catalyst.V2O5-WO3/TiO2Or V2O5-MoO3/TiO2Catalyst is in the practical application of denitration of boiler smoke, suitable geometry must be manufactured, make it have sufficiently large surface area while keeping compared with high abrasion resistance strength and mechanical strength, so could meet the requirement to SCR catalyst activity and life-span of the denitration engineer applied.This is to the major part TiO in SCR catalyst particularly catalyst2Tool has high requirements, and has both required TiO2For anatase crystal, it is also desirable to have bigger specific surface area and suitable crystal particle diameter size.Its TiO of manufacturer of domestic most SCR catalyst2Powder body relies primarily on import.Therefore the TiO that SCR catalyst requires is met2Be prepared by SCR catalyst technology emphasis and a difficult point of powder body.
The TiO bigger in order to prepare specific surface area2Powder body, tungstenic solution is mixed by Chinese invention patent CN101757907A with metatitanic acid slurry, and spray drying directly prepares powder body, and the metatitanic acid powder surface so obtained has been coated with tungsten compound equably, in follow-up roasting process, tungsten can stop TiO effectively2The carrying out of crystallization, thus obtaining bigger surface area.Chinese invention patent CN101318697A adds organic surface active agent when modulating metatitanic acid slurry in system, changes the physical arrangement of metatitanic acid, obtains the TiO of high-specific surface area after super-dry, calcining2.And can control for SCR catalyst TiO at present2The method of crystal particle diameter size, particularly to effectively control TiO simultaneously2Specific surface area and the method for crystal particle diameter size be rarely reported.
The present invention wet metatitanic acid from the Production By Sulfuric Acid Process technique of the current main flow of China, can control TiO respectively by adjusting heat treated condition2Specific surface area and crystal particle diameter size, this TiO2It is suitable for preparing denitrifying catalyst with selective catalytic reduction.This method has raw material and is easy to get, and preparation method is simple, and need not introduce the feature of other materials in preparation process.
Three, summary of the invention:
The present invention provides a kind of specific surface area and the controlled anatase crystal TiO of crystal particle diameter size2Preparation method.
The method have the characteristics that the wet metatitanic acid from the Production By Sulfuric Acid Process technique of the current main flow of China, by dry, many one-step bakings, select still air, moving air, flowing nitrogen time simultaneously as needed in roasting, moving air carries steam or flowing nitrogen carries the different atmospheres such as steam and adjusts and control target TiO2Specific surface area and crystal particle diameter size.The TiO that this method prepares2It is suitable for preparing denitrifying catalyst with selective catalytic reduction.Additionally also having raw material to be easy to get, method is simple, the advantage that need not introduce other materials in preparation process.
Anatase crystal TiO is set forth below2Preparation method.
With Production By Sulfuric Acid Process TiO2Wet metatitanic acid in technique is raw material, dry complete at 100-200 DEG C, obtains dry metatitanic acid.Putting in Muffle furnace by dry metatitanic acid, temperature programming to 250-400 DEG C, roasting was product A after 1-10 hour.Putting in Muffle furnace by product A, temperature programming to 300-700 DEG C, roasting was product B after 1-10 hour, and product B is the TiO of anatase crystal2.Carry out under a kind of atmosphere that roasting process can select still air, moving air, flowing nitrogen, moving air to carry steam or flowing nitrogen carries in steam.During water flowing steam, allow air or nitrogen by temperature be 30-95 DEG C between distilled water.
It is an advantage of the current invention that raw material is easy to get, preparation method is simple, need not introduce other materials, just can control target TiO respectively by adjusting heat treated condition in preparation process2Specific surface area and crystal particle diameter size, production has enough motilities and controllability, the TiO obtained2It is suitable for preparing denitrifying catalyst with selective catalytic reduction.
Four, detailed description of the invention:
The following examples are for being specifically described the present invention.Embodiment is not intended to the usage range of the present invention and is limited in the condition of embodiment narration.TiO in embodiment2Sample passes through N2Absorption representation, according to BET method calculated specific surface area；Characterized by powder X-ray RD diffraction, calculate TiO according to Scherrer formula2Crystal particle diameter size.
