阅读说明：本技术 一种基于钕铁硼油泥料制备的再生合金及其制备方法 (Recycled alloy prepared based on neodymium iron boron oil sludge and preparation method thereof ) 是由 王志 李世健 钱国余 王东 于 2021-01-11 设计创作，主要内容包括：本发明提供了一种基于钕铁硼油泥料制备的再生合金及其制备方法,所述制备方法包括以下步骤：(1)将钕铁硼油泥料进行预处理,得到固体粉末；(2)将步骤(1)所得固体粉末进行钙热还原处理,得到初级合金；(3)将步骤(2)所得初级合金进行电渣重熔处理,得到再生合金,且所述再生合金的氧含量≤0.1wt％。本发明提供的制备方法简化了操作流程,缩短了反应时间,进一步去除了非金属杂质,提高了再生合金的纯度。(The invention provides a recycled alloy prepared based on neodymium iron boron oil sludge and a preparation method thereof, wherein the preparation method comprises the following steps: (1) pretreating neodymium iron boron oil sludge to obtain solid powder; (2) carrying out calcium thermal reduction treatment on the solid powder obtained in the step (1) to obtain a primary alloy; (3) carrying out electroslag remelting treatment on the primary alloy obtained in the step (2) to obtain a regenerated alloy, wherein the oxygen content of the regenerated alloy is less than or equal to 0.1 wt%. The preparation method provided by the invention simplifies the operation process, shortens the reaction time, further removes the non-metallic impurities and improves the purity of the regenerated alloy.)

1. A method for preparing a regenerated alloy based on neodymium iron boron oil sludge is characterized by comprising the following steps:

(1) pretreating neodymium iron boron oil sludge to obtain solid powder;

(2) carrying out calcium thermal reduction treatment on the solid powder obtained in the step (1) to obtain a primary alloy;

(3) and (3) carrying out electroslag remelting treatment on the primary alloy obtained in the step (2) to obtain the regenerated alloy.

2. The method of claim 1, wherein the neodymium iron boron oil sludge of step (1) comprises any one of or a combination of at least two of a wire-cut oil sludge, a perforated oil sludge, a double-side mill oil sludge, a coreless mill oil sludge, or an oil-based slicing oil sludge.

3. The method according to claim 1 or 2, wherein the pretreatment of step (1) comprises washing and drying in sequence;

preferably, the washing solution used for washing comprises any one or a combination of at least two of ethanol, acetic acid or acetone, and further preferably acetone;

preferably, the solid-liquid volume ratio of the washing is 1 (4-6);

preferably, the temperature of the drying is 300-500 ℃;

preferably, the drying time is 3-5 h;

preferably, the drying is carried out in a first protective atmosphere;

preferably, the gas of the first protective atmosphere comprises any one of nitrogen, helium or argon or a combination of at least two of them, and further preferably argon.

4. The method according to any one of claims 1 to 3, wherein the specific process of the calcium thermal reduction treatment in the step (2) is as follows: and (3) mixing anhydrous chloride powder, metal calcium particles and the solid powder obtained in the step (1), and carrying out a calcium thermal reduction reaction in a second protective atmosphere to obtain a primary alloy.

5. The method according to claim 4, wherein the specific order of mixing is: firstly, mixing anhydrous chloride powder with the solid powder obtained in the step (1), and keeping the temperature for a first time period; adding metal calcium particles, and keeping the temperature for a second time period;

preferably, the anhydrous chloride powder comprises any one or a combination of at least two of anhydrous calcium chloride powder, anhydrous sodium chloride powder or anhydrous potassium chloride powder, and is further preferably anhydrous calcium chloride powder;

preferably, the mass ratio of the anhydrous chloride powder to the metal calcium particles to the solid powder obtained in the step (1) is (15-30): 3-7): 10.

