CN101767204B - Fluidized preparation method for WC-Co composite powder - Google Patents
Fluidized preparation method for WC-Co composite powder Download PDFInfo
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Abstract
The invention provides a fluidized preparation method for WC-Co composite powder, which comprises the following steps of: pouring tungsten-cobalt composite oxide powder serving as a raw material into a fluidized bed, and introducing hydrogen and inert gases at the temperature of between 600 and 900 DEG C to reduce the powder, wherein the reaction time is 1 to 3 hours; after the reduction process is finished, pouring a solid carbon source into the fluidized bed to perform continuous carbonization at the temperature of between 700 and 1,300 DEG C, wherein the reaction time is 30 to 150 minutes; and finally, introducing a carbonaceous gas, the hydrogen and the inert gases to regulate carbon to obtain the WC-Co composite powder, wherein the reaction temperature is between 600 and 1,000 DEG C and the reaction time is 10 to 60 minutes. The obtained WC- Co composite powder has uniform components, stable performance and lower impurity content, can meet the requirements of higher industrial production, and can be widely used for industrialization production of various kinds of ultrafine cemented carbide.
Description
Technical field
The present invention relates to the fluidized preparation method of a kind of industrialized process for preparing of cemented carbide powder, particularly a kind of WC-Co composite powder.
Background technology
Carbide alloy is a primary raw material with rare metals such as tungsten, cobalt, titaniums, wherein accounts for the principal status of public economy with the tungsten-cobalt carbide carbide alloy again.Carbide alloy has high rigidity, high density, property such as wear-resisting, is widely used in a plurality of fields such as machine-building, oil exploitation, military project, Aero-Space, is the novel force structure material with high-tech content, has very big market potential.The preparation method of tradition carbide alloy adopts methods such as fixed bed, rotary furnace, hydrogen plasma to make tungsten oxide become tungsten powder by hydrogen reducing; Tungsten (W) powder is mixed with carbon (C) sphere of powder mill; Change into tungsten carbide (WC) through pyrocarbon; Carry out ball mill mixing with prefabricated cobalt powder again, obtain WC-Co (WC-Co) carbide alloy mixed-powder, and then prepare carbide alloy through compacting sintering.The method preparation technology's long flow path, efficient are low, tungsten carbide (WC) is difficult to even distribution at cobalt (Co) in mutually in the mixed-powder, influences follow-up carbide alloy performance.In cemented carbide industry today to production high-performance, ultra-fine cemented carbide development cheaply; Conventional method is difficult to effectively prepare the suitable alloy powder that ultra-fine cemented carbide is used of producing, and the production of carbide alloy is now developing to the direction that adopts WC-Co composite powder to prepare carbide alloy gradually.
The method that the preparation of WC-Co composite powder is adopted usually mainly contains following method:
(1) mixes the intermediate powder that is uniformly mixed with the solid carbon dust as raw material with tungsten-cobalt composite oxide powder; Said intermediate powder under the hydrogen-containing gas effect, is carried out thermal chemical reaction on fixed bed, obtain the WC-Co nano composite powder.(" carbonization of low-temperature solid carbon prepares the method for tungsten-cobalt carbide nano composite powder " number of patent application 200410082959.0)
(2) on atomic level, mix W, Co and C element and process the carbide precursor body, adopt radially moving bed reactor to prepare nanometer WC/Co powder, and apply anti-oxidation film at nanometer WC/Co powder surface.(" making the method for WC/Co composite nanometre powder " number of patent application 97106622.1)
(3) once prepare the ultra-fine cemented carbide composite powder with fluid bed reduction and carbonization; Place fluid bed to raw material composite powder with the chemical method preparation; Make the fluidisation operating gas with inert gas or hydrogen and carry out hydrogen reduction, add the carbonaceous gas carbonization and obtain the ultra-fine cemented carbide composite powder.(" once preparing the WC-Co composite powder " number of patent application 93108446.6) with fluid bed reduction and carbonization
(4) compound and the crystallizing inhibitor with tungstenic, cobalt is raw material, processes the composite oxides precursor powder through spray pyrolysis, and it is placed fluid bed, feeds hydrogen at 450～850 ℃ and makes it reduction; Use the carbonaceous gas carbonization for 750～1500 ℃; 700～1200 ℃ with carbonaceous gas, hydrogen make carbonization; Regulate the carbon amount with carbonaceous gas, hydrogen for 500～900 ℃, make no η phase nanometer tungsten carbide Co composite powder.(" the preparation of industrialization technology of nm-class non-eta-phase compound powder of tungsten carbide and cobalt " number of patent application 99116597.7)
In preparation WC-Co composite powder numerous methods, than the perhaps radially moving bed method for preparing WC-Co composite powder of employings fixed bed, (3), (4) two kinds is raw material with the tungsten-cobalt composite oxide powder; It is simple to adopt fluid bed to carry out the method technological process of continuous reduction and carbonization, because gas fully contacts with powder in process of production, cobalt element is evenly distributed in composite powder and alloy; Powder grain is tiny evenly; Powder activity is high, is swift in response, and is suitable for industrial-scale production.But the said method carbonisation adopts carbonaceous gas to carry out carbonization, and carburizing reagent is slow, and gas consumption is big, and cost is high; The carbonization control accuracy is low, must replenish carbonization through one or many, has increased technological process and control difficulty, and the cooling that repeatedly heats up has simultaneously increased production cost also to having a negative impact the service life of equipment.