Embodiment 1
With Production By Sulfuric Acid Process TiO2Wet metatitanic acid in technique is raw material, and 120 DEG C dry 24 hours, obtain dry metatitanic acid.Putting in Muffle furnace by dry metatitanic acid, 5 DEG C/min is warming up to 300 DEG C of roastings 4 hours, obtains product A.Product A is put into 10 DEG C/min in Muffle furnace and is warming up to 500 DEG C of roastings 4 hours, obtain the TiO of anatase crystal2。
Embodiment 2
With Production By Sulfuric Acid Process TiO2Wet metatitanic acid in technique is raw material, and 120 DEG C dry 24 hours, obtain dry metatitanic acid.Putting in Muffle furnace by dry metatitanic acid, 5 DEG C/min is warming up to 300 DEG C of roastings 4 hours, obtains product A.Product A is put into 10 DEG C/min in Muffle furnace and is warming up to 550 DEG C of roastings 1 hour, obtain the TiO of anatase crystal2。
Embodiment 3
With Production By Sulfuric Acid Process TiO2Wet metatitanic acid in technique is raw material, and 120 DEG C dry 24 hours, obtain dry metatitanic acid.Putting in Muffle furnace by dry metatitanic acid, 5 DEG C/min is warming up to 300 DEG C of roastings 4 hours, obtains product A.Product A is put into 10 DEG C/min in Muffle furnace and is warming up to 600 DEG C of roastings 1 hour, obtain the TiO of anatase crystal2。
Embodiment 4
With Production By Sulfuric Acid Process TiO2Wet metatitanic acid in technique is raw material, and 120 DEG C dry 24 hours, obtain dry metatitanic acid.Putting in tube furnace by dry metatitanic acid, 5 DEG C/min is warming up to 250 DEG C of roastings 4 hours, obtains product A.Product A is put into 15 DEG C/min in tube furnace and is warming up to 500 DEG C, and blowing air carries the steam of 80 DEG C by sample, roasting 4 hours, obtains the TiO of anatase crystal2。
From table 1, can effectively control TiO respectively by the heat treatment condition and atmosphere changing metatitanic acid2Specific surface area and TiO2Crystal particle diameter size.
Table 1TiO2Physical data
Claims (5)
1. a specific surface area and the controlled anatase crystal TiO of crystal particle diameter size2Preparation method, it is characterized in that:
(1) with the wet metatitanic acid of Production By Sulfuric Acid Process for raw material, dry when 100-200 DEG C and must do metatitanic acid in 12-72 hour；
(2) roasting when 250-400 DEG C of dry metatitanic acid obtains product A in 1-10 hour；
(3) product A roasting when 300-700 DEG C obtains product B in 1-10 hour, and product B is the TiO of anatase crystal2；
(4) roasting process carries out under a kind of atmosphere that still air, moving air, flowing nitrogen, moving air carry steam or flowing nitrogen carries in steam.
2. method according to claim 1, takes the mode of temperature programming to heat when it is characterized in that roasting, heating rate is 0.5 DEG C/min-20 DEG C/min.
3. method according to claim 1 or claim 2, atmosphere when it is characterized in that roasting is that moving air carries steam or flowing nitrogen carries steam, and the temperature of steam is 30-95 DEG C.
4. method according to claim 1, is characterized in that step (2) roasting 2-8 hour when 250-350 DEG C.
5. method according to claim 1, is characterized in that step (3) roasting 2-8 hour when 400-600 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310144882.4A CN104108751B (en) | 2013-04-22 | 2013-04-22 | A kind of preparation method of anatase crystal titanium dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310144882.4A CN104108751B (en) | 2013-04-22 | 2013-04-22 | A kind of preparation method of anatase crystal titanium dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104108751A CN104108751A (en) | 2014-10-22 |
| CN104108751B true CN104108751B (en) | 2016-07-06 |
Family
ID=51705770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310144882.4A Active CN104108751B (en) | 2013-04-22 | 2013-04-22 | A kind of preparation method of anatase crystal titanium dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104108751B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111573722B (en) * | 2020-04-29 | 2021-03-16 | 华东理工大学 | Method for realizing particle size normalization of titanium dioxide |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6576589B1 (en) * | 1999-09-20 | 2003-06-10 | Lg Electronics Inc. | Method for making anatase type titanium dioxide photocatalyst |
| CN101318697A (en) * | 2008-07-11 | 2008-12-10 | 四川华铁钒钛科技股份有限公司 | Method for preparing titanium dioxide product for high-specific surface area denitrating catalyst |
| CN101318698A (en) * | 2008-07-11 | 2008-12-10 | 四川华铁钒钛科技股份有限公司 | Method for preparing anatase type nano-titanium dioxide |
| CN101757907A (en) * | 2008-12-26 | 2010-06-30 | 晶锐瓷业（北京）有限公司 | Titanium dioxide powder containing tungsten for preparing honeycomb SCR DeNOx catalyst and preparation method thereof |
