WO2024061035A1 - 一种砷铁合金、及制备方法和资源化处理方法 - Google Patents

一种砷铁合金、及制备方法和资源化处理方法 Download PDF

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WO2024061035A1
WO2024061035A1 PCT/CN2023/117915 CN2023117915W WO2024061035A1 WO 2024061035 A1 WO2024061035 A1 WO 2024061035A1 CN 2023117915 W CN2023117915 W CN 2023117915W WO 2024061035 A1 WO2024061035 A1 WO 2024061035A1
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arsenic
iron
powder
iron alloy
pretreated
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PCT/CN2023/117915
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English (en)
French (fr)
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闵小波
柴飞
赵飞平
柴立元
梁彦杰
彭聪
周艺伟
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中南大学
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C28/00Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/002Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Definitions

  • the present invention relates to an arsenic-iron alloy and the resource utilization of arsenic, and in particular to an arsenic-iron alloy, a preparation method and a resource utilization treatment method.
  • arsenic ends up in various hazardous wastes, with high pollution risks, and non-ferrous smelting companies are facing tremendous pressure. But arsenic is also a resource. How to effectively utilize arsenic and expand the ways to absorb arsenic resources is of great significance.
  • the main purpose of the present invention is to provide an arsenic-iron alloy, its preparation method and resource utilization treatment method, aiming to solve the above technical problem of difficulty in resource utilization of arsenic.
  • the present invention provides a method for preparing an arsenic-iron alloy, which includes the steps:
  • the vacuum hot pressing sintering process includes:
  • the pretreated object is placed in a vacuum environment; then, the pretreated object is sintered, and during the sintering process, a pressure of 30 to 50 MPa is applied to the pretreated object;
  • the sintering process includes:
  • the pretreated material is raised from room temperature to 400 ⁇ 500°C and kept at the temperature for 0.5 ⁇ 1 hour; then, the pretreated material is raised from 400 ⁇ 500°C to 600 ⁇ 800°C and kept at the temperature for 0.5 ⁇ 1 hour.
  • the molar ratio of the arsenic powder to the iron powder is 0.1-0.35:1.
  • the molar ratio of the arsenic powder and the iron powder is 0.35 ⁇ 2:1.
  • step S1 before the arsenic powder and the iron powder are subjected to the ball milling process, the arsenic powder and the iron powder are mixed to obtain mixed powder.
  • the ball milling treatment includes a plurality of ball milling cycles, the ball milling time of each ball milling cycle is 30 to 60 minutes, and the interval between two adjacent ball milling cycles is 5 to 15 minutes;
  • the rotating speed of the ball mill is 250 ⁇ 400r/min, the ball-to-material ratio is 10 ⁇ 20:1, and the total duration of the ball milling is 8 ⁇ 48h;
  • the particle size of the grinding balls used in the ball milling process is one or more of 3 mm, 6 mm, 10 mm and 15 mm.
  • the purity of the arsenic powder and the iron powder is not less than 98.0wt.%.
  • the inert atmosphere includes one or more of argon and nitrogen.
  • the invention provides an arsenic-iron alloy, which is prepared by the preparation method described in any one of the above.
  • the invention provides a resource recycling method for arsenic iron slag, which includes the steps:
  • the arsenic slag and iron slag are ball milled under the protection of an inert atmosphere according to the molar ratio of arsenic element in the arsenic slag to iron element in the iron slag at a ratio of 0.1 ⁇ 0.35:1 or 0.35 ⁇ 2:1 to obtain pretreatment. thing;
  • the vacuum hot pressing sintering process includes:
  • the pretreated object is placed in a vacuum environment; then, the pretreated object is sintered, and during the sintering process, a pressure of 30 to 50 MPa is applied to the pretreated object;
  • the sintering process includes:
  • the pretreated material is raised from room temperature to 400 ⁇ 500°C and kept at the temperature for 0.5 ⁇ 1 hour; then, the pretreated material is raised from 400 ⁇ 500°C to 600 ⁇ 800°C and kept at the temperature for 0.5 ⁇ 1 hour.
  • the molar ratio of the arsenic slag and the iron slag is 0.1 ⁇ 0.35:1.
  • the present invention at least has the following advantages:
  • the preparation cost of the present invention is low, and the purity requirements of the raw materials are low; in addition, the high-temperature treatment time of the present invention is short and the treatment temperature is relatively low.
  • the present invention only requires simple ball milling and hot-pressing sintering to obtain the arsenic-iron alloy of the present invention, and the preparation procedure is relatively simple.
  • the present invention can alloy arsenic, and the obtained arsenic-iron alloy has higher crystallinity and purity.
  • the arsenic-iron alloy obtained by the present invention has high performance and low leaching toxicity; in the present invention, the density of the arsenic-iron alloy at room temperature is higher than 7g cm -3 , the compressive strength can reach more than 140MPa, and the hardness can reach 899.4HV0.5, and The leaching toxicity is low, lower than the national standard (5mg L -1 ), and has unexpected effects.
  • arsenic-iron alloy of the present invention such as high density, high strength, high hardness and low leaching toxicity, it is expected to be applied as a high-end alloy.
  • Figure 1 shows the appearance and morphology of the arsenic-iron alloy in Embodiment 1 of the present invention; (a) is the appearance and (b) is the morphology magnified 10 kx times;
  • Figure 2 is an XRD pattern of the arsenic-iron alloy in Example 1 of the present invention.
  • Figure 3 shows the appearance and morphology of the arsenic-iron alloy in Embodiment 2 of the present invention; (a) is the appearance and (b) is the morphology magnified 10 kx times;
  • Figure 4 is an XRD pattern of the arsenic-iron alloy in Example 2 of the present invention.
  • Figure 5 shows the appearance and morphology of the arsenic-iron alloy in Embodiment 3 of the present invention; (a) is the appearance and (b) is the morphology magnified 10 kx times;
  • Figure 6 is an XRD pattern of the arsenic-iron alloy in Example 3 of the present invention.
  • Figure 7 shows the appearance and morphology of the arsenic-iron alloy in Embodiment 4 of the present invention; (a) is the appearance and (b) is the morphology magnified 5 kx times;
  • Figure 8 is an XRD pattern of the arsenic-iron alloy in Example 4 of the present invention.