6. The method as claimed in claim 5, wherein the temperature of the calcemic reduction reaction is 900-1200 ℃;

preferably, the first period of time is 5-15 min;

preferably, the second period of time is 40-60 min;

preferably, the gas of the second protective atmosphere comprises any one or a combination of at least two of nitrogen, helium or argon, and further preferably argon;

preferably, the primary alloy is further subjected to a crushing treatment before being subjected to step (3);

preferably, the average grain diameter of the primary alloy after the crushing treatment is less than or equal to 20 mm.

7. The method according to any one of claims 1 to 6, wherein the electroslag remelting treatment in the step (3) is carried out by the following specific process:

(A) mixing the molten salt slag main agent and the molten salt slag auxiliary agent to obtain first molten salt slag;

(B) carrying out slagging treatment on the first molten salt slag obtained in the step (A) by adopting an electrode to obtain second molten salt slag;

(C) and (3) mixing the primary alloy obtained in the step (2) with the second molten salt slag obtained in the step (B), and carrying out electroslag remelting reaction in a third protective atmosphere to obtain the regenerated alloy.

8. The method of claim 7, wherein the molten salt slag primary of step (A) comprises CaF₂、CaCl₂Or NdF₃Any one or a combination of at least two of them, more preferably CaF₂、CaCl₂And NdF₃A combination of (1);

preferably, the molten salt slag adjuvant in the step (A) comprises any one or a combination of at least two of KCl, KF, NaCl or NaF;

preferably, the mass ratio of the molten salt slag main agent to the molten salt slag auxiliary agent in the step (A) is (7-9) to 1;

preferably, the material of the electrode in the step (B) comprises any one of graphite, molybdenum or tantalum;

preferably, the current of the electrode in step (B) is set to 3500-4500A;

preferably, the voltage of the electrode of step (B) is set to 20-40V;

preferably, the time of the slagging treatment in the step (B) is 20-40 min;

preferably, the mass ratio of the primary alloy to the second molten salt slag in the step (C) is (35-40): 1;

preferably, the temperature of the electroslag remelting reaction in the step (C) is 1100-1300 ℃;

preferably, the third protective atmosphere in step (C) includes any one or a combination of at least two of nitrogen, helium, or argon, and further preferably argon.

9. Method according to any of claims 1-8, characterized in that the method comprises the steps of:

(1) washing and drying the neodymium iron boron oil sludge material in sequence to obtain solid powder; the washing liquid used for washing is acetone, and the solid-liquid volume ratio is 1 (4-6); the drying temperature is 300-500 ℃, the drying time is 3-5h, and the drying is carried out in the argon protection; the neodymium iron boron oil sludge comprises any one or combination of at least two of linear cutting oil sludge, perforating oil sludge, double-sided grinding oil sludge, coreless grinding oil sludge or oil-based slicing oil sludge;

(2) firstly, mixing anhydrous calcium chloride powder with the solid powder obtained in the step (1), and keeping the temperature for 5-15 min; adding metal calcium particles, and keeping the temperature for 40-60 min; carrying out 900-1200 ℃ calcium thermal reduction reaction in argon protection in the whole process, and crushing to obtain primary alloy with the average grain diameter of less than or equal to 20 mm; the mass ratio of the anhydrous calcium chloride powder to the metal calcium particles to the solid powder obtained in the step (1) is (15-30): (3-7): 10;

(3) carrying out electroslag remelting treatment on the primary alloy obtained in the step (2), wherein the specific process is as follows;

(A) mixing the molten salt slag main agent and the molten salt slag auxiliary agent according to the mass ratio of (7-9) to 1 to obtain first molten salt slag; the main agent of the molten salt slag is CaF₂、CaCl₂And NdF₃The molten salt slag auxiliary agent comprises any one or a combination of at least two of KCl, KF, NaCl or NaF;

(B) carrying out slag melting treatment on the first molten salt slag obtained in the step (A) for 20-40min by adopting a graphite, molybdenum or tantalum electrode under the conditions of 3500-4500A current and 20-40V voltage to obtain second molten salt slag;

(C) and (3) mixing the primary alloy obtained in the step (2) and the second molten salt slag obtained in the step (B) according to the mass ratio of (35-40) to 1, and carrying out an electroslag remelting reaction at 1100-1300 ℃ in the argon protection to obtain the regenerated alloy.