Summary of the invention
The object of the invention mainly is to solve above-mentioned existing fluidized-bed process to prepare the efficient that WC-Co composite powder exists low; Process is complicated; Consume greatly, cost high-technology problem proposes a kind of new fluidized preparation method that is suitable for industrialized WC-Co composite powder.
The present invention solves the problems of the technologies described above and adopts following technical proposals to be achieved: be raw material with the tungsten-cobalt composite oxide powder; Material powder is dropped in the fluid bed; Make it reduction at 600～900 ℃ of feeding hydrogen and inert gas, the reaction time is 1～3 hour; After reduction process finishes, drop into solid-state carbon source, under 700～1300 ℃ temperature, carry out continuous carbonization, the reaction time is 30～150 minutes; At last under 600～1000 ℃ temperature, feed carbonaceous gas, hydrogen and inert gas and transfer carbon, the reaction time is 10～60 minutes, obtains WC-Co (WC-Co) composite powder.
The present invention is when implementing, and fluid bed preferably adopts bubbling fluidized bed (BFB), or recirculating fluidized bed (CFB).
The present invention is when implementing, and in reduction process, inert gas can be selected Ar, He, Ne, Kr, Xe, N for use
2In a kind of or several.
No matter the present invention in reduction process, selects for use a kind of or several inert gases when implementing, and the optimum volume ratio of hydrogen and inert gas is controlled to be 1: 0.5～and 1: 5.
The present invention when implementing, the optional carbon black of using of the solid-state carbon source of adding, graphite, a kind of in the amorphous carbon or several.
No matter the present invention in carbonisation, selects for use a kind of or several carbon sources when implementing, and the optimal addn of solid-state carbon source is all 1.0～2.0 times of calculated value.
The present invention is when implementing, and the carbonaceous gas of transferring the carbon process to add can be selected CH for use
4, CO, CO
2In a kind of or several.
No matter the present invention in transferring the carbon process, selects for use a kind of or several carbonaceous gas when implementing, and the optimum volume ratio of carbonaceous gas and hydrogen is controlled to be 1: 10～and 1: 50.
Advantage of the present invention is that the overall process of reduction, carbonization, accent carbon is carried out in fluid bed continuously, and production efficiency is high; Carbonisation adopts solid-state carbon source, than gaseous carbon source, be swift in response, consume fewly, cost is low; Carbonation rate is high, and carbonisation only needs a carbonization, and carbonization is abundant, need not to replenish carbonization, has reduced technological process, does not have the process of the cooling that heats up repeatedly simultaneously, and is little to the loss of equipment, reduced maintenance cost; It is few to produce free carbon in the carbonisation, makes that follow-up accent carbon process burden is little, transfers carbon speed fast, has improved production efficiency; Therefore; The present invention possess skills the advanced person, technology is simple, flow process is short, be easy to control, characteristics such as consumption is little, production efficiency is high, cost of equipment maintenance is low; Be used in combination have purification, distribution, voltage stabilizing, Flow-rate adjustment, the circulating fluidized bed system of function such as control automatically, very suitable large-scale industrial production.
