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CN104003446B - Preparation method of high-purity molybdenum trioxide - Google Patents

Preparation method of high-purity molybdenum trioxide Download PDF

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CN104003446B
CN104003446B CN 201410234166 CN201410234166A CN104003446B CN 104003446 B CN104003446 B CN 104003446B CN 201410234166 CN201410234166 CN 201410234166 CN 201410234166 A CN201410234166 A CN 201410234166A CN 104003446 B CN104003446 B CN 104003446B
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preparation
method
high
purity
molybdenum
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CN104003446A (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

本发明公开了一种高纯三氧化钼的制备方法。 The present invention discloses a method for preparing high-purity molybdenum trioxide. 以金属钼单质粉末为原料,经氧化和纯化后得到。 Elemental molybdenum metal powder as raw material, obtained after oxidation and purification. 首先,在空气存在的条件下,钼单质经氧化反应得到三氧化钼,其中升温过程包括:1)将温度升至100℃~200℃,并保持恒温;2)继续升温至550℃~650℃,进行氧化反应;其次,纯化步骤包括:1)将所述三氧化钼置于一封闭容器中,并在所述容器中设置收集管;2)加热三氧化钼所在区域,使温度升至100~150℃;对容器抽真空至10Pa~100Pa,并保持恒温恒压;3)停止抽真空,并使三氧化钼所在区域的温度升至600℃~720℃,保持恒温;4)继续对所述容器抽真空至10Pa~100Pa,并保持恒压120~150min。 First, in the presence of air, elemental molybdenum, molybdenum trioxide by oxidation reaction, wherein the heating process comprising: 1) the temperature was raised to 100 ℃ ~ 200 ℃, and remains constant; 2) continue to heat up to 550 ℃ ~ 650 ℃ , an oxidation reaction; Secondly, the purification step comprises: a) the molybdenum trioxide are placed in a closed container, and the collection tube disposed in said container; 2) molybdenum trioxide heating zone where the temperature was raised to 100 ~ 150 ℃; of the container was evacuated to 10Pa ~ 100Pa, and maintaining constant temperature and pressure; 3) to stop the vacuum and the temperature was raised to the region where the molybdenum trioxide 600 ℃ ~ 720 ℃, remains constant; 4) continue the said container is evacuated to 10Pa ~ 100Pa, and to maintain constant pressure 120 ~ 150min. 本发明制备高纯三氧化钼的操作过程简单,能够满足实验室纯化或制备微量钼试剂的需求,所制得钼试剂纯度高达99.99%。 Preparation of high purity molybdenum trioxide operation of the present invention is simple, can be purified or prepared for laboratory reagents demand trace molybdenum, molybdenum reagent prepared purity 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钼的制备方法,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 molybdenum oxide belongs to the technical field of preparation of high purity metal oxides. 背景技术 Background technique