10. A recycled alloy as produced by the method of any of claims 1-9, wherein the recycled alloy has an oxygen content of 0.1 wt% or less.

Technical Field

The invention belongs to the technical field of industrial waste recycling, relates to a regenerated alloy, and particularly relates to a regenerated alloy prepared based on neodymium iron boron oil sludge and a preparation method thereof.

Background

The neodymium iron boron magnetic material has the advantages of high coercive force, high remanence, high magnetic energy product and the like, and is widely applied to various fields of national defense and military industry, electronic information, medical equipment, clean energy and the like. China is the biggest world-wide Nd-Fe-B producing country, and the yield in 2018 years reaches 17 million tons, which accounts for nearly 90% of the total world yield. According to statistics, more than 90 percent of the sintered neodymium iron boron is sintered neodymium iron boron. In the production process of the neodymium iron boron, waste materials are inevitably generated in each process from raw material pretreatment to final product detection. Wherein, 20-30% of oil sludge materials can be generated in the machining process, and are the largest type in the neodymium iron boron waste materials. According to different production processes, the oil sludge can be divided into linear cutting oil sludge, coreless oil sludge, double-sided oil sludge, perforating oil sludge and the like, and the oil sludge consists of neodymium-iron-boron particles oxidized to different degrees and cutting fluid (mainly organic matters and water), contains 20-25% of rare earth elements, and is a precious secondary resource. Meanwhile, long-term disordered mining of rare earth mineral resources has resulted in sharp reserves and severe ecological environment destruction. Therefore, the recycling of the rare earth secondary resource is enhanced, the current situation of rare earth resource shortage is favorably relieved, the ecological environment protection is facilitated, and the sustainable development of the rare earth industry in China is promoted.

The prior method for treating the neodymium iron boron oil sludge mainly comprises a wet method and a fire method. The wet method comprises a hydrochloric acid optimum dissolution method, a hydrochloric acid total dissolution method, a sulfuric acid double salt precipitation method and the like, and the common characteristic of the methods is that rare earth is separated from other elements by controlling the pH value. Obtaining single rare earth compound through multi-stage extraction, then adopting precipitant to convert rare earth into salt, and roasting to obtain single rare earth oxide. The method has strong adaptability to raw materials, high purity of rare earth products, long flow and no environmental friendliness. The pyrogenic process includes oxidation, chlorination, etc. and its principle is based on the difference of binding capacity of rare earth elements and other elements with oxygen, chlorine and alloy elements. The method has short flow and is relatively friendly to the environment, but the mixed rare earth compound is usually obtained, and the product purity is lower. Therefore, the traditional rare earth separation methods have certain problems, so that the development of a novel treatment mode is imperative.

In recent years, the preparation of recycled alloys or recycled neodymium iron boron magnetic materials based on neodymium iron boron waste has received increasing attention. Accordingly, the calcemic reduction method is widely used. CN 103882234A discloses a method for preparing neodymium iron boron oil sludge into regenerated neodymium iron boron magnetic powder, which comprises the steps of distillation separation, coprecipitation recovery of valuable elements, calcium thermal reduction, removal of calcium oxide, vacuum drying and the like, but the method has a long flow and unsatisfactory dynamic conditions of calcium thermal reduction. Since no flux is used, calcium oxide, which is a reaction product, adheres to the surface of the reactant, hindering the progress of the reaction, resulting in a prolonged reaction time.