  • FIG9 is an appearance picture and a morphology picture of the ferroarsenic alloy in Example 5 of the present invention; wherein (a) is an appearance picture, and (b) is a morphology picture magnified 5 kx times;
  • Figure 10 is an XRD pattern of the arsenic-iron alloy in Example 5 of the present invention.
  • Figure 11 shows the appearance and morphology of the arsenic-iron product in Example 6 of the present invention; (a) is the appearance and (b) is the morphology magnified 5 kx times;
  • Figure 12 is an XRD pattern of the arsenic-iron alloy in Example 6 of the present invention.
  • Figure 13 shows the appearance and morphology of the arsenic-iron alloy in Embodiment 7 of the present invention; (a) is the appearance and (b) is the morphology magnified 5 kx times;
  • Figure 14 is an XRD pattern of the arsenic-iron alloy in Example 7 of the present invention.
  • FIG15 is an appearance picture and morphology picture of the ferroarsenic alloy in Example 8 of the present invention; wherein (a) is an appearance picture, and (b) is a morphology picture magnified 5 kx times;
  • FIG16 is an XRD diagram of the ferroarsenic alloy in Example 8 of the present invention.
  • Figure 17 shows the appearance and morphology of the arsenic-iron alloy in Example 9 of the present invention; (a) is the appearance and (b) is the morphology magnified 5 kx times;
  • FIG18 is an XRD diagram of the ferroarsenic alloy in Example 9 of the present invention.
  • Figure 19 is the appearance picture and morphology diagram of the arsenic-iron alloy in Comparative Example 1 of the present invention; (a) is the appearance diagram, (b) is the morphology diagram magnified 5 kx times;
  • Figure 20 is an XRD pattern of the arsenic-iron alloy in Comparative Example 1 of the present invention.
  • Figure 21 is an appearance view of the arsenic-iron alloy in Comparative Example 2 of the present invention.
  • arsenic-containing pollutants and iron slag can be smelted through high-temperature melting to obtain arsenic-iron alloy blocks for further application.
  • This method can not only effectively treat a large amount of arsenic-containing pollutants and solve the problem of accumulation of arsenic-containing solid waste for enterprises, but can also make arsenic-iron alloy materials from the arsenic iron blocks obtained by this method, increasing profits for enterprises.
  • the traditional high-temperature melting method not only has high energy consumption, but the performance of the obtained arsenic-iron alloy needs to be improved; in addition, the secondary pollution of arsenic and the toxicity of arsenic leaching in arsenic-iron alloy also need to be effectively prevented and controlled.
  • the present invention provides a preparation method of arsenic-iron alloy, including the steps:
  • the arsenic powder and iron powder are mixed to obtain mixed powder.
  • the purity of the arsenic powder and the iron powder may not be less than 98.0 wt.%.
  • the ball milling process can be performed in a vacuum ball milling tank, that is, iron powder and arsenic powder are mixed at different molar ratios and put into a vacuum ball milling tank, and ball milled under the protection of an inert atmosphere to perform mechanical alloying. chemical reaction.
  • the inert atmosphere can be one or more of argon and nitrogen;
  • the lining material of the vacuum ball mill tank can be stainless steel, corundum or cemented carbide;
  • the grinding ball material can be stainless steel, corundum or cemented carbide.
  • the ball milling process may include multiple ball milling cycles, each of which lasts for 30 to 60 minutes, and the interval between two adjacent ball milling cycles is 5 to 15 minutes. That is, the ball milling process is continuously operated for 30 to 60 minutes, then paused for 5 to 15 minutes, and repeated until the ball milling is completed.
  • the rotation speed of the ball mill is 250 to 400 r/min; the ball to material ratio is 10 to 20:1; the total duration of the ball mill is 8 to 48 hours, including the pause duration.
  • the particle size of the grinding balls used in the ball milling process may be one or more of 3 mm, 6 mm, 10 mm and 15 mm.
  • the vacuum hot pressing sintering process comprises:
  • the pretreated material is placed in a vacuum environment.
  • the pretreated object is sintered, and during the sintering process, a pressure of 30 to 50 MPa is applied to the pretreated object.
  • the sintering process includes:
  • the pretreated material is raised from room temperature to 400 ⁇ 500°C and kept at the temperature for 0.5 ⁇ 1 h; then, the pretreated material is raised from 400 ⁇ 500°C to 600 ⁇ 800°C and kept at the temperature for 0.5 ⁇ 1h.
  • the vacuum hot pressing sintering process can be specifically understood as: the sintering is performed under vacuum conditions, and during the sintering process, a pressure of 30 to 50 MPa is continuously applied to the pretreated object; and the pretreated material is The object is raised from room temperature to 400°C and kept for 0.5 ⁇ 1h. After the 400°C insulation is completed, the pretreated object is raised from 400°C to 600 ⁇ 800°C and kept for 0.5 ⁇ 1h; the pressure and temperature controls can be started simultaneously, thereby Ensure the formation of hot pressing conditions to obtain arsenic-iron alloys with high performance and low leaching toxicity.
  • the pretreated material is placed in a vacuum hot-pressing sintering furnace for hot-pressing sintering.
  • the vacuum hot-pressing sintering furnace is evacuated for 10 to 20 minutes.
  • the temperature in the furnace is first raised to 400 ⁇ 500°C and kept for 0.5 ⁇ 1h; then the temperature is raised to 600 ⁇ 800°C and kept for 0.5 ⁇ 1h, and then cooled to room temperature in the furnace.
  • the pressure of the vacuum hot pressing sintering furnace is simultaneously raised to 30MPa ⁇ 50MPa, maintained for 1 ⁇ 3h, and then cooled to room pressure with the furnace.
  • the compressive strength of the arsenic-iron alloy in the present invention can reach 140MPa, but it does not mean that the compressive strength of the arsenic-iron alloy in the present invention can only reach 140MPa. It is only limited by the test conditions. Only the compressive strength of the iron alloy is The strength was tested up to 140MPa.
  • the present invention also provides an arsenic-iron alloy, which is characterized in that it is prepared by using the preparation method described in any of the above embodiments.
