CN102603005B - Method for preparing nanometer molybdenum trioxide - Google Patents
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- CN102603005B CN102603005B CN2012100576106A CN201210057610A CN102603005B CN 102603005 B CN102603005 B CN 102603005B CN 2012100576106 A CN2012100576106 A CN 2012100576106A CN 201210057610 A CN201210057610 A CN 201210057610A CN 102603005 B CN102603005 B CN 102603005B
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Abstract
The invention relates to the technical field of nonferrous metallurgy, in particular to a method for preparing nanometer molybdenum trioxide and using pure molybdenum trioxide as a raw material. The pure molybdenum trioxide is used as the raw material, the nanometer molybdenum trioxide is prepared by means of plasma sublimation, pure molybdenum trioxide powder is fed into a plasma subliming furnace via a feeding device and is sublimed in plasma flow, operation time ranges from 10ms to 100ms, obtained gaseous molybdenum trioxide is in shock cooling by the aid of shock cooling media and collected by a receiving device, the nanometer molybdenum trioxide is obtained, and content of MoO3 is higher than 99.80%. The molybdenum trioxide is prepared by the aid of a plasma sublimation method, the high-purity nanometer molybdenum trioxide with the granularity within 80nm can be obtained in a super-short time period, and automatic and continuous production is truly realized.
Description
Technical field
The present invention relates to the non-ferrous metallurgy technology field, especially relate to and a kind ofly take pure molybdic oxide and prepare the method for nanometer molybdic oxide as raw material.
Background technology
Molybdic oxide is most important intermediate in molybdenum metallurgy, and the compound of most of molybdenums all directly or indirectly take that it makes as raw material, and molybdic oxide all is widely used in fields such as catalyzer, display unit, sensor, dynamo batteries.
The industrial general method with the calcination ammonium molybdate is produced molybdic oxide, development along with Materials science and utilisation technology, the molybdic oxide that the method makes because particle is thick, be aggregating state and can not meet the Special use requirement, as Guo Guanghua etc. discloses a kind of preparation method of high-purity molybdenum trioxide used for hydrofining catalyst of petroleum in CN102198958, ammonium tetramolybdate is dry, send into the return bend electric furnace after sieving and carry out roasting, the one-pass finished rate reaches 98.5%.
There is significant vapour pressure at lower temperature due to molybdic oxide, so can be purified molybdic oxide by subliming method, under the operational condition of distillation, the common impurity of symbiosis or do not there is volatility (as silicate etc.) or can not condensation and be removed with it.
At present, the main raw material that industrial subliming method is produced pure molybdic oxide is that industrial molybdenum oxide is the molybdenum calcining, according to molybdenum oxide fusing point in the molybdenum calcining, boiling point is low, start distillation during lower than 795 ℃ of its fusing points in temperature, form with the trimerization molybdenum oxide enters gas phase, the molybdic oxide steam together enters in the fan housing that gathers dust together with air and enter cloth bag under the draft effect and collects, and most of impurity compounds are because of fusing point, the boiling point height is a lot stayed in solid phase, distillation is carried out in the rotation electric furnace, the sublimation temperature general control is at 900～1100 ℃, the general purity of the molybdic oxide of producing is to MoO
399.8%(opens to open and repaiies, Zhao Qinsheng chief editor, " tungsten metallurgy ", in September, 2005), the researchist of Korea S invents a kind of sublimation stove, and this stove ratio is large with the subliming furnace throughput at the bottom of rotary oven, energy consumption low (a civilian bell-shaped percussion instrument, used in ancient time by troops on march, Progress of Research And Development For Molybdenum Oxide, " China Molybdenum Industry ", 2006 years the 1st phases), US4551313 discloses a kind of slag ingredient (silicon that contains into, aluminium and heavy metal) the quick sublimation method of molybdic oxide, the first step: flow the molybdenum oxide particle of carrying by pneumatic suspension, the fuel of carrying by nozzle and oxygen-containing gas mixed flow enter in a sealing furnace chamber, fuel gas mixture is lighted and is produced temperature and be enough to make the molybdic oxide distillation 200 ℃～1800 ℃ of 1600 scholars, be melted into the flame of slag ingredient, collect the liquid slag in furnace chamber, second step: gas and the suspended solids of the molybdic oxide that comprises distillation that will produce enter a condensing chamber by above-mentioned furnace chamber, the temperature of condensing chamber (850～950 ℃) is higher than the condensing temperature of the molybdic oxide of distillation, volatilization temperature lower than volatile metal impurity, then condensation (150～500 ℃), collect solid-state molybdic oxide, separate waste gas, thereby realize separating of molybdic oxide and impurity, result shows, sneak into molybdenum in slag lower than 1%, obtain product molybdic oxide purity and reach MoO
399.95%.
