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CN104003446A - Preparation method of high-purity molybdenum trioxide - Google Patents

Preparation method of high-purity molybdenum trioxide Download PDF

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CN104003446A
CN104003446A CN 201410234166 CN201410234166A CN104003446A CN 104003446 A CN104003446 A CN 104003446A CN 201410234166 CN201410234166 CN 201410234166 CN 201410234166 A CN201410234166 A CN 201410234166A CN 104003446 A CN104003446 A CN 104003446A
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molybdenum
trioxide
constant
heating
container
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CN 201410234166
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CN104003446B (en )
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宋盼淑
王军
任同祥
周涛
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中国计量科学研究院
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Abstract

The invention discloses a preparation method of high-purity molybdenum trioxide. High-purity molybdenum trioxide is obtained by oxidizing and purifying molybdenum powder. The method comprises the following steps: firstly, performing oxidation reaction on molybdenum in the presence of air to obtain molybdenum trioxide, wherein a heating process comprises the following steps: (1) heating to 100-200 DEG C and keeping the constant temperature, and (2) further heating to 550-650 DEG C and performing oxidation reaction; secondly, purifying, wherein the purifying process comprises the following steps: (1) putting molybdenum trioxide into a closed container and arranging a collecting pipe in the container; (2) heating the region in which molybdenum trioxide is arranged, to 100-150 DEG C; vacuumizing the container to be 10Pa-100Pa and keeping the constant temperature and the constant pressure; (3) stopping vacuumizing, heating the region in which molybdenum trioxide is arranged, to 600-720 DEG C and keeping the constant temperature; (4) further vacuumizing the container to be 10Pa-100Pa and keeping the constant pressure for 120-150 minutes. The process for preparing molybdenum trioxide is simple, the requirement on purification or preparation of a micro molybdenum reagent in a lab can be met, and the purity of the prepared molybdenum reagent reaches up to 99.99%.

Description

一种高纯三氧化钼的制备方法 A method for preparing high-purity molybdenum trioxide

技术领域 FIELD

[0001] 本发明涉及一种高纯三氧化钥的制备方法,属于高纯金属氧化物制备技术领域。 [0001] The present invention relates to a method for preparing high-purity oxide key belongs to the technical field of preparation of high purity metal oxides. 背景技术 Background technique

[0002] 在自然界中,钥有7种稳定同位素,分别为92Mo、94Mo、95Mo、96Mo、97Mo、98Mo和iciqMo。 [0002] In nature, there are seven stable isotopes key, respectively, 92Mo, 94Mo, 95Mo, 96Mo, 97Mo, 98Mo and iciqMo. 当地质和海洋环境的氧化-还原状态发生变化时,可导致钥同位素的质量分馏。 When the oxidation of the marine environment and geological - restore state changes, can lead to mass isotope fractionation key. 同时,钥元素是植物、动物和人体内多种酶的重要组成部分。 Meanwhile, the key element is an important component of plants, animals and humans of many enzymes. 因此,建立钥元素含量和同位素丰度比测量方法对地球化学、地质学和生物学等领域的研究具有重要意义。 Therefore, establishing key element content and isotopic abundance ratio measurement research in the field of geochemistry, geology, and biology of great significance. 通常采用质量百分比^ 99.99%的钥金属单质或钥化合物,制备钥成分或同位素标准物质,从而提高测量结果的可靠性和准确度。 ^ Usually 99.99% by mass percentage key elemental metal or a compound key, the key ingredient or the preparation of isotope reference material, thereby improving the reliability and accuracy of measurement results. 由于目前市售的高纯钥试剂种类少,价格昂贵,且货期较长,建立钥元素纯化方法,制备纯度> 99.99%的钥试剂具有重要的应用价值。 Because less current commercially available high-purity reagents key species, expensive and longer delivery time, the establishment of key elements of the purification process, the preparation of a purity of> 99.99% of key reagents have important application value. 另一方面,高纯三氧化钥是一种重要的化工原料,主要用于生产高纯钥金属单质和钥的化合物,以及在石油工业中用作催化剂。 On the other hand, key trioxide of high purity is an important chemical raw materials, mainly for the production of high purity key elemental metal compound and the key, and the catalyst used in the petroleum industry.