  • the present invention also provides a resource treatment method for arsenic iron slag, which includes the steps:
  • the molar ratio of the arsenic slag and the iron slag is 0.1 ⁇ 0.35:1.
  • the molar ratio of the arsenic slag and the iron slag is 0.35 ⁇ 2:1.
  • the molar ratio of the arsenic slag to the iron slag can be the molar ratio of the arsenic element in the arsenic slag to the iron element in the iron slag; when there are a large number of impurities in the arsenic slag and the iron slag, it can be Before resource treatment, arsenic slag and iron slag are purified.
  • the iron slag may refer to iron powder; when only the iron slag is recycled, the arsenic slag may be referred to as arsenic powder.
  • the vacuum hot pressing sintering process may include: placing the pretreated object in a vacuum environment; then sintering the pretreated object, and applying a pressure of 30 to 50 MPa to the pretreated object during the sintering process;
  • the sintering process includes: raising the pretreated material from room temperature to 400 ⁇ 500°C and keeping it warm for 0.5 ⁇ 1h; then, raising the pretreated material from 400 ⁇ 500°C to 600 ⁇ 800°C and keeping it warm for 0.5 ⁇ 1h. 1h.
  • arsenic powder with a purity of 98wt.% and iron powder with a purity of 99.5wt.% mix them at a molar ratio of 0.1:0.9 and put them into a vacuum ball mill tank.
  • step 2 Place the vacuum ball milling tank in step 1 on the high-energy planetary ball mill.
  • the lining of the vacuum ball milling tank is made of stainless steel, and the grinding balls are made of stainless steel.
  • the grinding balls are 6mm and 10mm grinding balls distributed in a weight ratio of 1:1.
  • the material ratio is 20:1, and a rotation speed of 340r/min is used for the mechanical alloying reaction.
  • the reaction process runs continuously for 30 minutes and then pauses for 5 minutes.
  • the reaction time is 40h (including the pause time). After the mechanical alloying reaction is completed, the sample is taken out.
  • step 3 Place the sample obtained in step 2 into the vacuum hot-pressing sintering furnace mold, and maintain the vacuum for 20 minutes to avoid the presence of oxygen.
  • the vacuum hot-pressing sintering furnace was controlled to conduct vacuum hot-pressing sintering of the sample according to the following settings:
  • the temperature was raised to 400°C at a rate of 10°C/min and kept at that temperature for 30 min, then raised to 800°C at a rate of 10°C/min and kept at that temperature for 60 min, and finally cooled to room temperature with the furnace;
  • the synchronous control pressure was raised to 30MPa at a rate of 0.5MPa/s and maintained for 160min, and finally dropped to the room pressure at a rate of 0.5MPa/s.
  • the arsenic-iron alloy (A1) in this embodiment can be obtained.
  • the arsenic-iron alloy (A1) obtained in this example has a low arsenic content, so the physical phase is basically .
  • this example only adjusted the molar ratio of arsenic powder and iron powder in step 1 to 0.15:0.85.
  • this example only adjusted the molar ratio of arsenic powder and iron powder in step 1 to 0.25:0.75.
  • the main phase of the arsenic-iron alloy (A4) in this example is and Fe 2 As physical phase; compared with Examples 1 to 3, the characteristic peak intensity of Fe 2 As physical phase is enhanced, The intensity of the characteristic peaks of the physical phase decreases.
  • this example only adjusted the molar ratio of arsenic powder and iron powder in step 1 to 0.3:0.7.
  • the main phases of the arsenic-iron alloy (A5) in this example are Fe 2 As phase and weaker phase; compared with the phase of Example 4, the characteristic peak intensity of the Fe 2 As phase is enhanced, The intensity of the characteristic peaks of the physical phase is significantly reduced.
  • this example only adjusted the molar ratio of arsenic powder and iron powder in step 1 to 0.35:0.65.
  • the main phase of the arsenic-iron alloy (A6) in this example is Fe 2 As phase, without phase of matter.
  • this example only adjusted the molar ratio of arsenic powder and iron powder in step 1 to 0.4:0.6.
  • the main phases of the arsenic-iron alloy (A7) in this example are Fe 2 As phase and FeAs phase, without phase of matter.
  • the main phase of the arsenic-iron alloy (A8) in this example is FeAs phase, without and Fe 2 As phase.
  • Example 2 Compared with Example 1, this example only adjusted the molar ratio of arsenic powder and iron powder in step 1 to 0.6:0.4.
  • the main phases of the arsenic-iron alloy (A9) in this example are FeAs phase and FeAs 2 , without and Fe 2 As phase.
  • this comparative example only adjusted the molar ratio of arsenic powder and iron powder in step 1 to 0.7:0.3.
  • the main phase of the arsenic-iron alloy (A10) in this comparative example is FeAs 2 phase, without , Fe 2 As and FeAs phases.
  • Step 1 and step 2 of this comparative example are the same as those of Example 1.
  • step 3 of this comparative example the sample obtained in step 2 was put into the mold of a powder tablet press and cold pressed at 30 MPa for 20 minutes.
  • the obtained sample was placed in a quartz tube, vacuum-sealed, and finally placed in a tube furnace for sintering.
  • the tube furnace was used to sinter the samples according to the following settings:
  • the temperature was controlled to rise to 400°C at a heating rate of 10°C/min and kept for 30 minutes, then raised to 800°C at a heating rate of 10°C/min and kept for 60min, and finally cooled to room temperature in the furnace.
  • the arsenic iron product in this comparative example can be obtained.
  • the comparative example cannot obtain ferroarsenic alloy.
  • the appearance of the ferroarsenic product of the comparative example is shown in FIG21 . It can be seen that the ferroarsenic alloy block prepared by the ferroarsenic product in the comparative example has a loose surface and obvious holes, poor bonding after sintering, poor density, and obvious powder particles remaining. The original cylindrical sample is easily cracked after being taken out without pressure testing, and some powder falls off. It can be seen that the ferroarsenic alloy block prepared by the cold pressing sintering method has poor strength, and the mechanical properties cannot meet the requirements of conventional applications.