Although adopt above-mentioned these methods can obtain the molybdic oxide of higher degree, but still have following several problem: 1, molybdenum recovery is starkly lower than 75%, has offset product purity and improved the advantage of bringing; 2, owing to passing into large quantity of air stream in stove, most of heat is not for the product that distils, but is used to improve the temperature of introducing air; 3, the product molybdic oxide mean particle size made, at micron order, can not meet the particular requirement in the fields such as Materials science.
Existing research is found, there is anisotropic nanometer molybdic oxide, more demonstrate its special catalytic performance, can be widely used as catalyzer, conventional subliming method adopts gather dust fan housing and cloth bag collection molybdic oxide, because the particle coacervation only obtains the micron order product, for the preparing nano molybdic oxide, must the molybdic oxide gas of distillation is hurried cooling, prevent the coacervation of molybdic oxide particle or reunion, thereby obtain the nano level product.
US6468497 discloses a kind of production method of nanometer molybdic oxide, adopt distillation-quenching method to produce the nanometer molybdic oxide industrial molybdenum oxide, production technique is as follows: the industrial molybdenum oxide powder of about 24～260 μ m of granularity (usually being comprised of molybdic oxide and molybdenum dioxide) is sent in subliming furnace through controlled worm conveyer, blasting air through entrance makes molybdenum dioxide be oxidized to molybdic oxide, subliming furnace heats with electric power, detect temperature in stove with thermopair, when furnace temperature reaches 1100 ℃, molybdic oxide starts to distil and is deposited on like in membranaceous feed-pipe; The nanometer molybdic oxide liquid nitrogen stream quenching distilled, enter hopper, then inflow filter, through blower fan sucking-off cold air, nanometer molybdic oxide product is discharged through funnel, the reaction sublimation temperature is 1093～1260 ℃, and the activity duration of subliming furnace is 120min, but the approximately long 100nm of output, wide 25nm, high 20nm be strip nano level molybdic oxide.
Although aforesaid method can make the nano level product, the problem existed is: the distillation time is long, generally, more than 120min, can not carry out serialization production.
Zhao Qinsheng etc. propose a kind of method of molybdenum oxide plasma physics vapour deposition process high purity molybdic oxide, process commercially pure molybdenum oxide (being the molybdenum calcining) with air plasma, utilize the characteristics that the molybdic oxide boiling point is lower than most of impurity, make its volatilization rapidly in the air plasma flame, then introduce a large amount of freezing airs and make the quenching of gaseous state molybdic oxide outside flame passes, obtain superfine high-purity molybdic oxide powder.Because employing plasma method, estimate that the production time can shorten greatly, but the method: 1, for guaranteeing the rapid volatilization of molybdic oxide under condition of plasma, flame passes must keep comparatively high temps (more than 2000 ℃), cause most of impurity in raw material molybdenum calcining also to volatilize and enter gas phase, final condensation also follows molybdic oxide to enter in product, affects product purity; 2, the method is only an imagination, without industrial application, even without experimental installation (Zhang Qixiu, Zhao Qinsheng chief editor, " tungsten metallurgy ", in September, 2005).
Summary of the invention
On the basis of existing technology, the object of the present invention is to provide and a kind ofly take pure molybdic oxide and prepare the method for nanometer molybdic oxide as raw material using plasma distillation, ultra-short Time, can realize automatization, serialization production.
A kind of method for preparing the nanometer molybdic oxide, take pure molybdic oxide as raw material, by plasma body, distils and prepare the nanometer molybdic oxide, it is characterized in that:
Pure molybdic oxide powder is sent in the plasma body subliming furnace by feeding device, distilled in plasma flow, operating time 10～100ms, the gaseous state molybdic oxide of acquisition adopts the quenching medium quenching, and material collecting device is collected, and obtains the nanometer molybdic oxide, MoO
3>99.80%.
Sublimation condition is: 2000～10000 ℃ of temperature, vacuum tightness are 10
3～10
5Micro-negative pressure of Pa.
Further, described quenching medium is water, air or liquid nitrogen.
Further, described nanometer molybdic oxide granularity≤80nm.
Further, the plasma gas that produces described plasma flow is argon gas, nitrogen, air, oxygen or other suitable gas.
The alleged pure molybdic oxide of the present invention, refer to the pure molybdic oxide that adopts ammonium molybdate pyrolysis or additive method to make, and its chemical constitution meets corresponding industry standard.