[0003] 文献中主要采用离子交换法,如:阴、阳离子交换树脂法,螯合树脂法和阴离子交换树脂法,对复杂基体样品如土壤、血清中的钥元素进行分离和富集。 [0003] Document primarily by ion exchange, such as: anion and cation exchange resin, chelating resin and anion exchange resin method, for complex samples such as soil, serum separation and enrichment of the key elements. 这类方法操作复杂,通常需要使用两种树脂或重复操作2次才能达到高纯试剂的纯度要求;同时,纯化过程中使用硝酸、盐酸、氢氟酸或氨水等化学试剂,这些化学试剂中的杂质元素容易对样品产生污染。 Such methods are complicated to operate, generally require the use of two resins or repeat twice to achieve purity purity reagents; the same time, the purification process using nitric acid, hydrochloric acid, hydrofluoric acid, ammonia water, or the like chemical reagents, these chemical agents are prone to contamination of an impurity element samples. [0004] 在专利申请“一种钥粉的纯化方法”(公开号为“CN101347839A”)中公开了一种以普通钥粉为原料,经过水洗或酸洗除杂,烘干,高温氢气保护除杂或真空高温除杂,真空筛分等过程制得纯化的钥粉的方法。 [0004] The patent application discloses a "method for purifying a key powder" (Publication No. "CN101347839A") kind normal key powder as raw material, acid washing or cleaning, drying, high-temperature hydrogen in addition to the protection heteroaryl or high-temperature vacuum cleaning, vacuum sieving process to obtain purification of key powder. 采用该方法纯化后的钥粉中钥的质量百分比为99.94%~99.95%。 Using the key in the key mass percentage of the powder after the purification method was 99.94% to 99.95%.

[0005] 工业上主要采用两种工艺路线对三氧化钥粉末(又称钥焙砂)进行纯化,制备高纯三氧化钥。 [0005] Industrial process routes mainly in two key trioxide powder (also known as key calcine) purified preparation of high purity trioxide key. 一种称为湿法:即由钥焙砂经氨浸,湿法提纯净化,生产成仲钥酸铵,仲钥酸铵经加热分解,去除氨气,从而获得高纯三氧化钥;另一种称为火法,由钥焙砂直接加热,钥焙砂中杂质残留在焙烧渣中,而大部分三氧化钥经升华再结晶,生成高纯三氧化钥。 Called wet process: i.e. by ammonia leaching, purification is purified by wet-key calcine, ammonium produced as a secondary key, a secondary key by thermal decomposition of ammonium, ammonia is removed, to obtain a high-purity oxide key; the other species known as fire, calcine directly heated by the key, the key remaining in the calcine firing residue of impurities, and most trioxide key sublimated recrystallization, high purity oxide generated key. 由于反应温度对纯化效果的影响较大,在工业生产中采用湿法或火法纯化后得到的三氧化钥的纯度一般不闻于99.95%。 Since the reaction temperature is greater impact on the effect of purification, the purity trioxide using keys or a wet fire after purification obtained in industrial production generally is not heard in the 99.95%.

发明内容 SUMMARY

[0006] 本发明的目的是提供一种高纯三氧化钥的制备方法,利用本方法制备的三氧化钥纯度> 99.99%。 [0006] The object of the present invention is to provide a high-purity oxide key preparation, prepared using the method key trioxide purity> 99.99%. 基于钥单质的化学性质和三氧化钥易升华的性质,本发明采取两步法对普通纯度的钥试剂进行纯化。 Based on the nature of the chemical nature and the key trioxide simple substance easy sublimation of the key, the present invention is a two-step process for ordinary purity key reagents for purification.

[0007] 本发明提供的一种高纯三氧化钥的制备方法,包括如下步骤: [0007] A method for producing a high purity oxide keys provided by the present invention, comprising the steps of:

[0008] 第一步,在空气存在的条件下,钥金属单质粉末经氧化反应得到三氧化钥; [0008] The first step, in the presence of air, keyhole single metal powder is key trioxide oxidation reaction;

[0009] 所述氧化反应的升温过程如下:[0010] I)将温度升至100°C~200°C,并保持恒温; [0009] The oxidation reaction of the heating process is as follows: [0010] I) The temperature was raised to 100 ° C ~ 200 ° C, and held constant;

[0011] 2)继续升温至550°C~650°C,进行所述氧化反应。 [0011] 2) continue to heat up to 550 ° C ~ 650 ° C, for the oxidation reaction.

[0012] 第二步,对所述三氧化钥进行纯化: [0012] The second step, the purified trioxide key:

[0013] I)将所述三氧化钥置于一封闭的容器中,并在所述容器中设置收集管; [0013] I) the key trioxide was placed in a closed container, and the collection tube disposed in said container;

[0014] 2)加热所述三氧化钥所在区域,使温度升至100~150°C;对所述容器进行抽真空至IOPa~lOOPa,并保持恒温恒压; [0014] 2) heating the area where the key trioxide, the temperature was raised to 100 ~ 150 ° C; vacuuming IOPa ~ lOOPa to the vessel, and maintaining constant temperature and pressure;

[0015] 3)停止抽真空,并使所述三氧化钥所在区域的温度升至600°CC~720°C,保持恒温; [0015] 3) evacuation is stopped, and the temperature of the region where the key trioxide was raised 600 ° CC ~ 720 ° C, maintaining a constant temperature;

[0016] 4)继续对所述容器进行抽真空至IOPa~lOOPa,并保持恒压120~150min,即在所述收集管中收集得到升华提纯后的三氧化钥。 [0016] 4) continue the container was evacuated to IOPa ~ lOOPa, and to maintain constant pressure 120 ~ 150min, i.e. key trioxide was collected after sublimation purification in the collection tube.

