WO2011057462A1 - 一种超细碳化钨粉末的制备方法 - Google Patents

一种超细碳化钨粉末的制备方法 Download PDF

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WO2011057462A1
WO2011057462A1 PCT/CN2009/076278 CN2009076278W WO2011057462A1 WO 2011057462 A1 WO2011057462 A1 WO 2011057462A1 CN 2009076278 W CN2009076278 W CN 2009076278W WO 2011057462 A1 WO2011057462 A1 WO 2011057462A1
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powder
tungsten
ultrafine
tungsten carbide
carbon
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PCT/CN2009/076278
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English (en)
French (fr)
Inventor
魏柏万
林钊
李志峰
邹安石
吴毅
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江西稀有稀土金属钨业集团有限公司
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Priority to EP09851217.1A priority Critical patent/EP2502879A4/en
Priority to CN200980162447.6A priority patent/CN102652106B/zh
Priority to KR1020127012419A priority patent/KR101384006B1/ko
Priority to JP2012538164A priority patent/JP5595512B2/ja
Priority to AU2009355218A priority patent/AU2009355218B2/en
Priority to US13/509,621 priority patent/US8980215B2/en
Publication of WO2011057462A1 publication Critical patent/WO2011057462A1/zh

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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/90Carbides
    • C01B32/914Carbides of single elements
    • C01B32/949Tungsten or molybdenum carbides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic

Definitions

  • the present invention relates to a process for preparing a cemented carbide powder in the metallurgical field, particularly a method for preparing an ultrafine tungsten carbide powder.
  • Ultra-fine cemented carbide is a tool material developed in recent years, mainly based on ultra-fine WC powder.
  • the preparation method is divided into two categories: (1) Reductive carbonization two-step method: that is, the W powder is prepared from the tungsten-containing precursor, and then carbonized with the carbon-containing substance. A WC powder is produced.
  • the tungsten-containing precursor (such as W0 3 ) is directly reduced and carbonized to form WC powder.
  • This method generally requires preparation of a highly active tungsten precursor.
  • the ultrafine tungsten powder and the carbon powder precursor are generally mixed and then subjected to high-temperature carbonization to produce ultrafine tungsten carbide powder, but because of the method, the ultrafine tungsten powder has a large specific surface area and a strong surface activity, and is slightly different from air. Oxidation and spontaneous combustion occurs when contact occurs, which affects product quality and causes material loss.
  • An object of the present invention is to provide a method for producing an ultrafine tungsten carbide powder which reduces oxidation and autoignition reaction of a precursor, and the prepared ultrafine tungsten carbide powder is not easily pyrophoric and has a low oxygen content.
  • the present invention provides a method for preparing ultrafine tungsten carbide powder, which comprises ultrafine tungsten powder and carbon black as raw materials, and is characterized in that it comprises the following steps: (1) Passivation of ultrafine tungsten powder : After the ultra-fine tungsten powder is filled with pure carbon dioxide gas, it is allowed to stand to passivate the surface of the ultra-fine tungsten powder; (2) Charcoal: The passivated ultra-fine tungsten powder and carbon powder are put into the carbon dispenser, Cooling water is cooled, mixed with inert gas, mixed, natural after mixing Cooling; (3) Carbonization: High-temperature carbonization of mixed ultra-fine tungsten powder and carbon powder in a carbonization furnace to form massive tungsten carbide powder; (4) Crushing and sieving: loading block-shaped tungsten carbide powder into the pulverizer It is pulverized, cooled and sieved to obtain a tungsten carbide powder.
  • the ultrafine tungsten powder is filled with pure carbon dioxide gas, and is allowed to stand for 12 hours or more to passivate the surface of the ultrafine tungsten powder to prevent spontaneous combustion of the ultrafine tungsten powder.
  • the cooling water is continuously used to cool the barrel wall of the carbon blending machine to reduce the temperature of the precursor of the ultrafine tungsten powder and the carbon powder.
  • the precursor of the ultrafine tungsten powder and the carbon powder may be continuously filled with an inert gas to prevent the material from coming into contact with the air.
  • the pulverized tungsten carbide powder may be sieved by cooling water after cooling.
  • the ultrafine powder may also be sifted under the protection of an inert gas.
  • the method of the invention firstly passivates the ultrafine tungsten powder of the raw material with pure carbon dioxide gas, and in the subsequent step, the cooling temperature is lowered and the inert gas is introduced to reduce the powder temperature and surface activity, thereby avoiding the precursor and the air.
  • the contact prevents the oxidation and spontaneous combustion of the precursor formed by the ultrafine tungsten powder and the carbon powder, thereby improving the quality of the product and reducing the loss of the material.
  • the ultra-fine tungsten carbide powder produced by this method is not easy to self-ignite.
  • the oxygen content is reduced by 20-40%, and the ultra-fine tungsten powder in the mixed carbon-discharging equipment is added in the charcoal process.
  • the weight of the toner, the mixing amount of the ultra-fine tungsten powder and the carbon powder is 1 to 2 times that of the conventional method, and the production efficiency is improved.
  • Fig. 1 is a flow chart showing the production of ultrafine tungsten carbide powder according to the method of the present invention.
  • the steps of preparing ultrafine tungsten carbide powder by using ultrafine tungsten powder and carbon powder as raw materials according to the method of the present invention are as follows:
  • the Fischer particle size is 0.4 ⁇
  • the specific surface area is 5m2/g
  • the ultrafine tungsten powder of 300 ⁇ 500kg is charged into the carbon blending machine.
  • the cooling water is cooled. Inert gas protection, mixing 3 After ⁇ 5 hours, it will naturally cool 10 ⁇ 14 hours.
  • the additive may be a hard alloy grain growth inhibitor such as chromium or vanadium.
  • step (2) The ultrafine tungsten powder and carbon powder mixed in step (2) are loaded into the boat of the corresponding production specification, and the reaction is carried out at a high temperature of 1000 ⁇ 1400 °C in a high temperature molybdenum wire carbonization furnace, and the tungsten powder and the carbon powder are synthesized. It is a bulk tungsten carbide powder.
  • step (3) The bulk tungsten carbide powder prepared in step (3) is crushed into a crusher and pulverized for 2 ⁇ 4 hours, and then naturally cooled and passed through a 100-140 mesh stainless steel mesh to obtain ultrafine tungsten carbide powder, and an inert gas is introduced. well package.
  • Detection step (4) Preparation of ultra-fine tungsten carbide powder: Fisher's particle size is 0.4 ⁇ 0.5 ⁇ , specific surface area is 2 ⁇ 3 m 2 /g, oxygen content is 1500 1800ppm.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Description