  • AKD-220A touch screen high-precision solid density tester uses the Archimedes principle buoyancy method to measure the density of the samples of each embodiment.
  • Compressive strength tested using an electronic universal testing machine.
  • Hardness test Use Vickers hardness tester to test.
  • Leaching toxicity evaluated using the national standard method.
  • the iron content, grain size and relative leaching toxicity have a greater impact on the corresponding mechanical properties.
  • the arsenic-iron alloy is more stable and has better performance; compared with the Fe 2 As phase, FeAs and FeAs 2 phases have better corrosion resistance. is small, resulting in higher leaching toxicity; as the arsenic content increases, the grain size generally decreases, and the strength reaches the maximum when the As/Fe ratio is 0.6:0.4, which may be attributed to the thermal conductivity at this ratio.

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Abstract

本发明提供一种砷铁合金的制备方法,包括步骤:S1,将砷粉和铁粉按0.1~2:1的摩尔比,在惰性气氛的保护下进行球磨处理,得预处理物;S2,对所述预处理物进行真空热压烧结处理,得所述砷铁合金;其中,所述真空热压烧结处理包括:将所述预处理物置于真空环境中;然后对所述预处理物进行烧结,并在所述烧结的过程中,对所述预处理物施加30~50MPa的压强;所述烧结的过程包括:将所述预处理物自室温升至400~500℃,保温0.5~1h,然后将所述预处理物自400~500℃升至600~800℃,保温0.5~1h。本发明可以获得高性能和低浸出毒性的砷铁合金。

Description

一种砷铁合金、及制备方法和资源化处理方法 技术领域
本发明涉及砷铁合金及砷的资源化利用,尤其涉及一种砷铁合金、及制备方法和资源化处理方法。
背景技术
中国拥有世界上大部分的砷储量,但同时我国也是产生砷污染的主要来源之一。据研究报道,我国的有色金属,例如铜、锑、金、铅、锌、锡等矿石的冶炼过程,是最重要的砷污染源。据不完全数据统计,我国年产砷渣50多万吨,已囤积的砷渣200余万吨,对周边环境造成严重污染。
同时,由于砷的毒性,传统砷制品市场急剧萎缩,致使金属砷的价格长期低迷,砷最终以各类危废赋存,污染风险高,有色冶炼企业面临巨大压力。但砷同时也是一种资源,如何将砷有效的资源化和拓展砷资源的消纳途径具有重要的意义。
鉴于此,有必要提供一种砷铁合金、及制备方法和资源化处理方法,以解决或至少缓解上述砷资源化困难的技术缺陷。
发明内容
本发明的主要目的是提供一种砷铁合金、及制备方法和资源化处理方法,旨在解决上述砷资源化困难的技术问题。
为实现上述目的,本发明提供了一种砷铁合金的制备方法,包括步骤:
S1,将砷粉和铁粉按0.1~2:1的摩尔比,在惰性气氛的保护下进行球磨处理,得预处理物;
S2,对所述预处理物进行真空热压烧结处理,得所述砷铁合金;
其中,所述真空热压烧结处理包括:
将所述预处理物置于真空环境中;然后,对所述预处理物进行烧结,并在所述烧结的过程中,对所述预处理物施加30~50MPa的压强;
所述烧结的过程包括:
将所述预处理物自室温升至400~500℃,保温0.5~1h;然后,将所述预处理物自400~500℃升至600~800℃,保温0.5~1h。
进一步地,所述砷粉和所述铁粉的摩尔比为0.1~0.35:1。
进一步地,所述砷粉和所述铁粉的摩尔比为0.35~2:1。
进一步地,所述步骤S1中,在对所述砷粉和所述铁粉进行所述球磨处理之前,将所述砷粉和所述铁粉进行混合处理,得混合粉末。
进一步地,所述球磨处理包括多个球磨周期,各所述球磨周期的球磨时长为30~60min,相邻两个所述球磨周期的间隔时长为5~15min;
所述球磨处理的过程中,球磨的转速为250~400r/min,球料比为10~20:1,球磨的总时长为8~48h;
所述球磨处理采用的磨球的粒径为3mm、6mm、10mm和15mm中的一种或几种。
进一步地,所述砷粉和所述铁粉的纯度均不小于98.0wt.%。
进一步地,所述惰性气氛包括氩气和氮气中的一种或几种。
本发明提供一种砷铁合金,采用如上述任意一项所述的制备方法进行制备。
本发明提供一种砷铁渣的资源化处理方法,包括步骤:
S01,将砷渣和铁渣按砷渣中砷元素与铁渣中铁元素的摩尔比为0.1~0.35:1或0.35~2:1的比例,在惰性气氛的保护下进行球磨处理,得预处理物;
S02,对所述预处理物进行真空热压烧结处理,得砷处理物;
其中,所述真空热压烧结处理包括:
将所述预处理物置于真空环境中;然后,对所述预处理物进行烧结,并在所述烧结的过程中,对所述预处理物施加30~50MPa的压强;
所述烧结的过程包括:
将所述预处理物自室温升至400~500℃,保温0.5~1h;然后,将所述预处理物自400~500℃升至600~800℃,保温0.5~1h。
进一步地,所述砷渣和所述铁渣的摩尔比为0.1~0.35:1。
与现有技术相比,本发明至少具有以下优点:
1、本发明的制备成本较低,且对原料纯度要求较低;此外,本发明的高温处理时间短、处理温度相对较低。
2、本发明只需简单的球磨和热压烧结即可得到本发明的砷铁合金,制备程序相对较为简单。
3、本发明可以将砷合金化,得到的砷铁合金具有较高的结晶度和纯度。
4、本发明获得的砷铁合金具有高性能和低浸出毒性;本发明中,砷铁合金室温下的密度高于7g cm -3,抗压强度能够达140MPa以上,硬度可达899.4HV0.5,且浸出毒性较低,可低于国家标准(5mg L -1),具有意料不到的效果。
5、基于上述性能,有望将砷进行有效的资源化,拓展砷资源的消纳途径,从而有效减少企业处理砷渣和铁渣的成本,且有望将其做成砷产品进行售卖与应用,从而提高砷渣和铁渣的经济性。比如,基于本发明的砷铁合金高密度、高强度、高硬度性且浸出毒性低等性能,有望将其作为高端合金进行应用。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图示出的结构获得其他的附图。
图1为本发明实施例1中砷铁合金的外观图和形貌图;其中,(a)为外观图,(b)为放大10 kx倍的形貌图;
图2为本发明实施例1中砷铁合金的XRD图;
图3为本发明实施例2中砷铁合金的外观图和形貌图;其中,(a)为外观图,(b)为放大10 kx倍的形貌图;
图4为本发明实施例2中砷铁合金的XRD图;
图5为本发明实施例3中砷铁合金的外观图和形貌图;其中,(a)为外观图,(b)为放大10 kx倍的形貌图;
图6为本发明实施例3中砷铁合金的XRD图;
图7为本发明实施例4中砷铁合金的外观图和形貌图;其中,(a)为外观图,(b)为放大5 kx倍的形貌图;
图8为本发明实施例4中砷铁合金的XRD图;
图9为本发明实施例5中砷铁合金的外观图和形貌图;其中,(a)为外观图,(b)为放大5 kx倍的形貌图;
图10为本发明实施例5中砷铁合金的XRD图;
图11为本发明实施例6中砷铁产物的外观图和形貌图;其中,(a)为外观图,(b)为放大5 kx倍的形貌图;
图12为本发明实施例6中砷铁合金的XRD图;
图13为本发明实施例7中砷铁合金的外观图和形貌图;其中,(a)为外观图,(b)为放大5 kx倍的形貌图;
图14为本发明实施例7中砷铁合金的XRD图;
图15为本发明实施例8中砷铁合金的外观图和形貌图;其中,(a)为外观图,(b)为放大5 kx倍的形貌图;
图16为本发明实施例8中砷铁合金的XRD图;
图17为本发明实施例9中砷铁合金的外观图和形貌图;其中,(a)为外观图,(b)为放大5 kx倍的形貌图;
图18为本发明实施例9中砷铁合金的XRD图;
图19为本发明对比例1中砷铁合金的外观图和形貌图;其中,(a)为外观图,(b)为放大5 kx倍的形貌图;
图20为本发明对比例1中砷铁合金的XRD图;
图21为本发明对比例2中砷铁合金的外观图。
本发明目的的实现、功能特点及优点将结合实施方式,参照附图做进一步说明。
具体实施方式
下面将结合本发明实施方式中的附图,对本发明实施方式中的技术方案进行清楚、完整地描述,显然,所描述的实施方式仅仅是本发明的一部分实施方式,而不是全部的实施方式。基于本发明中的实施方式,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施方式,都属于本发明保护的范围。
并且,本发明各个实施方式之间的技术方案可以相互结合,但是必须是以本领域普通技术人员能够实现为基础,当技术方案的结合出现相互矛盾或无法实现时应当认为这种技术方案的结合不存在,也不在本发明要求的保护范围之内。
需了解的是,针对于含砷污染物,大多数企业采取的措施主要是对其进行固化稳定化等无害化处理,并设置专门的仓库进行堆积。但该方法除了增容比大、处理成本高以外,仍然无法有效的利用砷资源,造成严重的砷资源浪费。
为了将砷资源合金化,可将大量含砷污染物与铁渣通过高温熔融的方式进行熔炼,得到砷铁合金块,并进行进一步的应用。该方法不仅能够有效的处理大量的含砷污染物,为企业解决含砷固废堆积问题,而且还能够通过该方法得到的砷铁块制作成砷铁合金材料,为企业增加收益。
然而,传统高温熔融的方式不仅能耗高,且获取的砷铁合金的性能有待提高;另外,砷的二次污染、以及砷铁合金中砷的浸出毒性也需要得到有效防治。
基于此,本发明提供了一种砷铁合金的制备方法,包括步骤:
S1,将砷粉和铁粉按0.1~2:1的摩尔比,在惰性气氛的保护下进行球磨处理,得预处理物。
其中,在对所述砷粉和铁粉进行所述球磨处理之前,将所述砷粉和铁粉进行混合处理,得混合粉末。所述砷粉和所述铁粉的纯度均可以不小于98.0wt.%。
需了解的是,砷和铁的摩尔比对砷铁合金的性能和浸出毒性具有较大的影响。而且,试验证明,在本发明的条件下,砷粉和铁粉的比例达到临界比例后,砷铁合金的性能明显下降,砷的浸出毒性会显著增大。
当所述砷粉和所述铁粉的摩尔比为为0.1~0.35:1时,可以获得浸出毒性极低,密度、抗压强度和硬度优异的砷铁合金。
当所述砷粉和所述铁粉的摩尔比为0.35~2:1时,可以获得浸出毒性较低,密度和硬度更为优异的砷铁合金。
作为对所述球磨处理的说明,所述球磨处理可以在真空球磨罐中进行,即,将铁粉和砷粉按不同摩尔比混合后放入真空球磨罐内,惰性气氛保护下球磨进行机械合金化反应。所述惰性气氛可以为氩气和氮气中的一种或几种;真空球磨罐内衬材质可以为不锈钢、刚玉或硬质合金;磨球材质为不锈钢、刚玉或硬质合金。
