WO2017173948A1 - 一种催化还原硒的方法 - Google Patents

一种催化还原硒的方法 Download PDF

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WO2017173948A1
WO2017173948A1 PCT/CN2017/078689 CN2017078689W WO2017173948A1 WO 2017173948 A1 WO2017173948 A1 WO 2017173948A1 CN 2017078689 W CN2017078689 W CN 2017078689W WO 2017173948 A1 WO2017173948 A1 WO 2017173948A1
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selenium
solution
hexavalent
reduction
hydrogen peroxide
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郭学益
徐润泽
李栋
田庆华
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/02—Elemental selenium or tellurium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/01—Hydrogen peroxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the invention relates to a method for catalytically reducing selenium, in particular to a method for reducing hexavalent selenium into elemental selenium.
  • Selenium is a typical element between metal and non-metal. It is widely used in the glass and dyeing industry. It is irreplaceable in optimizing glass properties and preparing high temperature resistant red dye. In the field of materials, different proportions of selenium Adding steel, copper, rubber, etc. can significantly improve its oxidation resistance, mechanical properties and wear resistance; the most important development field of selenium is the optoelectronic industry, its special conductivity and excellent light absorption properties make it in semiconductors, lasers, and electrons. The device plays an important role, and these unique features bring its huge use value and demand.
  • the recovery of industrial selenium is mainly concentrated in the field of hydrometallurgy, mainly from the traditional copper anode slime distillation-reduction, complex selenium-containing slag leaching-reduction and selenium-containing secondary material oxidative leaching-reduction process. .
  • ferrous iron can effectively reduce hexavalent selenium to elemental, but the current research results show that ferrous reduction is only suitable for the treatment of ultra-low concentration hexavalent selenium solution, the reaction rate is slow And the reduction product is a complex compound of iron and selenium.
  • Selenium-iron separation needs to be continued to recover selenium separately, and the process flow is complicated; 3 the aluminum salt compound is used to adsorb and precipitate hexavalent selenium, and the problem is similar to the ferrous salt reduction process, that is, Low processing capacity, only suitable for processing ultra-low concentration selenium solution, the reaction rate is slow, and the reduction product is aluminum-selenium compound.
  • hexavalent selenium is difficult to use the existing selenium production process for effective recovery, which in turn causes hexavalent selenic acid or hexavalent selenate to enter the wastewater treatment process, resulting in a large amount of waste of resources. Due to the shortcomings of the prior art to reduce the hexavalent selenium requirements and the long recycling process, there is still no hexavalent selenium recovery technology with high recovery rate, short process flow and high industrial feasibility.
  • the technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a method for directly reducing hexavalent selenium, and A single element of selenium is prepared in one step.
  • the method is simple in operation and high in industrial feasibility, and effectively solves the technical problem in the existing selenium production process.
  • the technical solution proposed by the present invention is:
  • the use of hydrogen peroxide as a catalyst reduces the activation energy of hexavalent selenium reduction reaction, effectively reduces hexavalent selenium directly to selenium elemental substance, and reduces the rapid decline of the reduction process potential due to the presence of hydrogen peroxide, effectively avoiding the reduction of selenium. problem.
  • the standard redox potential of the reducing agent is lower than the standard redox potential of the hexavalent selenium converted to the elemental selenium, that is, the standard redox potential should be lower than the standard redox of Se 6+ /Se 0 Potential.
  • the reducing agent is one or more of hydrazine hydrate, sulfur dioxide, sulfite, and sodium borohydride.
  • the ratio of the volume of the hydrogen peroxide to the concentration of selenium in the solution is not less than 10 mL: 1 g/L.
  • the solution is a selenic acid or selenate solution containing hexavalent selenium, specifically a solution containing hexavalent selenium produced in chemical or metallurgical scientific research or industrial production, such as: sulfation roasting a solution containing hexavalent selenic acid or hexavalent selenate produced by the process of anode slime; a solution containing hexavalent selenic acid or hexavalent selenate produced in the process of desulfurization and de-selenization in the coal industry; A solution of hexavalent selenic acid or hexavalent selenate produced by oxidative leaching; a solution containing hexavalent selenium prepared by selenium-containing compound such as selenium dioxide or selenous acid or selenate during purification and purification of selenium.