[0002] 在自然界中,钼有7种稳定同位素,分别为92Mo、94Mo、95Mo、 96Mo、97Mo、98Mo和1(l°Mo。 当地质和海洋环境的氧化-还原状态发生变化时,可导致钼同位素的质量分馏。同时,钼元素是植物、动物和人体内多种酶的重要组成部分。因此,建立钼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宄具有重要意义。通常采用质量百分比多99. 99%的钼金属单质或钼化合物,制备钼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。由于目前市售的高纯钼试剂种类少,价格昂贵,且货期较长,建立钼元素纯化方法,制备纯度多99. 99%的钼试剂具有重要的应用价值。另一方面,高纯三氧化钼是一种重要的化工原料,主要用于生产高纯钼金属单质和钼的化合物,以及在石油工业中用作催化剂。 [0002] In nature, molybdenum has 7 stable isotopes, respectively, 92Mo, 94Mo, 95Mo, 96Mo, 97Mo, 98Mo, and 1 (l ° Mo as oxide geological and marine environment - at restoring a status change may result mass molybdenum isotope fractionation. Meanwhile, molybdenum is an important part of plants, animals and humans of many enzymes. Thus, the establishment of molybdenum content and isotopic abundance ratio measurement geochemical, geology, biology, and other fields a Subsidiary of great significance. multi usually 99.99% by mass percentage of elemental molybdenum metal or a molybdenum compound, or molybdenum component prepared isotope reference material, thereby improving the reliability and accuracy of measurement results due to the current commercially available high-purity molybdenum less reagent species, expensive and longer delivery time, the establishment of molybdenum purification process, the purity of the preparation of more than 99.99% of molybdenum reagent has an important value. on the other hand, high purity molybdenum trioxide is an important chemical raw materials, mainly for the production of high-purity molybdenum compounds and molybdenum, elemental metal, and as a catalyst 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、血清中的钼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 molybdenum. 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"一种钼粉的纯化方法"(公开号为"CN101347839A")中公开了一种以普通钼粉为原料,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钼粉的方法。 [0004] In the patent application "method for purifying molybdenum powder" (Publication No. "CN101347839A") discloses an ordinary molybdenum 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 molybdenum powder. 采用该方法纯化后的钼粉中钼的质量百分比为99. 94%~99. 95%。 The percentage by mass of molybdenum powder purified using the method molybdenum is 99.94% ~ 99.95%.

[0005]工业上主要采用两种工艺路线对三氧化钼粉末(又称钼焙砂)进行纯化,制备高纯三氧化钼。 [0005] industrially mainly in two process routes of molybdenum trioxide powder (also known as molybdenum calcine) purified preparation of high purity molybdenum trioxide. 一种称为湿法:即由钼焙砂经氨浸,湿法提纯净化,生产成仲钼酸铵,仲钼酸铵经加热分解,去除氨气,从而获得高纯三氧化钼;另一种称为火法,由钼焙砂直接加热,钼焙砂中杂质残留在焙烧渣中,而大部分三氧化钼经升华再结晶,生成高纯三氧化钼。 Called wet process: i.e. by ammonia leaching, purification is purified by wet-molybdenum calcine, produced as ammonium paramolybdate, ammonium paramolybdate by thermal decomposition, ammonia is removed, thereby obtaining a high-purity molybdenum trioxide; other species known as fire, molybdenum calcine is heated by direct, molybdenum calcine residual impurities in the firing residue, and most recrystallization sublimated molybdenum trioxide, molybdenum trioxide generating high purity. 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钼的纯度一般不高于99. 95%。 Since the reaction temperature is greater impact on the effect of purification, the purity of molybdenum trioxide using a wet or fire after purification obtained in industrial production generally not higher than 99.95%.

发明内容 SUMMARY

[0006] 本发明的目的是提供一种高纯三氧化钼的制备方法,利用本方法制备的三氧化钼纯度多99. 99%。 [0006] The object of the present invention is to provide a method for preparing high-purity molybdenum oxide, prepared using the method of multi-purity molybdenum trioxide 99.99%. 基于钼单质的化学性质和三氧化钼易升华的性质,本发明采取两步法对普通纯度的钼试剂进行纯化。 Based on the chemical nature of a molybdenum trioxide simple substance and easy sublimation property, a two-step process of the present invention the purity of molybdenum ordinary purification reagents.

[0007]本发明提供的一种高纯三氧化钼的制备方法,包括如下步骤: [0007] A method for producing a high-purity molybdenum oxide according to the present invention is provided, comprising the steps of:

[0008]第一步,在空气存在的条件下,钼金属单质粉末经氧化反应得到三氧化钼; [0008] The first step, in the presence of air, elemental molybdenum metal powder obtained by the oxidation reaction of molybdenum trioxide;

[0009] 所述氧化反应的升温过程如下: [0009] The oxidation reaction of the heating process is as follows:

[0010] 1)将温度升至100 °C~200 °C,并保持恒温; [0010] 1) 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,对所述三氧化钼进行纯化: [0012] The second step, the molybdenum trioxide and purified:

[0013] 1)将所述三氧化钼置于一封闭的容器中,并在所述容器中设置收集管; [0013] 1) the molybdenum trioxide are placed in a closed container, and the collection tube disposed in said container;

[0014] 2)加热所述三氧化钼所在区域,使温度升至100~150°C;对所述容器进行抽真空至10Pa~lOOPa,并保持恒温恒压; [0014] 2) heating the area where the molybdenum trioxide, the temperature was raised to 100 ~ 150 ° C; the vessel was evacuated to 10Pa ~ lOOPa, and maintaining constant temperature and pressure;

[0015] 3)停止抽真空,并使所述三氧化钼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 was raised to molybdenum trioxide Area 600 ° CC ~ 720 ° C, maintaining a constant temperature;

[0016] 4)继续对所述容器进行抽真空至10Pa~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钼。 [0016] 4) continue the container was evacuated to 10Pa ~ lOOPa, and to maintain constant pressure 120 ~ 150min, i.e. the molybdenum trioxide was collected after the 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1)中,在20~40min 内将温度升至l〇〇°C~200°C,具体可在30min内升温至150°C ; [0017] The above-described production method, the heating process in the first step of the oxidation reaction, Step 1), the inner temperature was raised to 20 ~ 40min l〇〇 ° C ~ 200 ° C, Specific within 30min heated to 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720min〇 [0020] The oxidation reaction time was 480 ~ 960min, may be particularly 480min ~ 720min, 480min ~ 540min, 540min ~ 720min, 480min, 540min or 720min〇

[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°〇、350°〇、370°〇或400°〇。 [0021] The above-described production method, the first step after the oxidation reaction is cooled to 300 ° C ~ 400 ° C, it can be reduced particularly 350 ° C ~ 400 ° square, 350 ° square, 370 ° or 400 ° square billion.

[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。 [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. . ;

[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〇 [0026] The above preparation method, the step of purifying the second step, step 4), the retention time of the constant voltage may be particularly 120min ~ 135min, 125min ~ 135min, 120min, 125min or 135min〇

[0027] 本发明方法制备得到的三氧化钼的纯度多99. 99%。 Purity molybdenum trioxide Preparation [0027] The method of the present invention obtained by a multi-99.99%.

[0028] 本发明制备高纯三氧化钼的操作过程简单,能够满足实验室纯化或制备几十毫克到几百毫克微量钼试剂的需求,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,纯化后可制得纯度彡99. 99%的高纯钼试剂。 [0028] During operation of the present invention prepared in high purity molybdenum trioxide simple, can be purified or prepared for laboratory tens of milligrams to several hundred milligrams of agent demand trace molybdenum, and because the purification process without adding any chemicals, impurities can be reduced introduction, can be obtained after purification the purity of 99.99% purity San molybdenum reagent.

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,三氧化钼纯化方法的回收率按照下述公式计算: [0030] The following embodiment of the present invention, the purification process of recovery of molybdenum trioxide calculated according to the following formula:

Figure CN104003446BD00041

[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钼金属单质粉末以及纯化后制得三氧化钼中杂质的含量。 Mass spectroscopy content before purification elemental molybdenum metal powder, and molybdenum trioxide was obtained after purification of impurities in high resolution inductively coupled plasma [0032] The following embodiment of the present invention 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宄院。 68 kinds of multi-element metal and non-metallic elements mixed solution of the standard substance (BW3197-BW3200) was purchased from China Metrology study based on hospital.

[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钼金属单质粉末以及纯化后三氧化钼的纯度。 By a standard curve method semiquantitative analysis impurity content of the samples is 67, so calculated prior to purification elemental molybdenum metal powder, and molybdenum trioxide purity after purification.

[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钼金属单质粉末原料颗粒度为100目。 Particle size of the raw material powder of molybdenum metal elements used in the following examples of embodiments [0036] The present invention is of 100 mesh.