CN 109338113A discloses a method for recycling neodymium iron boron trepanning oil sludge waste by a Ca-chloride reduction diffusion technology, which comprises the steps of drying neodymium iron boron oil sludge, reducing and diffusing calcium-chloride, soaking at low temperature to remove calcium, doping rare earth-rich powder and the like, and finally a regenerated neodymium iron boron magnet can be obtained. Although the reaction time can be reduced by using chloride as a low-melting-point assistant, the method does not consider the feeding sequence in the calcium thermal reduction process, and further soaking and calcium removal steps are required, so that the process is complicated. In addition, since rare earths are more reactive, Ca has a limited ability to reduce rare earth oxides, making it difficult to obtain a recycled alloy with a very low oxygen content.

Therefore, how to provide the recycled alloy prepared based on the neodymium iron boron oil sludge and the preparation method thereof can simplify the operation process, shorten the reaction time, further remove the non-metallic impurities and improve the purity of the recycled alloy, and becomes a problem which needs to be solved urgently by technical personnel in the field at present.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide the regenerated alloy prepared based on the neodymium iron boron oil sludge and the preparation method thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a method for preparing a recycled alloy based on a neodymium iron boron oil slurry material, which comprises the following steps:

(1) pretreating neodymium iron boron oil sludge to obtain solid powder;

(2) carrying out calcium thermal reduction treatment on the solid powder obtained in the step (1) to obtain a primary alloy;

(3) and (3) carrying out electroslag remelting treatment on the primary alloy obtained in the step (2) to obtain the regenerated alloy.

The invention provides a novel method for treating neodymium iron boron oil sludge by utilizing pretreatment, calcium thermal reduction and electroslag remelting, and on the basis of treating the neodymium iron boron oil sludge by the calcium thermal reduction, impurity elements in the alloy are further removed by the electroslag remelting treatment, so that the high-purity regenerated alloy is obtained. The method has the advantages of short flow, cleanness, wide applicability and the like, and is easy to realize high-valued regeneration and cyclic utilization of the neodymium iron boron oil sludge.

Preferably, the neodymium iron boron oil sludge in step (1) includes any one of or a combination of at least two of a wire-electrode cutting oil sludge, a punching oil sludge, a double-surface grinding oil sludge, a coreless grinding oil sludge or an oil-based slicing oil sludge, and typical but non-limiting combinations include a combination of a wire-electrode cutting oil sludge and a punching oil sludge, a combination of a punching oil sludge and a double-surface grinding oil sludge, a combination of a double-surface grinding oil sludge and a coreless grinding oil sludge, a combination of a coreless grinding oil sludge and an oil-based slicing oil sludge, a combination of a cutting oil sludge, a punching oil sludge and a double-surface grinding oil sludge, a combination of a punching oil sludge, a double-surface grinding oil sludge and a coreless grinding oil sludge, or a combination of a double-surface grinding oil sludge, a grinding oil sludge and an oil-based slicing oil sludge.

In the invention, because electroslag remelting has the capacity of obviously removing impurities, on the basis of calcium thermal reduction, the method can treat more types of oil sludge, widens the range of treatment objects and has good industrial application value.

Preferably, the pretreatment of step (1) comprises washing and drying which are performed sequentially.

Preferably, the washing solution used for the washing comprises any one of ethanol, acetic acid or acetone or a combination of at least two thereof, typical but non-limiting combinations include a combination of ethanol and acetic acid, a combination of acetic acid and acetone, a combination of ethanol and acetone or a combination of ethanol, acetic acid and acetone, further preferably acetone.

Preferably, the washing is carried out at a solid-liquid volume ratio of 1 (4-6), and may be, for example, 1:4, 1:4.2, 1:4.4, 1:4.6, 1:4.8, 1:5, 1:5.2, 1:5.4, 1:5.6, 1:5.8 or 1:6, but not limited to the values listed, and other values not listed within the range of values are also applicable.

In the invention, the washing liquid is fully mixed with the oil sludge material to wash organic impurities on the surface of the oil sludge material, so that the purity of the solid powder is improved.

In the present invention, the washing is accompanied by stirring.

Preferably, the stirring is performed using an electric stirrer.