  • selenic acid or selenate solution containing hexavalent selenium specifically a solution
  • the hexavalent selenium-containing solution may further contain a tetravalent selenite or selenite compound.
  • the temperature of the selenium-containing solution is controlled to be 0 to 100 ° C during the reduction.
  • the pH and reaction temperature of the solution have little effect on the catalytic reduction of hexavalent selenium.
  • the invention aims to reduce the activation energy of the reaction process, and selects hydrogen peroxide as a catalyst for reducing the activation energy of the hexavalent selenium reduction process, and successfully reduces the hexavalent selenium which is difficult to be reduced by the reaction kinetics to the selenium element.
  • Thermodynamic studies have found that the standard electrochemical reaction potential of many reducing agents, such as sulfur dioxide, sodium borohydride, etc., is lower than the potential of hexavalent selenium to selenium ( ⁇ [Se 6+ /Se 0 ]), but the actual The reduction of hexavalent selenium in the research process is very difficult. It needs high temperature, high acidity and high salt to quickly reduce it to simple substance.
  • the hexavalent selenium reduction process is mainly hindered by the reduction process kinetics.
  • the long-term study of the present invention found that hydrogen peroxide can effectively reduce the activation energy of the hexavalent selenium reduction process, so that hexavalent selenium can be reduced to some common reducing agents under normal temperature, low acid and low salt conditions. Elemental selenium.
  • the present invention realizes one-step reduction of a selenic acid or selenate solution containing hexavalent selenium into a single selenium product;
  • the invention adopts hydrogen peroxide as a catalyst, and the hydrogen peroxide effectively reduces the decrease rate of the solution reduction potential while catalyzing, so that the reduction reaction process is gentle, thereby effectively avoiding the reduction of selenium in the solution to produce negative divalent selenium ions or compounds thereof. It solves the problem of low recovery rate caused by selenium over-reduction.
  • Figure 1 is an X-ray diffraction detection chart of a reduced product of Example 1 of the present invention.
  • Fig. 2 is a view showing the X-ray diffraction detection of the reduced product of Example 2 of the present invention.
  • the various reagents and raw materials used in the present invention are commercially available products or products which can be obtained by a known method.
  • a method for catalytically reducing selenium according to the present invention the specific steps are as follows:
  • Sodium selenate Na 2 SeO 4 was dissolved in ultrapure water to prepare sodium selenate solution, so that the selenium content in the solution was 1 g/L, the initial pH of the solution was adjusted to 2, 100 mL of the solution was taken, and 15 mL was added with a constant flow pump. Analyze pure hydrogen peroxide, mix and pass into industrial grade sulfur dioxide gas (gas flow rate is 1L/min), and control the temperature of the reaction system to 60 °C by water bath for 2 hours. After filtration, detect the remaining selenium content in the solution, and finally the selenium reduction rate. For 99.97%, the reduced solid product was subjected to X-ray diffraction detection (as shown in Fig.
  • a method for catalytically reducing selenium according to the present invention the specific steps are as follows:
  • sodium selenate Na 2 SeO 4
  • the selenium content was 1 g / L
  • the initial pH of the solution was adjusted to 2
  • 100 mL of the solution was taken
  • 15 mL of analytical hydrogen peroxide was added by a constant flow pump.
  • the industrial grade sulfur dioxide gas is introduced (the gas flow rate is 1L/min), and the temperature of the reaction system is controlled by an ice water bath at 0 ° C for 2 hours.
  • the residual selenium content in the solution is detected, and the selenium reduction rate is calculated to be 99.89.
  • a method for catalytically reducing selenium according to the present invention the specific steps are as follows:
  • a method for catalytically reducing selenium according to the present invention the specific steps are as follows:
  • the selenium-containing waste material was treated by pressurized oxidizing acid leaching. After ion chromatography, 2.1 g/L hexavalent selenate ion and 5 g/L of selenite ion were detected. 200 mL of the solution was taken, 25 mL of hydrogen peroxide was added, and the reaction temperature was controlled by a water bath. 50 ° C, and added 5g of sodium borohydride, the reaction was filtered for 2 hours, the residual selenium content in the solution was measured, and the selenium reduction rate was calculated to be 99.35%.