Adopt technical scheme as above, the present invention at least has following beneficial effect:
1, ultrahigh-temperature is brought ultra-short Time
In the present invention, ultrahigh-temperature heating due to plasma body, when the molybdic oxide powder enters the plasma body subliming furnace, the transmission that completes heat within the extremely short time reaches the abundant heating to powder, but distillation operates moment and completes (≤100ms), ultrahigh-temperature is brought ultra-short Time, obviously is better than existing distillation or distillation-quench technique;
2, realize automatization, serialization production
Because the present invention replaces existing rotation electric furnace or sublimation stove with the plasma body subliming furnace, can complete once, fast the volatilization distillation of molybdic oxide, form constantly reinforced, as constantly to collect finished product serialization production process, produce molybdic oxide operating time length, can not serialization production compare with existing various sublimation methods, present method has really realized automatization, serialization production, produces the nanometer molybdic oxide per year more than 400 tons;
3, product granularity is thin
The present invention adopts the quenching collection to prepare molybdic oxide, has avoided coacervation or the reunion of molybdic oxide particle, thereby has obtained the nano level product, and product granularity can be controlled in 80nm, compared with prior art, can meet the particular requirement of material science.
The accompanying drawing explanation
Fig. 1: the processing unit schematic diagram of preparation nanometer molybdic oxide of the present invention.
Main numbering explanation in figure: 1 plasma body subliming furnace; 2 receive assorted device; 3 water-cooled collection devices; 4 vacuum systems; 5 plasma gass; 6 cooling systems; 7 power interfaces; 8 feeding devices; 9 material collecting devices; 10 purge gas.
Embodiment
Describe technical scheme of the present invention in detail below in conjunction with accompanying drawing 1 and embodiment, but protection scope of the present invention includes, but are not limited to this:
The processing unit of preparation nanometer molybdic oxide of the present invention is arranged as shown in Figure 1, distillation is carried out in plasma body subliming furnace 1, and production unit also comprises feeding device 8, material collecting device 9, receives assorted device 2, vacuum system 4, cooling system 6 and water-cooled collection device 3 etc.; Pure molybdic oxide raw material powder is sent in plasma body subliming furnace 1 by feeding device 8, distilled in 2000～10000 ℃ of plasma flows that produce at plasma gas 5 bright eruptions, operating time 10～100ms; The molybdic oxide that distillation is produced is introduced water-cooled collection device 3, uses water as the quenchant quenching, and material collecting device 9 is collected, and obtains the nanometer molybdic oxide; Vacuum system 4 Controlling System vacuum tightnesss are 10
3～10
5Pa, cooling system 6 is provided with water-in and water outlet; Water-cooled collection device 3 adopts water-cooled pulse backblowing strainer, constantly passes into purge gas 10 under working order and realizes gas solid separation.
In the present invention, vacuum degree control is 10
3～10
5Micro-negative pressure of Pa, can obtain extraordinary distillation effect; In the process of distillation molybdic oxide, due to the ultra high temp of plasma generation, rate of sublimation is very fast, in ultra-short Time is time of Millisecond, completes.
The concrete operations implementation process is as follows:
1, open the water coolant of waterworks 6;
2, close feed valve, the raw material molybdic oxide is added to feeding device 8;
3, vacuum system 4 is evacuated down to setting vacuum tightness;
4, pass into plasma gas 5, produced the plasma flow of design temperature by power interface 7 access plasma power supplies;
5, pass into pulse gas 10 to water-cooled collection device 3;
6, open feed valve, continue the material powder in feeding device 8 is added in plasma body subliming furnace 1 to the operation that distils;
7, collect the product molybdic oxide from material collecting device 9, from receiving assorted device 2, collect impurity.
Can also make quenching medium with air or liquid nitrogen in practice.
Embodiment 1:
Raw material: pure molybdic oxide powder, its chemical constitution is in Table 1.
Implementation process: pure molybdic oxide raw material is sent in the plasma body subliming furnace, and the temperature of controlling plasma flow is that 2000～10000 ℃, vacuum tightness are 10
3～10
5Pa, use water as quenchant, and quenching is collected, and obtains molybdic oxide, and sampling detects.
Implement parameter and the results are shown in table 2.
As can be seen from Table 2:
1, with MoO
399.82% pure molybdic oxide is raw material, the using plasma subliming method can 100ms with interior ultra-short Time make purity more than 99.80%, the high-purity nm molybdic oxide of granularity below 80nm;
2, along with the rising of plasma body sublimation temperature, rate of sublimation is accelerated, and vacuum tightness reduces, and production capacity improves.