[0017] 上述的制备方法中,所述第一步氧化反应的升温过程中,步骤I)中,在20~40min内将温度升至100°C~200°C,具体可在30min内升温至150°C ; [0017] The above-described production method, the first step of the process of heating the oxidation reaction in step I), within the temperature was raised to 20 ~ 40min 100 ° C ~ 200 ° C, allowed to warm to specifically in 30min 150 ° C;

[0018] 所述恒温的保持时间为30~60min,具体可为30min。 [0018] The temperature holding time is 30 ~ 60min, it may be particularly 30min.

[0019] 上述的制备方法中,所述第一步氧化反应的升温过程中,步骤2)中,在60~90min内将温度升至550°C~650°C,具体可在60min内升温至580°C或600°C ; [0019] The above-described production method, the first step of the process of heating the oxidation reaction in step 2), the inner temperature was raised to 60 ~ 90min 550 ° C ~ 650 ° C, allowed to warm to specifically within 60min 580 ° C or 600 ° C;

[0020] 所述氧化反应的时间为480~960min,具体可为480min~720min、480min~540min、540min ~720min、480min、540min 或720mino [0020] The oxidation reaction time was 480 ~ 960min, may be particularly 480min ~ 720min, 480min ~ 540min, 540min ~ 720min, 480min, 540min or 720mino

[0021] 上述的制备方法中,所述第一步氧化反应结束之后降温至300°C~400°C,具体可降至350°C~400°C、350°C、370°C或400°C。 [0021] The above-described production method, the first step after the oxidation reaction is cooled to 300 ° C ~ 400 ° C, can be reduced particularly 350 ° C ~ 400 ° C, 350 ° C, 370 ° C or 400 ° C.

[0022] 上述的制备方法中,所述第二步纯化的步骤中,步骤2)中,在20~40min内将温度升至100°C~150°C,具体可在30min内升温至至150°C ; [0022] The above-described production method, the second step of the purification step, step 2), the inner temperature was raised to 20 ~ 40min 100 ° C ~ 150 ° C, particularly 150 to be heated to within 30min ° C;

[0023] 所述恒温恒压的保持时间为30~60min,具体可为30min。 [0023] The holding time of constant temperature and pressure is 30 ~ 60min, it may be particularly 30min.

[0024] 上述的制备方法中,所述第二步纯化的步骤中,步骤3)中,在60~90min内将温度升至600°C~720°C,具体可在60min内将温度升至600°C~675°C、600°C、625°C或675 °C ; [0024] The above preparation method, the step of purifying the second step, step 3), the inside temperature was raised to 60 ~ 90min 600 ° C ~ 720 ° C, the temperature may be raised specifically within 60min 600 ° C ~ 675 ° C, 600 ° C, 625 ° C or 675 ° C;

[0025] 所述恒温的保持时间具体为30~60min,具体可为30min。 [0025] The temperature holding time is particularly 30 ~ 60min, it may be particularly 30min.

[0026] 上述的制备方法中,所述第二步纯化的步骤中,步骤4)中,所述恒压的保持时间具体可为120min ~135min、125min ~135min、120min、125min 或135min。 [0026] The above-described production method, the second step of the purification step, step 4), the retention time of the constant voltage may be particularly 120min ~ 135min, 125min ~ 135min, 120min, 125min or 135min.

[0027] 本发明方法制备得到的三氧化钥的纯度≥99.99%。 Purity trioxide key preparation process of the invention obtained [0027] The present ≥99.99%.

[0028] 本发明制备高纯三氧化钥的操作过程简单,能够满足实验室纯化或制备几十毫克到几百毫克微量钥试剂的需求,同时由于纯化过程中不加入任何化学试剂,能够减少杂质的引入,纯化后可制得纯度> 99.99%的高纯钥试剂。 [0028] Preparation of high-purity oxidized during operation of the present invention is simple keys can be purified or prepared for laboratory tens of milligrams to several hundred milligrams of agent demand trace key, and because the purification process without adding any chemicals, impurities can be reduced introducing, after purification with purity> 99.99% purity key reagents.

具体实施方式 detailed description

[0029] 下述实施例中所使用的实验方法如无特殊说明,均为常规方法。 [0029] The following experimental procedure used in Examples Unless otherwise specified, all conventional methods.