[0037] 实施例1、高纯三氧化钼的制备 Preparation Example 1, high-purity molybdenum oxide [0037] Embodiment

[0038] 原料为天然丰度钼金属单质,钼的质量百分比为99. 89%。 [0038] The raw materials for the natural abundance of molybdenum metal in elemental weight percentage of molybdenum is 99.89%. 称取钼粉末原料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。 Mo powder material was weighed in a quartz beaker 605. 64mg, placed in a muffle furnace heated air into the oxidation reaction. 升温过程如下: Heating process is as follows:

[0039] 1)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] 1) Open the 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,以确保钼粉末充分氧化; [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 molybdenum powder;

[0041] 3)停止加热,马弗炉内温度降温至400°C时,打开马弗炉,将装有三氧化钼粉末的烧杯取出,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 furnace is opened, with the molybdenum 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钼粉末进行纯化,具体步骤如下: [0042] the oxidation of molybdenum trioxide powder obtained was purified by the following steps:

[0043] 1)称取116. 22mg三氧化钼粉末置于石英舟内; [0043] 1) weighed 116. 22mg molybdenum 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,使三氧化钼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 powder starts to sublime the molybdenum trioxide and deposited in the sample collection tube;

[0048] 6)停止加热,保持石英管内真空为lOOPa,三氧化钼粉末在样品石英收集管内自然冷却至室温; [0048] 6) the heating was stopped, the vacuum is maintained in the quartz tube Loopa, molybdenum trioxide powder was allowed to cool to room temperature in a quartz sample collection 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钼晶体。 [0049] 7) closing mechanical vacuum pump and a tube furnace, a quartz sample taken from the collection tube into the quartz tube, high purity molybdenum trioxide crystals.

[0050] 纯化后三氧化钼纯度分析: [0050] After purification trioxide purity analysis:

[0051] 称量收集管中三氧化钼晶体,质量为102. 59mg,计算得到利用上述方法制备的三氧化钼的回收率为88. 27 %。 [0051] The collection tubes were weighed molybdenum trioxide crystals, the quality of 102. 59mg, calculate the recovery of molybdenum trioxide was prepared by the above method 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钼金属单质粉末以及纯化后制得三氧化钼中杂质的含量。 [0052] The molybdenum content before purification elemental metal powder, and molybdenum trioxide obtained after purification by impurities in high resolution inductively coupled plasma mass spectrometer. 结果表明,纯化前钼试剂中钼金属单质的质量百分比为99. 89%;纯化后制得三氧化钼样品中三氧化钼的质量百分比为99. 99%。 The results showed that the percentage by mass of molybdenum before purification reagent is elemental molybdenum metal 99.89%; molybdenum trioxide obtained after purification by mass percent molybdenum trioxide 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.纯化前钼粉末原料及纯化后三氧化钼中主要杂质元素的质量百分比(% ) [0054] After purification percentage weight of the stock and major impurity element Molybdenum trioxide powder before Table 1. Purification (%)

Figure CN104003446BD00061

[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、高纯三氧化钼的制备 Preparation Example 2, high-purity molybdenum oxide [0057] Embodiment

[0058] 原料为天然丰度钼金属单质,钼的质量百分比为99. 89%。 [0058] The raw materials for the natural abundance of molybdenum metal in elemental weight percentage of molybdenum is 99.89%. 称取钼粉末原料939. 93 mg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。 Mo powder material weighed 939. 93 mg 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] 1)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] 1) Open the 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,以确保钼粉末充分氧化; [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 molybdenum powder;

[0061] 3)停止加热,马弗炉内温度降温至350°C时,打开马弗炉,将装有三氧化钼粉末的烧杯取出,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 furnace is opened, with the molybdenum 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钼粉末进行纯化,具体步骤如下: [0062] the oxidation of molybdenum trioxide powder obtained was purified by the following steps:

[0063] 1)称取121. 41mg三氧化钼粉末置于石英舟内; [0063] 1) weighed 121. 41mg molybdenum 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,使三氧化钼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 powder starts to sublime the molybdenum trioxide and deposited in the sample collection tube;

[0068] 6)停止加热,保持石英管内真空为lOOPa,三氧化钼粉末在样品石英收集管内自然冷却至室温; [0068] 6) the heating was stopped, the vacuum is maintained in the quartz tube Loopa, molybdenum trioxide powder was allowed to cool to room temperature in a quartz sample collection 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钼晶体。 [0069] 7) closing mechanical vacuum pump and a tube furnace, a quartz sample taken from the collection tube into the quartz tube, high purity molybdenum trioxide crystals.