说明书
Title of Invention:一种超细碳化钨粉末的制备方法 技术领域
技术领域
[1] 本发明涉及冶金领域硬质合金粉末的制备工艺, 特别是超细碳化钨粉末的制备 方法。
背景技术
背景技术
[2] 超细硬质合金是近年来发展起来的工具材料, 主要以超细 WC粉末为基础原料
, 并添加适当的粘结剂 (如 Co) 和晶粒长大抑制剂来生产高硬度、 高耐磨性和 高韧性的硬质合金材料, 其性能比常规硬质合金高, 在难加工金属材料工具、 电子行业的微型钻头、 精密模具、 医用牙钻等领域已呈现出越来越广泛的应用 前景。 据超细 WC粉末在还原碳化过程是否连续, 将其制备方法分成两大类: ( 1) 还原碳化两步法: 即由含钨前驱体先制备出 W粉, 再与含碳的物质进行碳化 生成 WC粉末。 (2) 还原碳化一步法: 即含钨的前驱体 (如 W03) 直接被还原 碳化生成 WC粉末, 该方法一般需要制备较高活性的钨前驱体。 目前在工业生产 中, 一般使用超细钨粉和炭粉的前驱体混合后经高温碳化生产超细碳化钨粉, 但是因为该方法超细钨粉比表面积大、 表面活性强, 与空气稍有接触即发生氧 化自燃现象, 影响产品质量, 造成物料损失。
对发明的公开
发明内容
[3] 本发明的目的是提供一种超细碳化钨粉末的制备方法, 所述方法减少了前驱体 的氧化和自燃反应, 制备出的的超细碳化钨粉末不易自燃且含氧量低。
[4] 为此, 本发明提供了一种超细碳化钨粉末的制备方法, 以超细钨粉和炭黑为原 料, 其特征为, 包括以下步骤: (1) 超细钨粉的钝化: 在超细钨粉中充入纯净 二氧化碳气体后静置, 使超细钨粉末表面钝化; (2) 配炭: 将钝化后的超细钨 粉和炭粉装入配炭机中, 冷却水降温, 通入惰性气体保护后混合, 混合后自然 冷却; (3) 碳化: 将混合好的超细钨粉和炭粉在炭化炉中高温碳化合成块状碳 化钨粉; (4) 粉碎过筛: 将块状的碳化钨粉装入粉碎机中粉碎, 冷却后过筛得 到碳化钨粉末。
[5] 所述超细钨粉的钝化步骤中, 超细钨粉充入纯净二氧化碳气体, 静置 12小吋以 上, 使超细钨粉表面钝化, 防止超细钨粉自燃。
[6] 所述配炭步骤中, 不断使用冷却水冷却配炭机器桶壁, 降低超细钨粉和炭粉的 前驱体的温度。 所述配炭步骤中, 也可以向超细钨粉和炭粉的前驱体中不断填 充惰性气体, 避免物料与空气接触。
[7] 所述粉碎过筛步骤中, 粉碎后碳化钨粉末可釆用冷却水降温后过筛。
[8] 所述粉碎过筛步骤中, 也可以充入惰性气体保护下过筛保护超细粉末。
[9] 本发明方法先将原料超细钨粉用纯净二氧化碳气体钝化, 在后续的步骤中釆用 冷却水降温和通入惰性气体的方法降低粉末温度和表面活性, 避免了前驱体与 空气的接触, 防止超细钨粉和炭粉形成的前驱体的氧化和自燃反应, 提高了产 品的质量, 减少了物料的损失。 釆用本方法生产的超细碳化钨粉末不易自燃, 与传统方法制备的超细产品碳化钨粉比较氧含量降低 20~40%, 配炭工序中增加 了混合配炭设备中超细钨粉和碳粉的重量, 超细钨粉和碳粉的混合量是传统方 法的 1~2倍, 提高了生产效率。
附图说明
[10] 图 1是根据本发明方法制备超细碳化钨粉的生产流程图。
具体实施例
[11] 如图 1所示, 根据本发明方法以超细钨粉和炭粉为原料制备超细碳化钨粉步骤 如下:
[12] (1) 超细钨粉的钝化
[13] 在超细钨粉中通入纯净二氧化碳气体, 静置 12小吋以上, 使超细钨粉表面钝化 降低钨粉表面活性。
[14] (2) 配炭
[15] 将步骤 (1) 钝化后费氏粒度为 0.4μηι, 比表面积 5m2/g, 300~500kg的超细钨粉 装入配炭机中, 加入炭粉及添加剂后, 冷却水降温, 通入惰性气体保护, 混合 3 ~5小吋后, 自然冷却 10~14小吋。 所述添加剂可以是铬、 钒等硬质合金晶粒长大 抑制剂等。
[16] (3) 碳化
[17] 将步骤 (2) 中混合均匀的超细钨粉和炭粉装入相应生产规格的舟皿中, 高温 钼丝碳化炉中 1000~1400°C高温下反应, 钨粉与炭粉合成为块状碳化钨粉。
[18] (4) 粉碎过筛
[19] 将步骤 (3) 制备的块状碳化钨粉装入破碎机中粉碎 2~4小吋, 自然冷却后通过 100~140目不锈钢筛网, 得到超细碳化钨粉, 通入惰性气体包装好。
[20] 检测步骤 (4) 制备的超细碳化钨粉: 费氏粒度为 0.4 ~ 0.5μηι, 比表面积 2~3 m2/g , 氧含量 1500 1800ppm。