[0030] 本发明下述实施例中,三氧化钥纯化方法的回收率按照下述公式计算: [0030] The following embodiment of the present invention, a method of recovery of purified trioxide key calculated according to the following formula:

[0031] [0031]

Figure CN104003446AD00041

[0032] 本发明下述实施例中采用高分辨电感耦合等离子体质谱仪分析纯化前钥金属单质粉末以及纯化后制得三氧化钥中杂质的含量。 [0032] The following embodiment of the present invention, a mass spectrometer metal content key before purification and after purification by elemental powders prepared trioxide key impurities by high resolution ICP embodiment employed.

[0033] 具体测试条件如下:在2% (v/v)的硝酸中配置浓度分别为lng/g的铍、铟和铋的混合溶液,对高分辨电感耦合等离子体质谱仪的仪器条件进行最佳化选择。 [0033] The specific test conditions were as follows: Configuration concentration 2% (v / v) nitric acid in a mixed solution lng / g beryllium, indium and bismuth, respectively, of the instrument conditions high resolution inductively coupled plasma mass spectrometer is most best choice. 68种金属、非金属元素的多元素混合溶液标准物质(BW3197-BW3200)购买自中国计量科学研究院。 68 kinds of multi-element metal and non-metallic elements mixed solution of the standard substance (BW3197-BW3200) was purchased from China Institute of Metrology.

[0034] 具体测试方法如下:在2% (v/v)的硝酸中将上述多元素混合溶液标准物质稀释至浓度分别为lng/g, 5ng/g, 10ng/g作为标准溶液。 [0034] The specific test methods are as follows: the multi-element in the nitric acid in 2% (v / v) mixed solution was diluted to a concentration of the standard substance were lng / g, 5ng / g, 10ng / g as a standard solution. 通过标准曲线法半定量分析样品中67种杂质的含量,从而计算得到纯化前钥金属单质粉末以及纯化后三氧化钥的纯度。 By a standard curve method semiquantitative analysis impurity content of the samples is 67, so as to calculate the purity of elemental metal key before purification and after purification trioxide powder keys.

[0035] 下述实施例中所用的材料、试剂等,如无特殊说明,均可从商业途径得到。 [0035] Example materials used, reagents and the like, no special instructions such as the following, can be obtained from commercial sources.

[0036] 本发明下述实施例中使用的钥金属单质粉末原料颗粒度为100目。 Particle size of the raw material powder of single metal key using the following examples of embodiments [0036] The present invention is of 100 mesh.

[0037] 实施例1、高纯三氧化钥的制备 [0037] Preparation of a high purity trioxide key Example

[0038] 原料为天然丰度钥金属单质,钥的质量百分比为99.89%。 [0038] The key starting material for the natural abundance of metal elements, the mass percentage of key 99.89%. 称取钥粉末原料605.64mg置于石英烧杯中,放入马弗炉内加热,通入空气进行氧化反应。 605.64mg key weighed powder raw material was placed in a quartz beaker, placed in a muffle furnace heated air into the oxidation reaction. 升温过程如下: Heating process is as follows:

[0039] I)打开马弗炉,30min将温度由室温升温至150°C,稳定30min以除去其中吸附的水分及其他可能的气体杂质; [0039] I) to open a muffle furnace, 30min the temperature was raised from room temperature to 150 ° C, 30min to remove moisture stable and possibly other impurities, wherein the gas adsorption;

[0040] 2)60min将温度由150°C升温至600°C,氧化时间为480min,以确保钥粉末充分氧化; [0040] 2) 60min the temperature was elevated from 150 ° C to 600 ° C, the oxidation time is 480min, in order to ensure full oxidation of the key powder;

[0041] 3)停止加热,马弗炉内温度降温至400°C时,打开马弗炉,将装有三氧化钥粉末的烧杯取出,放入真空保干器内冷却至室温; When the [0041] 3) heating was stopped, muffle furnace cooled until the temperature 400 ° C, the muffle opening, with the key trioxide powder beaker was taken, cooled to room temperature into a vacuum desiccator;

[0042] 对上述氧化得到的三氧化钥粉末进行纯化,具体步骤如下: [0042] The oxidation of the above-described key trioxide powder was purified by the following steps:

[0043] I)称取116.22mg三氧化钥粉末置于石英舟内; [0043] I) weighing 116.22mg key trioxide powder was placed in a quartz boat;