[0070] 纯化后三氧化钼样品纯度分析: [0070] Sample purity after purification trioxide Analysis:

[0071] 称量收集管中三氧化钼晶体,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 molybdenum trioxide crystals, the quality of 104. 98mg, recovery was calculated by the method described above 86.47%.

[0072] 采用高分辨电感耦合等离子体质谱仪分析纯化前钼金属单质粉末以及纯化后制得三氧化钼中杂质的含量。 [0072] The molybdenum content before purification elemental metal powder, and molybdenum trioxide obtained after purification by impurities in high resolution inductively coupled plasma mass spectrometer. 结果表明,纯化前钼试剂中钼金属单质的质量百分比为99. 89% ;纯化后制得三氧化钼样品中三氧化钼的质量百分比为99. 99%。 The results showed that the percentage by mass of molybdenum before purification reagent is elemental molybdenum metal 99.89%; molybdenum trioxide obtained after purification by mass percent molybdenum trioxide 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.纯化前钼粉末原料及纯化后三氧化钼中主要杂质元素的质量百分比(% ) [0074] Table 2. Percentage of raw materials and the quality of the purified major impurity element Molybdenum trioxide powder before purification (%)

Figure CN104003446BD00071

[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、高纯三氧化钼的制备 Preparation Example 3, high-purity molybdenum oxide [0078] Embodiment

[0079] 原料为98M〇丰度为98. 15%的浓缩钼同位素(金属单质),钼的质量百分比为99. 89%。 [0079] The feedstock is 98M〇 abundance of 98.15% of molybdenum isotopes concentrate (elemental metal), mass percent molybdenum is 99.89%. 称取钼粉末原料380. 8lmg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。 Mo powder were weighed in a quartz material 380. 8lmg beaker, placed in a muffle furnace heated air into the oxidation reaction. 升温过程如下: Heating process is as follows:

[0080] 1)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] 1) Open the 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,以确保钼粉末充分氧化; [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 molybdenum powder;

[0082] 3)停止加热,马弗炉内温度降温至370°C时,打开马弗炉,将装有三氧化钼粉末的烧杯取出,放入真空保干器内冷却至室温; When the [0082] 3) heating was stopped, muffle furnace cooled until the temperature 370 ° C, the muffle furnace is opened, with the molybdenum trioxide powder beaker was taken, cooled to room temperature into a vacuum desiccator;

[0083] 对上述氧化得到的三氧化钼粉末进行纯化,具体步骤如下: [0083] the oxidation of molybdenum trioxide powder obtained was purified by the following steps:

[0084] 1)称取139. 04mg三氧化钼粉末置于石英舟内; [0084] 1) weighed 139. 04mg molybdenum 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lOOPa,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 Loopa, 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,使三氧化钼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 powder starts to sublime the molybdenum trioxide and deposited in the sample collection tube;

[0089] 6)停止加热,保持石英管内真空为lOOPa,三氧化钼粉末在样品石英收集管内自然冷却至室温; [0089] 6) the heating was stopped, the vacuum is maintained in the quartz tube Loopa, molybdenum trioxide powder was allowed to cool to room temperature in a quartz sample collection 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钼晶体。 [0090] 7) closing mechanical vacuum pump and a tube furnace, a quartz sample taken from the collection tube into the quartz tube, high purity molybdenum trioxide crystals.