Preferably, the stirring rate is 400-500rpm, which may be, for example, 400rpm, 410rpm, 420rpm, 430rpm, 440rpm, 450rpm, 460rpm, 470rpm, 480rpm, 490rpm or 500rpm, but is not limited to the recited values, and other values not recited in the range are also applicable.

Preferably, the stirring time is 40-80min, for example 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min or 80min, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.

In the invention, still standing and layering are carried out after stirring.

Preferably, the time for standing and layering is 8-12min, such as 8min, 8.5min, 9min, 9.5min, 10min, 10.5min, 11min, 11.5min or 12min, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

In the invention, the filtration is also carried out after the standing and the layering.

Preferably, the suction filtration is carried out in a vacuum suction filter.

Preferably, the drying temperature is 300-500 deg.C, such as 300 deg.C, 320 deg.C, 340 deg.C, 360 deg.C, 380 deg.C, 400 deg.C, 420 deg.C, 440 deg.C, 460 deg.C, 480 deg.C or 500 deg.C, but is not limited to the recited values, and other values not recited in the range of values are also applicable.

Preferably, the drying time is 3-5h, for example 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8h or 5h, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.

Preferably, the drying is carried out in a first protective atmosphere.

Preferably, the gas of the first protective atmosphere comprises any one or a combination of at least two of nitrogen, helium or argon, typical but non-limiting combinations include a combination of nitrogen and helium, a combination of helium and argon, a combination of nitrogen and argon, or a combination of nitrogen, helium and argon, and further preferably argon.

Preferably, the calcium thermal reduction treatment in the step (2) comprises the following specific processes: and (3) mixing anhydrous chloride powder, metal calcium particles and the solid powder obtained in the step (1), and carrying out a calcium thermal reduction reaction in a second protective atmosphere to obtain a primary alloy.

In the invention, the calcium thermal reduction treatment is carried out in a molybdenum crucible, and the molybdenum crucible is placed in a vacuum induction furnace.

Preferably, the specific order of mixing is: firstly, mixing anhydrous chloride powder with the solid powder obtained in the step (1), and keeping the temperature for a first time period; then adding metal calcium particles, and keeping the temperature for a second time period.

According to the invention, the specific mixing sequence of the materials subjected to the calcium thermal reduction treatment preferentially generates transition phase neodymium oxychloride, so that the transition phase neodymium oxychloride is efficiently reduced by calcium, the recovery rate of the alloy is improved, and the reaction time is reduced.

Preferably, the anhydrous chloride powder includes any one or a combination of at least two of anhydrous calcium chloride powder, anhydrous sodium chloride powder or anhydrous potassium chloride powder, and typical but non-limiting combinations include anhydrous calcium chloride powder and anhydrous sodium chloride powder, anhydrous sodium chloride powder and anhydrous potassium chloride powder, anhydrous calcium chloride powder and anhydrous potassium chloride powder, or anhydrous calcium chloride powder, anhydrous sodium chloride powder and anhydrous potassium chloride powder, and further preferably anhydrous calcium chloride powder.

Preferably, the mass ratio of the anhydrous chloride powder, the metal calcium particles and the solid powder obtained in the step (1) is (15-30): (3-7):10, for example, 15:3:10, 20:4.5:10, 25:5.5:10 or 30:7:10, but the method is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.

In the invention, the mass ratio of the three materials also has a certain promotion effect on the purity improvement of the regenerated alloy and the shortening of the reaction time.

Preferably, the temperature of the calthermic reduction reaction is 900-1200 deg.C, such as 900 deg.C, 950 deg.C, 1000 deg.C, 1050 deg.C, 1100 deg.C, 1150 deg.C or 1200 deg.C, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.

Preferably, the first period of time is 5-15min, such as 5min, 7min, 9min, 10min, 11min, 13min or 15min, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.