Description of drawings
Accompanying drawing 1 is a process flow diagram of the present invention.
The specific embodiment
Embodiment 1:
With the tungsten-cobalt composite oxide powder is raw material, and wherein the oxide W content is 74.90%, and cobalt content is 4.24%, and loose specific weight is 2.596g/cm
3, mobile 25.61s/50g.Material powder is dropped in the recirculating fluidized bed, make it reduction at 600～750 ℃ of feeding hydrogen and nitrogen, the ratio of hydrogen and nitrogen is 1: 2,2 hours reduction reaction time; After reduction process finishes, drop into carbon black, the carbon black input amount is 1.5 times of theoretical value, under 800～1000 ℃ temperature, carries out continuous carbonization, 75 minutes carburizing reagent time; At last under 700～800 ℃ temperature, feed carbon dioxide, hydrogen and nitrogen and transfer carbon, the ratio of carbon dioxide and hydrogen is 1: 50,30 minutes reaction time.Obtain being fit to WC-Co (WC-Co) composite powder of preparation WC-5Co carbide alloy, record powder mean grain size (following examples are identical) with x-ray powder polycrystalline diffractometer and be 55.7nm.
Embodiment 2:
With the tungsten-cobalt composite oxide powder is raw material, and wherein the oxide W content is 72.65%, and cobalt content is 6.74%, and loose specific weight is 2.473g/cm
3, mobile 27.33s/50g.Material powder is dropped in the recirculating fluidized bed, make it reduction at 650～800 ℃ of feeding hydrogen and nitrogen, the ratio of hydrogen and nitrogen is 1: 3,3 hours reduction reaction time; After reduction process finishes, drop into carbon black, the carbon black input amount is 1.2 times of theoretical value, under 850～1200 ℃ temperature, carries out continuous carbonization, 45 minutes carburizing reagent time; At last under 800～900 ℃ temperature, feed carbon dioxide, hydrogen and nitrogen and transfer carbon, the ratio of carbon dioxide and hydrogen is 1: 30,20 minutes reaction time.Obtain being fit to WC-Co (WC-Co) composite powder of preparation WC-8Co carbide alloy, mean grain size is 45.4nm.
Embodiment 3:
With the tungsten-cobalt composite oxide powder is raw material, and wherein the oxide W content is 76.25%, and cobalt content is 2.53%, and loose specific weight is 2.397g/cm
3, mobile 28.18s/50g.Material powder is dropped in the recirculating fluidized bed, make it reduction at 700～900 ℃ of feeding hydrogen and nitrogen, the ratio of hydrogen and nitrogen is 1: 4,3 hours reduction reaction time; After reduction process finishes, drop into carbon black, the carbon black input amount is 2 times of theoretical value, under 750～1100 ℃ temperature, carries out continuous carbonization, 90 minutes carburizing reagent time; At last under 750～950 ℃ temperature, feed carbon monoxide, hydrogen and nitrogen and transfer carbon, the ratio of carbon monoxide and hydrogen is 1: 40,25 minutes reaction time.Obtain being fit to WC-Co (WC-Co) composite powder of preparation WC-3Co carbide alloy, mean grain size is 71.3nm.
Embodiment 4:
With the tungsten-cobalt composite oxide powder is raw material, and wherein the oxide W content is 74.12%, and cobalt content is 4.98%, and loose specific weight is 2.594g/cm
3, mobile 25.45s/50g.Material powder is dropped in the fluid bed, make it reduction at 750～950 ℃ of feeding hydrogen and argon gas, the ratio of hydrogen and argon gas is 1: 2,2 hours reduction reaction time; After reduction process finishes, drop into graphite, the graphite input amount is 1.8 times of theoretical value, under 750～1000 ℃ temperature, carries out continuous carbonization, 90 minutes carburizing reagent time; At last under 700～900 ℃ temperature, feed methane, hydrogen and nitrogen and transfer carbon, the ratio of methane and hydrogen is 1: 30,20 minutes reaction time.Obtain being fit to WC-Co (WC-Co) composite powder of preparation WC-6Co carbide alloy, mean grain size is 59.4nm.