所述球磨处理可以包括多个球磨周期,各所述球磨周期的球磨时长为30~60min,相邻两个所述球磨周期的间隔时长为5~15min。即,球磨过程中连续运行30~60min后暂停5~15min,重复直至球磨结束。
所述球磨处理的过程中,球磨的转速为250~400r/min;球料比为10~20:1;球磨的总时长为8~48h,球磨的总时长包括暂停时长。
所述球磨处理采用的磨球的粒径可以为3mm、6mm、10mm和15mm中的一种或几种。
S2,对所述预处理物进行真空热压烧结处理,得所述砷铁合金。
其中,所述真空热压烧结处理包括:
将所述预处理物置于真空环境中。
然后,对所述预处理物进行烧结,并在所述烧结的过程中,对所述预处理物施加30~50MPa的压强。
所述烧结的过程包括:
将所述预处理物自室温升至400~500℃,保温0.5~1h;然后,将所述预处理物自400~500℃升至600~800℃,保温0.5~1h。
所述真空热压烧结处理具体可以理解为:所述烧结在真空条件下进行,且在所述烧结的过程中,对所述预处理物持续施加30~50MPa的压强;并将所述预处理物自室温升至400℃,保温0.5~1h,400℃保温完成后,将所述预处理物自400℃升至600~800℃,保温0.5~1h;压强和温度温度控制可以同步启动,从而保证热压条件的形成,以获得高性能和低浸出毒性的砷铁合金。
即,将所述预处理物置于真空热压烧结炉中进行热压烧结。在热压烧结过程中,首先,对真空热压烧结炉进行抽真空10~20min。
抽真空结束后,将炉内温度先升温至400~500℃保温0.5~1h;然后升温至600~800℃保温0.5~1h,随炉冷却至室温。并且,随着温度的控制,同步将真空热压烧结炉的压强升至30MPa~50MPa,保持1~3h,随炉冷却至室压。
需了解的是,通过进行上述实施方式中的特定工艺,并结合热压调控,可以避免砷的挥发,同时能够保证强度、高硬度、低浸出毒性砷铁合金的获取。
还需了解的是,本发明中砷铁合金的抗压强度可以达140MPa,但并不代表本发明中砷铁合金的抗压强度仅可以达到140MPa,只是受限于试验条件,仅对铁合金的抗压强度进行了最高140MPa的测试。
本发明还提供一种砷铁合金,其特征在于,采用如上述任意实施方式所述的制备方法进行制备。
为了实现对砷渣的有效利用,避免砷资源的浪费,以及避免砷的二次污染,降低砷的浸出毒性,本发明还提供一种砷铁渣的资源化处理方法,包括步骤:
S01,将砷渣和铁渣按0.1~2:1的摩尔比,在惰性气氛的保护下进行球磨处理,得预处理物。
进一步地,为了在获取砷铁合金的同时,充分降低砷的浸出毒性,所述砷渣和所述铁渣的摩尔比为0.1~0.35:1。作为另一可选方案,所述砷渣和所述铁渣的摩尔比为0.35~2:1。
需说明的是,所述砷渣与所述铁渣的摩尔比可以为砷渣中砷元素与铁渣中铁元素的摩尔比;当所述砷渣和所述铁渣中具有大量杂质时,可以在进行资源化处理之前,对砷渣和铁渣进行纯化处理。
另,当仅对所述砷渣进行资源化处理时,所述铁渣可以指代铁粉;当仅对所述铁渣进行资源化处理时,可以将所述砷渣指代为砷粉。
S02,对所述预处理物进行真空热压烧结处理,得砷处理物。
其中,所述真空热压烧结处理可以包括:将所述预处理物置于真空环境中;然后,对所述预处理物进行烧结,并在所述烧结的过程中,对所述预处理物施加30~50MPa的压强;
所述烧结的过程包括:将所述预处理物自室温升至400~500℃,保温0.5~1h;然后,将所述预处理物自400~500℃升至600~800℃,保温0.5~1h。
需说明的是,本发明中砷铁合金制备方法中的所有制备过程均可以部分或全部应用于砷铁渣的资源化处理方法。在应用过程中,可以仅将砷粉替换为砷渣,和/或将铁粉替换为铁渣。
为便于本领域技术人员对本发明做具体理解,现举例说明:
需指出的是,本发明说明书附图中的a Fe指代下述各实施例中的
实施例1
1、采用纯度为98wt.%的砷粉和纯度为99.5wt.%的铁粉,按0.1:0.9的摩尔比混合后放入真空球磨罐内。
2、将步骤1中的真空球磨罐置于高能行星球磨机上,真空球磨罐内衬材质为不锈钢,磨球材质为不锈钢,磨球为按1:1重量比分配的6mm和10mm磨球,球料比为20:1,采用340r/min的自转速度进行机械合金化反应,反应过程中连续运行30min后暂停5min,反应时间为40h(包含暂停时长),机械合金化反应结束后,取出样品。
3、将步骤2中所得样品放入真空热压烧结炉模具中,并抽真空保持20min,避免氧气的存在。
随后,控制真空热压烧结炉按以下设定对样品进行真空热压烧结:
控制温度以10℃/min升温速率升至400℃保温30min,再以10℃/min升温速率升至800℃保温60min,最后随炉冷却至室温;
在控制温度时,同步控制压强以0.5MPa/s速率升至30MPa保持160min,最后以0.5MPa/s速率降至室压。
当温度冷却至室温,且压强降至室压(不再施加压强)后,即可获得本实施例中的砷铁合金(A1)。
试验结果:
本实施例中砷铁合金的外观参见图1(a)所示,可以看出,本实施例中得到的砷铁合金为直径为12mm左右的圆柱体形状;
从图1(b)的形貌图中可以看出,在该比例下得到的砷铁合金,总体来说较为均匀,有部分铁单质团聚,表面存在少量晶粒且孔径尺寸较大;
从图2的XRD图谱中,可以看出,本实施例得到的砷铁合金(A1)由于砷含量较低,因此,物相基本为
本实施例中砷铁合金的性能参见分析例1,可以看出,本实施例中的砷铁合金具有优异的合金性能,且具有极低的浸出毒性。
实施例2
在试验过程中,本实施例相较于实施例1,仅将步骤1中砷粉和铁粉的摩尔比调整为0.15:0.85。
试验结果:
本实施例中砷铁合金的外观参见图3(a)所示,可以看出,本实施例中的砷铁合金外观和实施例1的外观图一样,均为直径为12mm左右的圆柱体形状;
从图3(b)的形貌图中可以看出,总体来说较为均匀,与实施例1相比,团聚程度降低,表面晶粒增加且晶粒尺寸减小;
从图4的XRD图谱中,可以看出,由于砷含量的增加,本实施例中砷铁合金(A2)主要物相为 和较弱的Fe 2As物相。
本实施例中砷铁合金的性能参见分析例1,可以看出,本实施例中的砷铁合金具有优异的合金性能,且具有极低的浸出毒性;硬度的增强可能归因于晶粒尺寸的减小,细晶强化作用效果增加。
实施例3
在试验过程中,本实施例相较于实施例1,仅将步骤1中砷粉和铁粉的摩尔比调整为0.2:0.8。
试验结果:
本实施例中砷铁合金的外观参见图5(a)所示,可以看出,本实施例中的砷铁合金外观和实施例1的外观图一样,均为直径为12mm左右的圆柱体形状;
从图5(b)的形貌图中可以看出,总体来说较为均匀,与实施例1相比,团聚程度降低,表面晶粒尺寸增加,导致硬度降低;
从图6的XRD图谱中,可以看出,随着砷含量的增加,本实施例中砷铁合金(A3)主要物相为 和Fe 2As物相;与实施例2物相相比,Fe 2As物相特征峰强度增强。
本实施例中砷铁合金的性能参见分析例1,可以看出,本实施例中的砷铁合金具有优异的合金性能,且具有极低的浸出毒性。
实施例4
在试验过程中,本实施例相较于实施例1,仅将步骤1中砷粉和铁粉的摩尔比调整为0.25:0.75。
试验结果:
本实施例中砷铁合金的外观参见图7(a)所示,可以看出,本实施例中的砷铁合金外观和实施例1的外观图一样,均为直径为12mm左右的圆柱体形状;
从图7(b)的形貌图中可以看出,总体来说较为均匀,与实施例1相比,团聚程度降低,表面晶粒增加且晶粒尺寸进一步减小;
从图8的XRD图谱中,可以看出,随着砷含量的增加,本实施例中砷铁合金(A4)主要物相为 和Fe 2As物相;与实施例1~3相比,Fe 2As物相特征峰强度增强, 物相特征峰强度降低。
本实施例中砷铁合金的性能参见分析例1,可以看出,本实施例中的砷铁合金具有优异的合金性能,且具有极低的浸出毒性。
实施例5
在试验过程中,本实施例相较于实施例1,仅将步骤1中砷粉和铁粉的摩尔比调整为0.3:0.7。
试验结果:
本实施例中砷铁合金的外观参见图9(a)所示,可以看出,本实施例中的砷铁合金外观和实施例1的外观图一样,均为直径为12mm左右的圆柱体形状;
从图9(b)的形貌图中可以看出,总体来说较为均匀,与实施例1相比,无铁单质团聚,表面晶粒尺寸较小;
从图10的XRD图谱中可以看出,随着砷含量的增加,本实施例中砷铁合金(A5)主要物相为Fe 2As物相和较弱的 相;与实施例4的物相相比,Fe 2As物相特征峰强度增强, 物相特征峰强度明显降低。
本实施例中砷铁合金的性能参见分析例1,可以看出,本实施例中的砷铁合金具有突出的合金性能,且具有较低的浸出毒性。
实施例6
在试验过程中,本实施例相较于实施例1,仅将步骤1中砷粉和铁粉的摩尔比调整为0.35:0.65。
试验结果:
本实施例中砷铁合金外观参见图11(a)所示,可以看出,本实施例中的砷铁合金外观和实施例1的外观图一样,均为直径为12mm左右的圆柱体形状;
从图11(b)的形貌图中可以看出,总体来说较为均匀,与实施例1相比,无铁单质团聚,表面晶粒增加且粒径较小;
从图12的XRD图谱中可以看出,随着砷含量的增加,本实施例中砷铁合金(A6)主要物相为Fe 2As物相,无 物相。
本实施例中砷铁合金的性能参见分析例1,可以看出,本实施例中的砷铁合金具有突出的合金性能,且具有较低的浸出毒性。
实施例7
在试验过程中,本实施例相较于实施例1,仅将步骤1中砷粉和铁粉的摩尔比调整为0.4:0.6。
试验结果:
本实施例中砷铁合金的外观参见图13(a)所示,可以看出,本实施例中的砷铁合金外观和实施例1的外观图一样,均为直径为12mm左右的圆柱体形状;
从图13(b)的形貌图中可以看出,总体来说较为均匀,与实施例1相比,无铁单质团聚,表面晶粒增加且粒径较小;
从图14的XRD图谱中可以看出,随着砷含量的增加,本实施例中砷铁合金(A7)主要物相为Fe 2As物相和FeAs物相,无 物相。
本实施例中砷铁合金的性能参见分析例1,可以看出,本实施例中的砷铁合金具有突出的合金性能,且具有较低的浸出毒性。
实施例8
在试验过程中,本实施例相较于实施例1,仅将步骤1中砷粉和铁粉的摩尔比调整为0.5:0.5。
试验结果:
本实施例中砷铁合金的外观参见图15(a)所示,可以看出,本实施例中的砷铁合金外观和实施例1的外观图一样,均为直径为12mm左右的圆柱体形状;
从图15(b)的形貌图中可以看出,总体来说较为均匀,与实施例1相比,无铁单质团聚,表面晶粒增加且粒径较小;
从图16的XRD图谱中可以看出,随着砷含量的增加,本实施例中砷铁合金(A8)主要物相为FeAs物相,无 和Fe 2As物相。
本实施例中砷铁合金的性能参见分析例1,可以看出,本实施例中的砷铁合金具有突出的合金性能,且具有较低的浸出毒性。
实施例9
在试验过程中,本实施例相较于实施例1,仅将步骤1中砷粉和铁粉的摩尔比调整为0.6:0.4。
试验结果:
本实施例中砷铁合金的外观参见图17(a)所示,可以看出,本实施例中的砷铁合金外观和实施例1的外观图一样,均为直径为12mm左右的圆柱体形状;
从图17(b)的形貌图中可以看出,总体来说较为均匀,与实施例1相比,无铁单质团聚,表面晶粒增加且粒径较小;
从图18的XRD图谱中可以看出,随着砷含量的增加,本实施例中砷铁合金(A9)主要物相为FeAs物相和FeAs 2,无 和Fe 2As物相。
本实施例中砷铁合金的性能参见分析例1,可以看出,本实施例中的砷铁合金具有突出的合金性能,且具有较低的浸出毒性。
对比例1