  • the X-ray detection result of selenium was the same as that of Example 1, inductively coupled plasma atomic emission. The spectral detection results are shown in Table 1.
  • a method for catalytically reducing selenium according to the present invention the specific steps are as follows:
  • the selenium bismuth mixture was acid oxidized and leached. After filtering the insoluble matter, the detection solution contained 5.2 g/L hexavalent selenium ion and 18.9 g/L tetravalent selenium ion. After reduction with conventional sulfur dioxide, 5.1 g/L hexavalent selenium remained in the solution. Ion, take 200mL of this solution, add 55mL hydrogen peroxide, control the reaction temperature to 90 °C in water bath, pass industrial grade sulfur dioxide (gas flow rate is 1.5L/min), filter for 1 hour, filter, detect residual selenium content in solution, calculate selenium reduction The rate was 99.53%, and the X-ray detection results of selenium were the same as in Example 1. The results of inductively coupled plasma atomic emission spectrometry were as shown in Table 1.
  • a method for catalytically reducing selenium according to the present invention the specific steps are as follows:
  • Example 5 Using 200 mL of the same hexavalent selenium solution as in Example 5, adding 50 mL of hydrogen peroxide, controlling the reaction temperature to 20 ° C in a water bath, introducing industrial grade sulfur dioxide (gas flow rate of 1.5 L/min), filtering after 1 hour, and detecting the remaining in the solution.
  • the selenium content was calculated to be 99.49%.
  • the X-ray detection results of selenium were the same as those in Example 2.
  • the results of inductively coupled plasma atomic emission spectrometry were as shown in Table 1.
  • a method for catalytically reducing selenium according to the present invention the specific steps are as follows:
  • the selenium-containing acid sludge is oxidized and leached by sodium hydroxide-hydrogen peroxide. After leaching, the pH is adjusted to be neutral, and the ruthenium is precipitated. After filtration, the detection solution contains 2.2 g/L of hexavalent selenium ion, 200 mL of the solution is taken, and 25 mL of hydrogen peroxide solution is added. After mixing evenly, add 50mL of hydrazine hydrate solution with a concentration of 40%, control the reaction temperature at 80 °C in water bath, filter for 2 hours, and measure the residual selenium content in the solution to calculate the selenium reduction rate of 97.89%.
  • the results of inductively coupled plasma atomic emission spectrometry were as shown in Table 1 as in Example 1.
  • Example 1 99.91 0.09
  • Example 2 99.87 0.13
  • Example 3 98.35 1.65
  • Example 4 96.92 3.08
  • Example 5 97.93 2.07
  • Example 6 98.01 1.99
  • Example 7 92.35 7.65

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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  • Removal Of Specific Substances (AREA)

Abstract

一种催化还原硒的方法，用双氧水作为催化剂，在含六价硒的溶液中加入还原剂进行反应使硒还原成硒单质，所述还原剂的标准氧化还原电位低于六价硒转化为硒单质的标准氧化还原电位。本方法能够将含有六价硒元素的硒酸或硒酸盐溶液一步还原制成单质硒产品。本方法中双氧水在起催化作用的同时有效降低了溶液还原电位的下降速度，使得还原反应过程温和地进行，有效避免了溶液中硒过还原产生负二价硒离子或其化合物，解决了硒过还原引起的回收率低等问题。

Description

一种催化还原硒的方法 技术领域
本发明涉及一种催化还原硒的方法，尤其涉及一种将六价硒还原成单质硒的方法。
背景技术
硒为典型的介于金属与非金属之间的元素，被广泛应用于玻璃及染色行业，在优化玻璃性能、制备耐高温纯红色染料等方面具有不可替代性；在材料领域，不同比例的硒加入钢、铜、橡胶等可以显著提高其抗氧化、机械性能与耐磨程度；硒最重要的发展领域为光电产业，其特殊的电导性能、优异的吸光性能使其在半导体、激光、电子原器件中占有举足轻重的作用，这些独特的特性带来了其巨大的利用价值及需求量。
目前，工业硒的回收主要集中于湿法冶金领域，主要从传统的铜阳极泥蒸硒-还原、复杂含硒渣料的浸出-还原与含硒二次物料氧化浸出-还原等工艺中提取制备。
但目前溶液中硒还原过程出现两类难解决的问题：
(1)溶液中硒还原过程中易产生负二价的硒，使还原获得的单质硒再次以离子形式溶解，或与铜等重金属生成难溶化合物，进而直接降低了硒的回收率，后续处理过程加长了生产工艺流程，增加了硒回收过程难度。
(2)在含硒物料的提取分离过程中，多利用硒及其化合物易氧化分解的特点，采用氧化浸出或焙烧等方式将硒分离，但氧化过程中部分硒过氧化生成六价硒，目前处理该类六价硒酸或六价硒酸盐的方法有：①利用高浓度盐酸蒸煮还原的方式获得硒单质，但还原过程中会产生大量酸雾，操作不当还可能产生氯气等有害气体外漏，实际应用可能性低；②采用亚铁吸附还原，亚铁可以将六价硒有效还原为单质，但目前研究结果表明亚铁还原只适合处理超低浓度的六价硒溶液，反应速度慢，且还原产物为铁与硒的复杂化合物，单独回收硒需要继续进行硒-铁分离，工艺流程复杂；③采用铝盐的化合物将六价硒吸附沉淀，其问题类似亚铁盐还原过程，即处理能力低，只适合处理超低浓度的硒溶液，反应速度慢，还原产物为铝-硒的化合物。所以实际工业生产中，六价硒很难利用现有的硒生产流程进行有效回收，进而造成六价硒酸或六价硒酸盐只能进入废水处理流程，造成大量的资源浪费。正是由于现有技术还原六价硒条件要求高、回收流程长等缺点，导致目前仍未出现一种回收率高、工艺流程短、工业可行性高的六价硒回收技术。