| CN102583522A (en) * | 2012-01-09 | 2012-07-18 | 四川华铁钒钛科技股份有限公司 | Preparation method for titanium dioxide serving as catalyst carrier |
-
2013
- 2013-04-22 CN CN201310144882.4A patent/CN104108751B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6576589B1 (en) * | 1999-09-20 | 2003-06-10 | Lg Electronics Inc. | Method for making anatase type titanium dioxide photocatalyst |
| CN101318697A (en) * | 2008-07-11 | 2008-12-10 | 四川华铁钒钛科技股份有限公司 | Method for preparing titanium dioxide product for high-specific surface area denitrating catalyst |
| CN101318698A (en) * | 2008-07-11 | 2008-12-10 | 四川华铁钒钛科技股份有限公司 | Method for preparing anatase type nano-titanium dioxide |
| CN101757907A (en) * | 2008-12-26 | 2010-06-30 | 晶锐瓷业（北京）有限公司 | Titanium dioxide powder containing tungsten for preparing honeycomb SCR DeNOx catalyst and preparation method thereof |
| CN102583522A (en) * | 2012-01-09 | 2012-07-18 | 四川华铁钒钛科技股份有限公司 | Preparation method for titanium dioxide serving as catalyst carrier |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104108751A (en) | 2014-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5844457B2 (en) | Method for producing surface-deposited honeycomb flue gas denitration catalyst | |
| CN104014331B (en) | The preparation method of the Mn-Ce-W composite oxides denitrating catalyst of mesoporous TiO 2 ball load | |
| WO2019006895A1 (en) | Preparation method and use of trifolium-shaped catalyst for cooperatively controlling nox and cvocs | |
| CN107282034A (en) | A kind of preparation method and applications of wide temperature catalyst for denitrating flue gas | |
| CN103191718A (en) | Preparation method of low-cost honeycomb denitration catalyst | |
| CN106475129B (en) | Using hexagonal boron nitride as the preparation method of the composite oxides denitrating catalyst of carrier | |
| CN104174442A (en) | Low-temperature flue gas denitration catalyst forming process | |
| CN105854874B (en) | Denitrating catalyst and preparation method thereof and the application in denitrating flue gas | |
| CN105771961B (en) | A kind of CeO2Nanotube supported denitrating catalyst and preparation method thereof | |
| CN111036192A (en) | Coating type wear-resistant vanadium denitration catalyst and preparation method and application thereof | |
| CN105396579A (en) | Fire coal flue gas denitration demercuration catalyst and preparation method and application thereof | |
| CN105289586B (en) | Spherical cerium manganese composite oxides low-temperature denitration catalyst and its preparation method and application | |
| CN104128188A (en) | Denitration catalyst used in waste incineration power plant and preparation method thereof | |
| CN106732709B (en) | A kind of preparation process of corrugated plate dst denitrating catalyst | |
| CN104108751B (en) | A kind of preparation method of anatase crystal titanium dioxide | |
| CN104368334B (en) | A kind of denitrating catalyst and preparation method thereof | |
| CN105776311A (en) | Method for preparing copper oxide nano material | |
| CN105032398B (en) | A kind of sheet-like morphology is carrier V2O5/TiO2Low temperature NH3The preparation of SCR catalyst and its application in denitration | |
| CN109078631A (en) | The Ce base catalyst preparation and NOx of efficient cryogenic eliminate performance study | |
| CN102698759A (en) | Preparation method of expanded perlite loaded nanometer TiO2 compound photocatalysis material | |
| CN105126813A (en) | High-specific-surface denitration catalyst and preparation and application thereof | |
| CN205235760U (en) | Air purification device and air conditioner | |
| CN105771956A (en) | Tin-titanium denitration catalyst and preparation method therefor | |
| CN108671965A (en) | A kind of semicoke low temperature SCR denitration catalyst and preparation method thereof | |
| CN105339083A (en) | Denitration catalyst and method for producing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 211900, No. 9, Central Avenue, Yangzhou chemical industry park, Jiangsu, Yizheng Applicant after: YANGZHOU INSTITUTE OF CHEMISTRY AND CHEMICAL ENGINEERING, NANJING University Address before: 211900 No. 1, the Great Wall Road, Yangzhou chemical industry park, Jiangsu, Yizheng Applicant before: YANGZHOU INSTITUTE OF CHEMISTRY AND CHEMICAL ENGINEERING, NANJING University |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231122 Address after: 225000 9 Central Avenue, Qingshan Town, Yizheng City, Yangzhou City, Jiangsu Province Patentee after: Yangzhou Bokele Bio-pharmaceutical Technology Co.,Ltd. Address before: No. 9 Central Avenue, Yangzhou Chemical Industry Park, Yizheng City, Jiangsu Province, 211900 Patentee before: YANGZHOU INSTITUTE OF CHEMISTRY AND CHEMICAL ENGINEERING, NANJING University |
|
| TR01 | Transfer of patent right |