[0044] 2)将石英舟缓慢放入一端封闭的石英管内,并推动至可温控管式炉的加热中心区域;将石英样品收集管放入石英管内,推动至可温控管式炉加热区域外端;之后,将石英管放入可温控管式炉中,石英管管口与机械真空泵相连; [0044] 2) placed in a quartz boat was slowly quartz tube closed at one end, and to promote the temperature controlled center of the heating zone of the tube furnace; quartz sample collection tube was placed in a quartz tube, push tube furnace to a temperature controlled heating an outer end region; then, the quartz tube may be placed in a temperature-controlled tube furnace, a quartz tube connected to a mechanical vacuum pump port;

[0045] 3)打开管式炉,30min将温度由室温升温至150°C,打开机械真空泵,抽真空至lOOPa,稳定30min,以除去其中吸附的水分及其他可能的气体杂质; [0045] 3) Open the tube furnace, 30min the temperature was raised from room temperature to 150 ° C, the mechanical vacuum pump is opened, evacuated to Loopa, stable 30min, wherein in order to remove adsorbed moisture and possibly other gaseous impurities;

[0046] 4)关闭真空泵,60min将温度由150°C升温至625°C,稳定30min ; [0046] 4) the vacuum pump, 60min the temperature was raised to 150 ° C by the 625 ° C, stable for 30 min;

[0047] 5)打开机械真空泵,抽真空至lOOPa,蒸发提纯时间为120min,使三氧化钥粉末开始升华并沉积在样品收集管内; [0047] 5) the mechanical vacuum pump is opened, evacuated to Loopa, the evaporation time is 120min purification, so that the three key oxide powder starts to sublime and be deposited within the sample collection tube;

[0048] 6)停止加热,保持石英管内真空为lOOPa,三氧化钥粉末在样品石英收集管内自然冷却至室温; [0048] 6) Stop heating, a vacuum is maintained Loopa, key trioxide powder was allowed to cool to room temperature in a quartz sample collection tube into the quartz tube;

[0049]7)关闭机械真空泵和管式炉,从石英管内取出石英样品收集管,获得高纯度的三氧化钥晶体。 [0049] 7) closing mechanical vacuum pump and a tube furnace, a quartz sample taken from the collection tube into the quartz tube, high purity crystals key trioxide.

[0050] 纯化后三氧化钥纯度分析: [0050] After purification trioxide key Purity Analysis:

[0051] 称量收集管中三氧化钥晶体,质量为102.59mg,计算得到利用上述方法制备的三氧化钥的回收率为88.27%。 [0051] The collection tubes were weighed key trioxide crystals, the quality of 102.59mg, the recovery rate is calculated by the above method of preparing key trioxide was 88.27%.

[0052] 采用高分辨电感耦合等离子体质谱仪分析纯化前钥金属单质粉末以及纯化后制得三氧化钥中杂质的含量。 [0052] The mass spectrometer metal content key before purification and after purification by elemental powders prepared trioxide key impurities by high resolution inductively coupled plasma. 结果表明,纯化前钥试剂中钥金属单质的质量百分比为99.89% ;纯化后制得三氧化钥样品中三氧化钥的质量百分比为99.99%。 The results showed that the percentage by mass prior to purification agent key in key elemental metal is 99.89%; purified by mass percentage trioxide keys key trioxide prepared sample was 99.99%. [0053] 其中主要杂质元素的含量如表1所示: [0053] wherein the content of the main impurity element as shown in Table 1:

[0054] 表1.纯化前钥粉末原料及纯化后三氧化钥中主要杂质元素的质量百分比) [0054] TABLE 1 mass% and the powder raw material before purification key main key trioxide impurities after purification)

[0055] [0055]

Figure CN104003446AD00061

[0056] a “一”表示在所述实验条件下该元素的含量低于检测限 [0056] a "a" represents the contents of the elements under the experimental conditions below the detection limit

[0057] 实施例2、高纯三氧化钥的制备 Preparation Example 2, the key trioxide of high purity [0057] Embodiment

[0058] 原料为天然丰度钥金属单质,钥的质量百分比为99.89%。 [0058] The key starting material for the natural abundance of metal elements, the mass percentage of key 99.89%. 称取钥粉末原料939.93mg置于石英烧杯中,放入马弗炉内加热,通入空气进行氧化反应。 939.93mg key weighed powder raw material was placed in a quartz beaker, placed in a muffle furnace heated air into the oxidation reaction. 升温过程如下: Heating process is as follows:

[0059] I)打开马弗炉,30min将温度由室温升温至150°C,稳定30min以除去其中吸附的水分及其他可能的气体杂质; [0059] I) to open a muffle furnace, 30min the temperature was raised from room temperature to 150 ° C, 30min to remove moisture stable and possibly other impurities, wherein the gas adsorption;

[0060] 2)60min将温度由150°C升温至600°C,氧化时间为720min,以确保钥粉末充分氧化; [0060] 2) 60min the temperature was elevated from 150 ° C to 600 ° C, the oxidation time is 720min, in order to ensure full oxidation of the key powder;