发明内容
本发明要解决的技术问题是克服现有技术的不足，提供一种直接还原六价硒的方法，并 一步制备出硒单质产品。该方法操作简便、工业可行性高，有效的解决了现有硒生产过程中的技术难题。
为解决上述技术问题，本发明提出的技术方案为：
一种催化还原硒的方法，用双氧水作为催化剂，在含六价硒的溶液中加入还原剂进行反应使硒还原成硒单质。用双氧水作为催化剂，降低了六价硒还原反应活化能，有效的将六价硒直接还原为硒单质，并且由于双氧水的存在，降低了还原过程电位快速下降情况，有效避免了硒被过还原的问题。
上述的方法，优选的，所述还原剂的标准氧化还原电位低于六价硒转化为硒单质的标准氧化还原电位，即其标准氧化还原电位应低于Se6+/Se0的标准氧化还原电位。
上述的方法，优选的，所述还原剂为水合肼、二氧化硫、亚硫酸盐、硼氢化钠中的一种或几种。
上述的方法，优选的，所述双氧水体积与溶液中硒浓度的值比不低于10mL:1g/L。
上述的方法，优选的，所述溶液为含六价硒的硒酸或硒酸盐溶液，具体指化工或冶金类科学研究或工业生产中产生的含有六价硒的溶液，如：硫酸化焙烧处理阳极泥过程产生的含有六价硒酸或六价硒酸盐的溶液；煤炭行业脱硫脱硒过程中产生的含六价硒酸或六价硒酸盐的溶液；含硒废料回收处理过程中氧化浸出产生的六价硒酸或六价硒酸盐的溶液；硒净化提纯过程中用二氧化硒或亚硒酸或硒酸盐等含硒化合物配制的含六价硒的溶液等等。
上述的方法，优选的，所述含六价硒的溶液中还可以含有四价的亚硒酸或亚硒酸盐化合物。
上述的方法，优选的，所述还原过程中控制含硒溶液的温度为0～100℃。催化还原过程中，溶液的酸碱度与反应温度对于催化还原六价硒的方法影响不大。
本发明是基于降低反应过程活化能为目标，选择双氧水作为六价硒还原过程降低活化能的催化剂，成功地将反应动力学上难以还原的六价硒成功还原为硒单质。通过热力学的研究发现，许多还原剂，如二氧化硫、硼氢化钠等还原物质的标准电化学反应电位低于六价硒还原为硒单质的电位(Ψ[Se6+/Se0])，但实际研究过程中六价硒的还原非常困难，需要高温、高酸、高盐等条件才能快速的将其还原为单质，由此可以看出，六价硒还原过程阻碍主要为还原过程动力学阻碍。基于此研究结果，本发明通过长期研究发现，双氧水可以有效降低六价硒还原过程反应活化能，使得六价硒可以被一些常见还原剂，在常温、低酸、低盐的条件下被还原为单质硒。
与现有技术相比，本发明的优点在于：
(1)本发明实现了将含有六价硒元素的硒酸或硒酸盐溶液一步还原制成单质硒产品；本 发明由于采用双氧水为催化剂，双氧水在起催化作用的同时有效降低了溶液还原电位的下降速度，使得还原反应过程温和的进行，进而有效避免了溶液中硒过还原产生负二价硒离子或其化合物，解决了硒过还原引起的回收率低等问题。
(2)本发明的还原过程所需条件温和、反应流程短效果好、所需试剂及设备均为常见的湿法冶金工业设备及试剂，整体非常容易实现工业化生产应用。
附图说明
图1为本发明实施例1还原产物的X射线衍射检测图。
图2为本发明实施例2还原产物的X射线衍射检测图。
具体实施方式
除非另有定义，下文中所使用的所有专业术语与本领域技术人员通常理解的含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的，并不是旨在限制本发明的保护范围。
除有特别说明，本发明中用到的各种试剂、原料均为可以从市场上购买的商品或者可以通过公知的方法制得的产品。
为了便于理解本发明，下文将结合说明书附图和较佳的实施例对本发明作更全面、细致地描述，但本发明的保护范围并不限于以下具体的实施例。
实施例1：
一种本发明的催化还原硒的方法，具体步骤如下：
将硒酸钠(Na2SeO4)用超纯水溶解配制成硒酸钠溶液，使溶液中硒含量为1g/L，调节溶液的初始pH为2，取溶液100mL，用恒流泵加入15mL分析纯双氧水，混合均匀后通入工业级二氧化硫气体(气体流速为1L/min)，同时采用水浴控制反应体系温度为60℃，反应2小时，过滤后检测溶液中剩余硒含量，最终硒还原率为99.97％，对还原固体产物进行X射线衍射检测(如图1所示)、扫描电镜检测与电感耦合等离子体原子发射光谱检测结果(见表1)，由表1检测发现，还原产物为纯度较高的硒单质，纯度达99.91％，由图1可以看出，该产物为三方晶型的黑硒单质。