Claims (6)
1. the fluidized preparation method of a WC-Co composite powder; It is characterized in that: it is to be raw material with the tungsten-cobalt composite oxide powder; Material powder is dropped in the fluid bed, make it reduction, 1～3 hour reaction time at 600～900 ℃ of feeding hydrogen and inert gas; After reduction process finishes; Drop into solid-state carbon source, said solid-state carbon source is a kind of in graphite, the amorphous carbon or several, and the addition of said carbon source is 1.0～2.0 times of calculated value; Under 700～1300 ℃ temperature, carry out continuous carbonization, 30～150 minutes reaction time; At last under 600～1000 ℃ temperature, feed carbonaceous gas, hydrogen and inert gas and transfer carbon, in 10～60 minutes reaction time, obtain WC-Co (WC-Co) composite powder.
2. the fluidized preparation method of WC-Co composite powder according to claim 1, it is characterized in that: said fluid bed is a bubbling fluidized bed, or recirculating fluidized bed.
3. the fluidized preparation method of WC-Co composite powder according to claim 1, it is characterized in that: said inert gas is selected Ar, He, Ne, Kr, Xe, N for use
2In a kind of or several.
4. according to the fluidized preparation method of claim 1 or 3 described WC-Co composite powders, it is characterized in that: in reduction process, the volume ratio of hydrogen and inert gas is controlled to be 1: 0.5～and 1: 5.
5. the fluidized preparation method of WC-Co composite powder according to claim 1, it is characterized in that: said carbonaceous gas is selected CH for use
4, CO, CO
2In a kind of or several.
6. according to the fluidized preparation method of claim 1 or 5 described WC-Co composite powders, it is characterized in that: to transfer in the carbon process, the volume ratio of carbonaceous gas and hydrogen is controlled to be 1: 10～and 1: 50.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102963895B (en) * | 2012-11-19 | 2014-07-02 | 锦州新桥高纯材料有限公司 | Preparation method of chromium carbide powder |
| CN103056376B (en) * | 2013-01-04 | 2015-04-08 | 湖南顶立科技有限公司 | Method for preparing spherical nanostructure tungsten/cobalt carbide compound powder |
| CN104439263A (en) * | 2014-12-09 | 2015-03-25 | 株洲硬质合金集团有限公司 | Preparation method for WC-Co composite powder |
| CN105290413A (en) * | 2015-11-13 | 2016-02-03 | 株洲硬质合金集团有限公司 | Method for preparing tungsten carbide-cobalt composite powder through direct reduction and carbonization |
| CN111036931A (en) * | 2019-12-04 | 2020-04-21 | 上大新材料(泰州)研究院有限公司 | Tungsten-cobalt alloy powder and preparation method thereof |
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| CN1254628A (en) * | 1999-08-13 | 2000-05-31 | 武汉工业大学 | Industrilized process for preparing nm-class non-eta-phase compound powder of tungsten carbide and cobalt |
| CN1789461A (en) * | 2004-12-14 | 2006-06-21 | 中国科学院金属研究所 | Method for preparing tungsten carbide-cobalt nano composite powder by low-temperature carbonization of solid carbon |
| CN1907604A (en) * | 2006-08-18 | 2007-02-07 | 谭天翔 | Direct reduction carbonization manufacture method for tungsten carbide or tungsten carbide-cobalt ultrafine particle powder |
| WO2007108575A1 (en) * | 2006-03-17 | 2007-09-27 | Nanotech Co., Ltd. | Manufacturing method for ultra fine composite powder of tungsten carbide and cobalt |
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Patent Citations (4)
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| CN1254628A (en) * | 1999-08-13 | 2000-05-31 | 武汉工业大学 | Industrilized process for preparing nm-class non-eta-phase compound powder of tungsten carbide and cobalt |
| CN1789461A (en) * | 2004-12-14 | 2006-06-21 | 中国科学院金属研究所 | Method for preparing tungsten carbide-cobalt nano composite powder by low-temperature carbonization of solid carbon |
| WO2007108575A1 (en) * | 2006-03-17 | 2007-09-27 | Nanotech Co., Ltd. | Manufacturing method for ultra fine composite powder of tungsten carbide and cobalt |
| CN1907604A (en) * | 2006-08-18 | 2007-02-07 | 谭天翔 | Direct reduction carbonization manufacture method for tungsten carbide or tungsten carbide-cobalt ultrafine particle powder |
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