[0061] 3)停止加热,马弗炉内温度降温至350°C时,打开马弗炉,将装有三氧化钥粉末的烧杯取出,放入真空保干器内冷却至室温; When the [0061] 3) heating was stopped, muffle furnace cooled until the temperature 350 ° C, the muffle opening, with the key trioxide powder beaker was taken, cooled to room temperature into a vacuum desiccator;

[0062] 对上述氧化得到的三氧化钥粉末进行纯化,具体步骤如下: [0062] The oxidation of the above-described key trioxide powder was purified by the following steps:

[0063] I)称取121.4Img三氧化钥粉末置于石英舟内; [0063] I) weighed 121.4Img key trioxide powder was placed in a quartz boat;

[0064] 2)将石英舟缓慢放入一端封闭的石英管内,并推动至可温控管式炉的加热中心区域;将石英样品收集管放入石英管内,推动至可温控管式炉加热区域外端;之后,将石英管放入可温控管式炉中,石英管管口与机械真空泵相连; [0064] 2) placed in a quartz boat was slowly quartz tube closed at one end, and to promote the temperature controlled center of the heating zone of the tube furnace; quartz sample collection tube was placed in a quartz tube, push tube furnace to a temperature controlled heating an outer end region; then, the quartz tube may be placed in a temperature-controlled tube furnace, a quartz tube connected to a mechanical vacuum pump port;

[0065] 3)打开管式炉,30min将温度由室温升温至150°C,打开机械真空泵,抽真空至lOOPa,稳定30min,以除去其中吸附的水分及其他可能的气体杂质; [0065] 3) Open the tube furnace, 30min the temperature was raised from room temperature to 150 ° C, the mechanical vacuum pump is opened, evacuated to Loopa, stable 30min, wherein in order to remove adsorbed moisture and possibly other gaseous impurities;

[0066] 4)关闭真空泵,60min将温度由150°C升温至600°C,稳定30min ; [0066] 4) the vacuum pump, 60min the temperature was raised to 150 ° C by the 600 ° C, stable for 30 min;

[0067] 5)打开机械真空泵,抽真空至lOOPa,蒸发提纯时间为135min,使三氧化钥粉末开始升华并沉积在样品收集管内; [0067] 5) the mechanical vacuum pump is opened, evacuated to Loopa, the evaporation time is 135min purification, so that the three key oxide powder starts to sublime and be deposited within the sample collection tube;

[0068] 6)停止加热,保持石英管内真空为lOOPa,三氧化钥粉末在样品石英收集管内自然冷却至室温; [0068] 6) Stop heating, a vacuum is maintained Loopa, key trioxide powder was allowed to cool to room temperature in a quartz sample collection tube into the quartz tube;

[0069] 7)关闭机械真空泵和管式炉,从石英管内取出石英样品收集管,获得高纯度的三氧化钥晶体。 [0069] 7) closing mechanical vacuum pump and a tube furnace, a quartz sample taken from the collection tube into the quartz tube, high purity crystals key trioxide.

[0070] 纯化后三氧化钥样品纯度分析: [0070] After purification trioxide key Sample purity analysis:

[0071] 称量收集管中三氧化钥晶体,质量为104.98mg,计算得到上述方法的回收率为86.47%。 [0071] The collection tubes were weighed key trioxide crystals, the quality of 104.98mg, the recovery method described above is calculated 86.47%.

[0072] 采用高分辨电感耦合等离子体质谱仪分析纯化前钥金属单质粉末以及纯化后制得三氧化钥中杂质的含量。 [0072] The mass spectrometer content key elemental metal prior to purification and after purification powder prepared trioxide key impurities by high resolution inductively coupled plasma. 结果表明,纯化前钥试剂中钥金属单质的质量百分比为99.89% ;纯化后制得三氧化钥样品中三氧化钥的质量百分比为99.99%。 The results showed that the percentage by mass prior to purification agent key in key elemental metal is 99.89%; purified by mass percentage trioxide keys key trioxide prepared sample was 99.99%.