实施例2：
一种本发明的催化还原硒的方法，具体步骤如下：
将硒酸钠(Na2SeO4)用超纯水溶解配制成为硒酸钠溶液，使硒含量为1g/L，调节溶液初始pH＝2，取溶液100mL，用恒流泵加入15mL分析纯双氧水，混合均匀后通入工业级二氧化硫气体(气体流速为1L/min)，同时采用冰水浴控制反应体系温度为0℃，反应2小时，过滤后检测溶液中剩余硒含量，计算硒还原率为99.89％，对固体产物进行X射线衍射检测(如 图2所示)、扫描电镜检测与电感耦合等离子体原子发射光谱检测结果(见表1)，由表1可以看出，还原产物为较纯的硒单质，由图2可以看出，此硒单质为没有固定晶型的红硒单质。
实施例3：
一种本发明的催化还原硒的方法，具体步骤如下：
取某冶炼厂含六价硒废水1L，其中硒浓度为5.5g/L，其他杂质有砷离子、钠离子、铬离子及有机物等，通过常见的中和、除杂等工序后，硒离子浓度为3.6g/L，加入过量的双氧水500mL分解其中的有机物等杂质后，加入30g亚硫酸钠，水浴控温50℃，反应2小时后过滤，检测溶液中剩余硒含量，计算硒还原率为97.87％，硒单质X射线检测结果与实施例1相同，电感耦合等离子体原子发射光谱检测结果如表1所示。
实施例4：
一种本发明的催化还原硒的方法，具体步骤如下：
采用加压氧化酸浸处理含硒碲废料，经过离子色谱检测其中含有2.1g/L六价硒酸根离子，5g/L的亚硒酸根离子，取该溶液200mL，加入25mL双氧水，水浴控制反应温度为50℃，并加入5g硼氢化钠，反应2小时后过滤，检测溶液中剩余硒含量，计算硒还原率为99.35％，硒单质X射线检测结果与实施例1相同，电感耦合等离子体原子发射光谱检测结果如表1所示。
实施例5：
一种本发明的催化还原硒的方法，具体步骤如下：
将硒碲混合物酸性氧化浸出，过滤不溶物后检测溶液中含有5.2g/L六价硒离子，18.9g/L四价硒离子，采用常规二氧化硫还原后，溶液中剩余5.1g/L六价硒离子，取该溶液200mL，加入55mL双氧水，水浴控制反应温度为90℃，通入工业级二氧化硫(气体流量为1.5L/min)，反应1小时后过滤，检测溶液中剩余硒含量，计算硒还原率为99.53％，硒单质X射线检测结果与实施例1相同，电感耦合等离子体原子发射光谱检测结果如表1所示。
实施例6：
一种本发明的催化还原硒的方法，具体步骤如下：
采用与实施例5相同的六价硒溶液200mL，加入50mL双氧水，水浴控制反应温度为20℃，通入工业级二氧化硫(气体流量为1.5L/min)，反应1小时后过滤，检测溶液中剩余硒含量，计算硒还原率为99.49％，硒单质X射线检测结果与实施例2相同，电感耦合等离子体原子发射光谱检测结果如表1所示。
实施例7：
一种本发明的催化还原硒的方法，具体步骤如下：
将含硒碲的酸泥采用氢氧化钠-双氧水氧化浸出，浸出后调节pH为中性，沉淀碲，过滤后检测溶液中含有2.2g/L六价硒离子，取该溶液200mL，加入25mL双氧水，混合均匀后缓慢加入50mL浓度为40％的水合肼溶液，水浴控制反应温度80℃，反应2小时后过滤，检测溶液中剩余硒含量，计算硒还原率为97.89％，硒单质X射线检测结果与实施例1相同，电感耦合等离子体原子发射光谱检测结果如表1所示。
表1实施例1-7中还原产物的电感耦合等离子体原子发射光谱检测结果
实例名 硒含量％ 杂质含量％
实施例1 99.91 0.09
实施例2 99.87 0.13
实施例3 98.35 1.65
实施例4 96.92 3.08
实施例5 97.93 2.07
实施例6 98.01 1.99
实施例7 92.35 7.65

Claims (5)

  1. 一种催化还原硒的方法，其特征在于，用双氧水作为催化剂，在含六价硒的溶液中加入还原剂进行反应使硒还原成硒单质；所述溶液为含六价硒的硒酸或硒酸盐溶液，包括化工或冶金类科学研究或工业生产中产生的含有六价硒的溶液；所述双氧水体积与溶液中硒浓度的比值不低于10mL:1g/L。
  2. 如权利要求1所述的方法，其特征在于，所述还原剂的标准氧化还原电位低于六价硒转化为硒单质的标准氧化还原电位。
  3. 如权利要求2所述的方法，其特征在于，所述还原剂为水合肼、二氧化硫、亚硫酸盐、硼氢化钠中的一种或几种。
  4. 如权利要求1～3任一项所述的方法，其特征在于，所述溶液中还含有四价的亚硒酸或亚硒酸盐化合物。
  5. 如权利要求1～3任一项所述的方法，其特征在于，所述反应过程中控制溶液的温度为0～100℃。
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