在试验过程中,本对比例相较于实施例1,仅将步骤1中砷粉和铁粉的摩尔比调整为0.7:0.3。
试验结果:
本对比例中砷铁合金的外观参见图19(a)所示,可以看出,本对比例中的砷铁合金外观和实施例1的外观图一样,均为直径为12mm左右的圆柱体形状;
从图19(b)的形貌图中可以看出,总体来说较为均匀,与实施例1相比,无铁单质团聚,表面晶粒粒径较大;
从图20的XRD图谱中可以看出,随着砷含量的增加,本对比例中砷铁合金(A10)主要物相为FeAs 2物相,无 、Fe 2As和FeAs物相。
本对比例中砷铁合金的性能参见分析例1,可以看出,本对比例中的砷铁合金合金性能出现下降,且具有较高的浸出毒性。
对比例2
本对比例的步骤1和步骤2与实施例1相同。
本对比例的步骤3中,将步骤2中所得样品放入粉末压片机的模具中,进行30MPa冷压20min。
随后,将所得的样品放置石英管中,并真空封管,最后放入管式炉进行烧结。
其中,管式炉按以下设定对样品进行烧结:
控制温度以10℃/min升温速率升至400℃保温30min,再以10℃/min升温速率升至800℃保温60min,最后随炉冷却至室温。
当温度冷却至室温,即可获得本对比例中的砷铁产物。
本对比例并不能获得砷铁合金。本对比例砷铁产物的外观参见图21所示,可以看出,本对比例中的砷铁产物制备出的砷铁合金块表面疏松并存在明显的孔洞,烧结后结合程度较差,致密度较差,同时残存有明显的粉末颗粒,在无需压力测试情况下原本圆柱状的样品取出后轻易就裂解,并有部分的粉末掉落,可以看出,冷压烧结方法制备得到的砷铁合金块强度较差,力学性能不能满足常规应用需求。
分析例1
对实施例1-9和对比例1中砷铁合金的性能进行性能测试:
密度:AKD-220A触摸屏高精度固体密度测试仪,利用阿基米德原理浮力法测得各个实施例样品的密度。
抗压强度:采用电子万能试验机测试。
硬度测试:采用维氏硬度计测试。
浸出毒性:采用国标法进行评估。
测试结果如下表所示:
综上所述,铁元素含量、晶粒尺寸大小和物相对浸出毒性和相应的机械性能有着较大的影响。当有铁元素含量较多、晶粒尺寸较小和物相为Fe 2As时,砷铁合金较为稳定且性能较好;与Fe 2As物相相比,FeAs和FeAs 2物相抗腐蚀性较小,从而导致浸出毒性较高;随着砷含量的增加,晶粒尺寸总体上随之降低,在As/Fe比为0.6:0.4时,强度达到最大,这可能归因于在该比例进行热压烧结时,形成了As-Fe-As角接近于109.4°的规则的FeAs 4四面体;但继续增加砷含量,硬度大幅度降低;这可能归因于,高含量的砷回削弱晶界内聚力并导致合金脆化,且导致FeAs 4四面体偏离规则形状,从而导致硬度大幅度下降。
本发明的上述技术方案中,以上仅为本发明的优选实施例,并非因此限制本发明的专利范围,凡是在本发明的技术构思下,利用本发明说明书及附图内容所作的等效结构变换,或直接/间接运用在其他相关的技术领域均包括在本发明的专利保护范围。

Claims (9)

  1. 一种砷铁合金的制备方法,其特征在于,包括步骤:
    S1,将砷粉和铁粉按0.1~2:1的摩尔比,在惰性气氛的保护下进行球磨处理,得预处理物;
    S2,对所述预处理物进行真空热压烧结处理,得所述砷铁合金;
    其中,所述真空热压烧结处理包括:
    将所述预处理物置于真空环境中;然后,对所述预处理物进行烧结,并在所述烧结的过程中,对所述预处理物施加30~50MPa的压强;
    所述烧结的过程包括:
    将所述预处理物自室温升至400~500℃,保温0.5~1h;然后,将所述预处理物自400~500℃升至600~800℃,保温0.5~1h。
  2. 根据权利要求1所述的砷铁合金的制备方法,其特征在于,所述砷粉和所述铁粉的摩尔比为0.1~0.35:1。
  3. 根据权利要求1所述的砷铁合金的制备方法,其特征在于,所述砷粉和所述铁粉的摩尔比为0.35~2:1。
  4. 根据权利要求1所述的砷铁合金的制备方法,其特征在于,所述步骤S1中,在对所述砷粉和所述铁粉进行所述球磨处理之前,将所述砷粉和所述铁粉进行混合处理,得混合粉末。
  5. 根据权利要求1所述的砷铁合金的制备方法,其特征在于,所述球磨处理包括多个球磨周期,各所述球磨周期的球磨时长为30~60min,相邻两个所述球磨周期的间隔时长为5~15min;
    所述球磨处理的过程中,球磨的转速为250~400r/min,球料比为10~20:1,球磨的总时长为8~48h;
    所述球磨处理采用的磨球的粒径为3mm、6mm、10mm和15mm中的一种或几种。
  6. 根据权利要求1所述的砷铁合金的制备方法,其特征在于,所述砷粉和所述铁粉的纯度均不小于98.0wt.%。
  7. 根据权利要求1-6任意一项所述的砷铁合金的制备方法,其特征在于,所述惰性气氛包括氩气和氮气中的一种或几种。
  8. 一种砷铁合金,其特征在于,采用如权利要求1-7任意一项所述的制备方法进行制备。
  9. 一种砷铁渣的资源化处理方法,其特征在于,包括步骤:
    S01,将砷渣和铁渣按砷渣中砷元素与铁渣中铁元素的摩尔比为0.1~0.35:1或0.35~2:1的比例,在惰性气氛的保护下进行球磨处理,得预处理物;
    S02,对所述预处理物进行真空热压烧结处理,得砷处理物;
    其中,所述真空热压烧结处理包括:
    将所述预处理物置于真空环境中;然后,对所述预处理物进行烧结,并在所述烧结的过程中,对所述预处理物施加30~50MPa的压强;
    所述烧结的过程包括:
    将所述预处理物自室温升至400~500℃,保温0.5~1h;然后,将所述预处理物自400~500℃升至600~800℃,保温0.5~1h。
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