It should be noted last that: above explanation is only unrestricted in order to the present invention to be described; although with reference to better embodiment, the present invention is had been described in detail; those of ordinary skill in the art is to be understood that; can modify or be equal to replacement the present invention; and not breaking away from the spirit and scope of the present invention, it all should be encompassed in the middle of protection scope of the present invention.
Table 1 raw material chemical constitution
Table 2 embodiment 1 parameter and result
Claims (3)
1. a method for preparing the nanometer molybdic oxide, take pure molybdic oxide as raw material, by plasma body, distils and prepare the nanometer molybdic oxide, and the method realizes by following equipment: plasma body subliming furnace (1), receive assorted device (2); Water-cooled collection device (3); Vacuum system (4); Plasma gas (5); Cooling system (6); Power interface (7); Feeding device (8); Material collecting device (9); Purge gas (10);
Pure molybdic oxide raw material powder is sent in plasma body subliming furnace (1) by feeding device (8), distilled in 2000～10000 ℃ of plasma flows that produce at plasma gas (5) bright eruption, operating time 10～100ms; The molybdic oxide that distillation is produced is introduced water-cooled collection device (3), uses water as the quenchant quenching, and material collecting device (9) is collected, and obtains the nanometer molybdic oxide; Wherein, vacuum system (4) Controlling System vacuum tightness is 10
3～10
5Pa, cooling system (6) is provided with water-in and water outlet; Water-cooled collection device (3) adopts water-cooled pulse backblowing strainer, constantly passes into purge gas (10) under working order and realizes gas solid separation.
2. the method for preparing the nanometer molybdic oxide according to claim 1, it is characterized in that: further, the plasma gas that produces described plasma flow is argon gas, nitrogen, air or oxygen.
3. the method for preparing the nanometer molybdic oxide according to claim 1 is characterized in that: further, and described nanometer molybdic oxide granularity≤80nm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104495934B (en) * | 2014-12-12 | 2016-02-03 | 江西省鼎力金属有限公司 | The quenching of gasification state molybdenum oxide nanoparticles, collection device |
| CN105347400B (en) * | 2015-12-04 | 2016-11-09 | 湖北中澳纳米材料技术有限公司 | A kind of device and method producing high-purity nm molybdenum trioxide |
| CN105758176B (en) * | 2016-05-04 | 2017-12-29 | 湖北中澳纳米材料技术有限公司 | A kind of device for preparing high-purity nano molybdenum trioxide |
| CN109415207B (en) * | 2016-06-29 | 2023-04-04 | Dic株式会社 | Apparatus for producing metal oxide and method for producing the same |
| CN108387431A (en) * | 2018-02-27 | 2018-08-10 | 南昌工程学院 | The device for filtering and collecting of nano material |
| US10287177B1 (en) * | 2018-05-08 | 2019-05-14 | Robert Ten | Method and apparatus for extracting high-purity molybdenum oxide powders and nanopowders from low-grade concentrates |
| CN111747759B (en) * | 2019-05-14 | 2021-04-16 | 中南大学 | Method for preparing mullite-based light refractory material and synchronously purifying molybdenum calcine |
| CN112520789B (en) * | 2020-12-29 | 2022-05-31 | 杭州电子科技大学 | Preparation method of molybdenum trioxide nano film |
| CN113511680B (en) * | 2021-08-10 | 2022-11-25 | 郑州大学 | Preparation method of high-purity molybdenum trioxide |
| CN115108586B (en) * | 2022-05-13 | 2023-07-25 | 郑州大学 | Method for separating molybdenum trioxide by activating roasting |
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| US6468497B1 (en) * | 2000-11-09 | 2002-10-22 | Cyprus Amax Minerals Company | Method for producing nano-particles of molybdenum oxide |
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2012
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Patent Citations (2)
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|---|---|---|---|---|
| US6468497B1 (en) * | 2000-11-09 | 2002-10-22 | Cyprus Amax Minerals Company | Method for producing nano-particles of molybdenum oxide |
| CN101092249A (en) * | 2007-04-27 | 2007-12-26 | 中山大学 | Method for preparing Nano structure and thin film of molybdenum trioxide by using infrared sintering furnace |
Non-Patent Citations (4)
| Title |
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| "高频等离子体固相分解仲钼酸铵制备MoO3、MoO2超微细粉";马兵等;《化工冶金》;19960531;第17卷(第2期);第168-172页 * |
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Application publication date: 20120725 Assignee: Songxian Blazers Molybdenum Industry Co., Ltd. Assignor: Luoyang pioneer management of investment Co., Ltd. Contract record no.: 2015410000015 Denomination of invention: Method for preparing nanometer molybdenum trioxide Granted publication date: 20131204 License type: Exclusive License Record date: 20150326 |
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