[0073] 其中主要杂质元素的含量如表2所示: [0073] wherein the content of the main impurity element as shown in Table 2:

[0074] 表2.纯化前钥粉末原料及纯化后三氧化钥中主要杂质元素的质量百分比) [0074] Table 2. Percentage by mass material powder and pre-purification key main impurities trioxide key after purification)

[0075] [0075]

Figure CN104003446AD00071

[0076] [0076]

[0077] a “一”表示在所述实验条件下该元素的含量低于检测限 [0077] a "a" represents the contents of the elements under the experimental conditions below the detection limit

[0078] 实施例3、高纯三氧化钥的制备 Preparation Example 3, high-purity oxide keys [0078] Embodiment

[0079] 原料为98Mo丰度为98.15%的浓缩钥同位素(金属单质),钥的质量百分比为99.89%。 [0079] The starting material is 98.15% of 98Mo abundance isotopic enrichment key (elemental metal), the percentage of 99.89% by mass key. 称取钥粉末原料380.8Img置于石英烧杯中,放入马弗炉内加热,通入空气进行氧化反应。 Key 380.8Img weighed powder raw material was placed in a quartz beaker, placed in a muffle furnace heated air into the oxidation reaction. 升温过程如下: Heating process is as follows:

[0080] I)打开马弗炉,30min将温度由室温升温至150°C,稳定30min以除去其中吸附的水分及其他可能的气体杂质; [0080] I) to open a muffle furnace, 30min the temperature was raised from room temperature to 150 ° C, 30min to remove moisture stable and possibly other impurities, wherein the gas adsorption;

[0081] 2)60min将温度由150°C升温至580°C,氧化时间为540min,以确保钥粉末充分氧化; [0081] 2) 60min the temperature was elevated from 150 ° C to 580 ° C, the oxidation time is 540min, in order to ensure full oxidation of the key powder;

[0082] 3)停止加热,马弗炉内温度降温至370°C时,打开马弗炉,将装有三氧化钥粉末的烧杯取出,放入真空保干器内冷却至室温;[0083] 对上述氧化得到的三氧化钥粉末进行纯化,具体步骤如下: When the [0082] 3) heating was stopped, muffle furnace cooled until the temperature 370 ° C, the muffle furnace is opened, the beaker containing the key trioxide powder taken out, cooled to room temperature placed in a vacuum dessicator; [0083] of the oxidation key trioxide powder obtained was purified by the following steps:

[0084] I)称取139.04mg三氧化钥粉末置于石英舟内; [0084] I) weighing 139.04mg key trioxide powder was placed in a quartz boat;

[0085] 2)将石英舟缓慢放入一端封闭的石英管内,并推动至可温控管式炉的加热中心区域;将石英样品收集管放入石英管内,推动至可温控管式炉加热区域外端;之后,将石英管放入可温控管式炉中,石英管管口与机械真空泵相连; [0085] 2) placed in a quartz boat was slowly quartz tube closed at one end, and to promote the temperature controlled center of the heating zone of the tube furnace; quartz sample collection tube was placed in a quartz tube, push tube furnace to a temperature controlled heating an outer end region; then, the quartz tube may be placed in a temperature-controlled tube furnace, a quartz tube connected to a mechanical vacuum pump port;

[0086] 3)打开管式炉,30min将温度由室温升温至150°C,打开机械真空泵,抽真空至IOOPa,稳定30min,以除去其中吸附的水分及其他可能的气体杂质; [0086] 3) Open the tube furnace, 30min the temperature was raised from room temperature to 150 ° C, the mechanical vacuum pump is opened, evacuated to IOOPa, stable 30min, wherein in order to remove adsorbed moisture and possibly other gaseous impurities;

[0087] 4)关闭真空泵,60min将温度由150°C升温至675°C,稳定30min ; [0087] 4) the vacuum pump, 60min the temperature was raised to 150 ° C by the 675 ° C, stable for 30 min;

[0088] 5)打开机械真空泵,抽真空至lOOPa,蒸发提纯时间为125min,使三氧化钥粉末开始升华并沉积在样品收集管内; [0088] 5) the mechanical vacuum pump is opened, evacuated to Loopa, the evaporation time is 125min purification, so that the three key oxide powder starts to sublime and be deposited within the sample collection tube;

[0089] 6)停止加热,保持石英管内真空为lOOPa,三氧化钥粉末在样品石英收集管内自然冷却至室温; [0089] 6) Stop heating, a vacuum is maintained Loopa, key trioxide powder was allowed to cool to room temperature in a quartz sample collection tube into the quartz tube;

[0090] 7)关闭机械真空泵和管式炉,从石英管内取出石英样品收集管,获得高纯度的三氧化钥晶体。 [0090] 7) closing mechanical vacuum pump and a tube furnace, a quartz sample taken from the collection tube into the quartz tube, high purity crystals key trioxide.

[0091] 纯化后三氧化钥纯度分析: [0091] After purification trioxide key Purity Analysis:

[0092] 称量收集管中三氧化钥晶体,质量为121.66mg,计算得到上述方法的回收率为87.50%。 [0092] The collection tubes were weighed key trioxide crystals, the quality of 121.66mg, the recovery method described above is calculated 87.50%.