Claims

权利要求书 一种超细碳化钨粉末的制备方法, 以超细钨粉和炭黑为原料, 其 特征在于, 包括以下步骤:
(1) 超细钨粉的钝化: 在超细钨粉中充入纯净二氧化碳气体后静 置, 使超细钨粉末表面钝化;
(2) 配炭: 将钝化后的超细钨粉和炭粉装入配炭机中, 冷却水降 温, 通入惰性气体保护后混合, 混合后自然冷却;
(3) 碳化: 将混合好的超细钨粉和炭粉在炭化炉中高温碳化合成 块状碳化钨粉;
(4) 粉碎过筛: 将块状的碳化钨粉装入粉碎机中粉碎, 冷却后过 筛得到碳化钨粉末。
根据权利要求 1所述的制备方法, 其特征在于: 步骤 (1) 中超细 钨粉充入纯净二氧化碳气体, 使超细钨粉表面钝化。
根据权利要求 1所述的制备方法, 其特征在于: 步骤 (2) 中超细 钨粉和炭黑在混合过程中经过冷却水降温。
根据权利要求 1所述的制备方法, 其特征在于: 步骤 (2) 中超细 钨粉和炭黑在混合过程中通入惰性气体保护。
根据权利要求 1所述的制备方法, 其特征在于: 步骤 (4) 中粉碎 后碳化钨粉末可釆用冷却水降温后过筛。
根据权利要求 1所述的制备方法, 其特征在于: 步骤 (4) 中粉碎 后碳化钨粉末在充入惰性气体保护下过筛。
PCT/CN2009/076278 2009-11-16 2009-12-30 一种超细碳化钨粉末的制备方法 WO2011057462A1 (zh)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP09851217.1A EP2502879A4 (en) 2009-11-16 2009-12-30 PROCESS FOR THE PREPARATION OF ULTRAFINE TUNGSTEN CARBIDE POWDER
CN200980162447.6A CN102652106B (zh) 2009-11-16 2009-12-30 一种超细碳化钨粉末的制备方法
KR1020127012419A KR101384006B1 (ko) 2009-11-16 2009-12-30 초미립 탄화텅스텐 분말 제조방법
JP2012538164A JP5595512B2 (ja) 2009-11-16 2009-12-30 超微粉タングステンカーバイドの作製方法
AU2009355218A AU2009355218B2 (en) 2009-11-16 2009-12-30 Method for preparing ultrafine tungsten carbide powder
US13/509,621 US8980215B2 (en) 2009-11-16 2009-12-30 Method for preparing ultrafine tungsten carbide powder

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CN200910223448A CN101723368A (zh) 2009-11-16 2009-11-16 一种超细碳化钨粉末的制备方法
CN200910223448.9 2009-11-16

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US (1) US8980215B2 (zh)
EP (1) EP2502879A4 (zh)
JP (1) JP5595512B2 (zh)
KR (1) KR101384006B1 (zh)
CN (3) CN101723368A (zh)
AU (1) AU2009355218B2 (zh)
WO (1) WO2011057462A1 (zh)

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CN114132927A (zh) * 2021-11-15 2022-03-04 赣州海盛钨钼集团有限公司 一种碳化钨粉的制备系统
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CN113501523A (zh) * 2021-08-12 2021-10-15 赣州江钨友泰新材料有限公司 一种连续动态还原钨粉制备超细颗粒碳化钨的工艺
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US8980215B2 (en) 2015-03-17
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