[0091] 纯化后三氧化钼纯度分析: [0091] After purification trioxide purity analysis:

[0092] 称量收集管中三氧化钼晶体,质量为121. 66mg,计算得到上述方法的回收率为87. 50%〇 [0092] The collection tubes were weighed molybdenum trioxide crystals, the quality of 121. 66mg, the recovery method described above is calculated 87.50% billion

[0093] 采用高分辨电感耦合等离子体质谱仪分析纯化前钼金属单质粉末以及纯化后制得三氧化钼中杂质的含量。 [0093] The molybdenum content before purification elemental metal powder, and molybdenum trioxide obtained after purification by impurities in high resolution inductively coupled plasma mass spectrometer. 结果表明,纯化前钼试剂中钼金属单质的质量百分比为99. 88% ;纯化后制得三氧化钼样品中三氧化钼的质量百分比为99. 99%。 The results showed that the percentage by mass of molybdenum before purification reagent is elemental molybdenum metal 99.88%; molybdenum trioxide obtained after purification by mass percent molybdenum trioxide 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.纯化前钼粉末原料及纯化后三氧化钼中主要杂质元素的质量百分比(% ) [0094] Table 3. The percentage weight of the stock and major impurities after purification Molybdenum trioxide powder before purification (%)

Figure CN104003446BD00081

[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 (5)

1. 一种高纯三氧化钼的制备方法,其特征在于,包括如下步骤: 在空气存在的条件下,钼金属单质粉末经氧化反应得到三氧化钼; 所述氧化反应的升温过程如下: 1) 将温度升至100°c~200°C,并保持恒温; 2) 继续升温至550°C~650°C,进行所述氧化反应; 所述方法还包括对所述三氧化钼进行纯化的步骤: 1) 将所述三氧化钼置于一封闭的容器中,并在所述容器中设置收集管; 2) 加热所述三氧化钼所在区域,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,并使所述三氧化钼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钼。 1. A method for preparing high-purity molybdenum trioxide, which is characterized by comprising the steps of: in the presence of air, elemental molybdenum metal powder obtained by the oxidation reaction of molybdenum trioxide; heating process of the oxidation reaction as follows: ) the temperature was raised to 100 ° c ~ 200 ° C, and held constant; 2) continue to heat up to 550 ° C ~ 650 ° C, the oxidation reaction is carried out; the method further comprising the purification of molybdenum trioxide step: 1) the molybdenum trioxide are placed in a closed container, and the collection tube disposed in said container; 2) the molybdenum trioxide heating zone where the temperature was increased to 100 ~ 150 ° C; for the vessel was evacuated to 10 ~ lOOPa, and maintaining constant temperature and pressure; 3) to stop the vacuum and the temperature of the molybdenum trioxide area raised to 600 ° C ~ 720 ° C, and held constant; 4) to proceed with the vessel was evacuated to 10 ~ lOOPa, and to maintain constant pressure 120 ~ 150min, i.e. the molybdenum trioxide was collected after the sublimation purification in the collection tube.
2. 根据权利要求1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1) 中,在20~40min内将温度升至100°C~200°C ; 所述恒温的时间为30~60min。 The production method according to claim 1, wherein: the heating process of the oxidation reaction in step 1), the inner temperature was raised to 20 ~ 40min 100 ° C ~ 200 ° C; the thermostat the time is 30 ~ 60min.
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 claim 1 or claim 2, wherein: the heating process of the oxidation reaction in step 2), the inside temperature was raised to 60 ~ 90min 550 ° C ~ 650 ° C; the said oxidation reaction time was 480 ~ 960min.
4. 根据权利要求1或2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 of claim 1 or claim 2, wherein: the purification step, step 2), the inner temperature was raised to 20 ~ 40min 100 ° C ~ 150 ° C; the thermostat the retention time of the constant voltage 30 ~ 60min.
5. 根据权利要求1或2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 of claim 1 or claim 2, wherein: the purification step, step 3), the inside temperature was raised to 60 ~ 90min 600 ° C ~ 720 ° C; the thermostat the retention time of 120 ~ 150min.
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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
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