[0093] 采用高分辨电感耦合等离子体质谱仪分析纯化前钥金属单质粉末以及纯化后制得三氧化钥中杂质的含量。 [0093] The mass spectrometer metal content key before purification and after purification by elemental powders prepared trioxide key impurities by high resolution inductively coupled plasma. 结果表明,纯化前钥试剂中钥金属单质的质量百分比为99.88% ;纯化后制得三氧化钥样品中三氧化钥的质量百分比为99.99%。 The results showed that the percentage by mass prior to purification agent key in key elemental metal is 99.88%; purified by mass percentage trioxide keys key trioxide prepared sample was 99.99%. 其中主要杂质元素的含量如表3所示: Wherein the content of the main impurity element as shown in Table 3:

[0094] 表3.纯化前钥粉末原料及纯化后三氧化钥中主要杂质元素的质量百分比) [0094] Table 3 mass% before purification key powdery material and an impurity element trioxide main key after purification)

[0095] [0095]

Figure CN104003446AD00081

[0096] a “一”表示在所述实验条件下该元素的含量低于检测限。 [0096] a "a" represents the contents of the elements under the experimental conditions below the detection limit.

Claims (6)

  1. 1.一种高纯三氧化钥的制备方法,包括如下步骤: 在空气存在的条件下,钥金属单质粉末经氧化反应得到三氧化钥; 所述氧化反应的升温过程如下: 1)将温度升至100°C~20(TC,并保持恒温; 2)继续升温至550°C~650°C,进行所述氧化反应。 1. A method for preparing high-purity oxide keys, comprising the steps of: in the presence of air, keyhole single metal powder is key trioxide oxidation reaction; heating process of the oxidation reaction as follows: 1) The temperature was raised to 100 ° C ~ 20 (TC, and maintain constant temperature; 2) continue to heat up to 550 ° C ~ 650 ° C, for the oxidation reaction.
  2. 2.根据权利要求1所述的制备方法,其特征在于:所述方法还包括对所述三氧化钥进行纯化的步骤: 1)将所述三氧化钥置于一封闭的容器中,并在所述容器中设置收集管; 2)加热所述三氧化钥所在区域,使温度升至100~150°C ;对所述容器进行抽真空至10~lOOPa,并保持恒温恒压; 3)停止抽真空,并使所述三氧化钥所在区域的温度升至600°C~720°C,且保持恒温; 4)继续对所述容器进行抽真空至10~lOOPa,并保持恒压120~150min,即在所述收集管中收集得到升华提纯后的三氧化钥。 The production method according to claim 1, characterized in that: said method further comprises the purification trioxide key steps: 1) the key trioxide was placed in a closed container, and the collecting pipe is provided in the container; 2) heating the key area trioxide, the temperature was raised to 100 ~ 150 ° C; the vessel was evacuated to 10 ~ lOOPa, and maintaining constant temperature and pressure; 3) stop vacuum, and the temperature of the region where the key trioxide was raised 600 ° C ~ 720 ° C, and held constant; 4) continue the vacuum vessel was evacuated to 10 ~ lOOPa, and to maintain constant pressure 120 ~ 150min , that is collected in the collection tube trioxide key obtained after the sublimation purification.
  3. 3.根据权利要求1或2所述的制备方法,其特征在于:所述氧化反应的升温过程中,步骤I)中,在20~40min 内所述恒温的时间为30~60min。 The production method according to claim 1 or claim 2, wherein: heating of said oxidation reaction process, step I), the time in the constant temperature of 20 ~ 40min 30 ~ 60min.
  4. 4.根据权利要求1-3中任一项所述的制备方法,其特征在于:所述氧化反应的升温过程中,步骤2)中,在60~90min内将温度升至550°C~650°C ; 所述氧化反应的时间为480~960min。 The production method according to any one of the preceding claims, characterized in that: the heating process of the oxidation reaction in step 2), the inside temperature was raised to 60 ~ 90min 550 ° C ~ 650 ° C; time of the oxidation reaction is 480 ~ 960min.
  5. 5.根据权利要求2-4中任一项所述的制备方法,其特征在于:所述纯化的步骤中,步骤2)中,在20~40min内将温度升至100°C~150°C ; 所述恒温恒压的保持时间为30~60min。 The production method according to any one of the 2-4 claims, characterized in that: the purification step, step 2), the inner temperature was raised to 20 ~ 40min 100 ° C ~ 150 ° C ; retention time of the constant temperature and pressure is 30 ~ 60min.
  6. 6.根据权利要求2-5中任一项所述的制备方法,其特征在于:所述纯化的步骤中,步骤3)中,在60~90min内将温度升至600°C~720°C ; 所述恒温的保持时间为120~150min。 The production method according to any one of claims 2-5 claims, characterized in that: the purification step, step 3), the inside temperature was raised to 60 ~ 90min 600 ° C ~ 720 ° C ; the temperature holding time of 120 ~ 150min.
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