Preferably, the second period of time is 40-60min, for example 40min, 42min, 44min, 46min, 48min, 50min, 52min, 54min, 56min, 58min or 60min, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

Preferably, the gas of the second protective atmosphere comprises any one or a combination of at least two of nitrogen, helium or argon, typical but non-limiting combinations include a combination of nitrogen and helium, a combination of helium and argon, a combination of nitrogen and argon, or a combination of nitrogen, helium and argon, and further preferably argon.

Preferably, the primary alloy is further subjected to a crushing treatment before being subjected to step (3).

Preferably, the average grain size of the crushed primary alloy is 20mm or less, and may be, for example, 5mm, 7mm, 9mm, 10mm, 11mm, 13mm, 15mm, 17mm, 19mm or 20mm, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.

In the invention, the average grain diameter of the crushed primary alloy is less than or equal to 20mm, so that the alloy is fully melted when passing through a molten salt slag pool in the electroslag remelting process, and impurity phases in the primary alloy are removed as much as possible.

Preferably, the electroslag remelting treatment in the step (3) comprises the following specific processes:

(A) mixing the molten salt slag main agent and the molten salt slag auxiliary agent to obtain first molten salt slag;

(B) carrying out slagging treatment on the first molten salt slag obtained in the step (A) by adopting an electrode to obtain second molten salt slag;

(C) and (3) mixing the primary alloy obtained in the step (2) with the second molten salt slag obtained in the step (B), and carrying out electroslag remelting reaction in a third protective atmosphere to obtain the regenerated alloy.

In the invention, the electroslag remelting treatment is a typical special refining technology, is widely applied in the field of steel, and has the advantage of obviously removing non-metallic impurities due to the existence of a plurality of dynamic interfaces.

Preferably, the electroslag remelting treatment is non-consumable electrode electroslag remelting.

Preferably, the electroslag remelting treatment is performed in a copper crystallizer.

Preferably, the molten salt slag main agent in the step (A) comprises CaF₂、CaCl₂Or NdF₃Any one or a combination of at least two of the above, typical but not limiting combinations include CaF₂With CaCl₂In combination of (1), CaCl₂And NdF₃A combination of (1), CaF₂And NdF₃Combinations of (A) or CaF₂、CaCl₂And NdF₃More preferably CaF₂、CaCl₂And NdF₃Combinations of (a) and (b).

In the present invention, CaCl₂Is added mainly to dissolve residual Nd in the primary alloy₂O₃；NdF₃Is added mainly to react with residual calcium in the primary alloy, thus ensuring a lower calcium content in the secondary alloy.

Preferably, the molten salt slag adjuvant of step (a) comprises any one or a combination of at least two of KCl, KF, NaCl, or NaF, typical but non-limiting combinations include combinations of KCl and KF, KF and NaCl, NaCl and NaF, KCl, KF and NaCl, or KF, NaCl and NaF.

Preferably, the mass ratio of the molten salt slag main agent to the molten salt slag auxiliary agent in the step (A) is (7-9):1, and for example, may be 7:1, 7.2:1, 7.4:1, 7.6:1, 7.8:1, 8:1, 8.2:1, 8.4:1, 8.6:1, 8.8:1 or 9:1, but is not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.

Preferably, the material of the electrode in step (B) includes any one of graphite, molybdenum or tantalum.

Preferably, the current of the electrode in step (B) is set to 3500-.

Preferably, the voltage of the electrode in step (B) is set to 20-40V, for example, 20V, 22V, 24V, 26V, 28V, 30V, 32V, 34V, 36V, 38V or 40V, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the slagging time in the step (B) is 20-40min, such as 20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min or 40min, but not limited to the recited values, and other non-recited values in the range of the values are also applicable.

Preferably, the mass ratio of the primary alloy to the second molten salt slag in the step (C) is (35-40):1, and may be, for example, 35:1, 36:1, 37:1, 38:1, 39:1 or 40:1, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

In the present invention, the primary alloy obtained in step (2) is added to the second molten salt slag obtained in step (B) from the edge of the copper crystallizer at a rate of 0.03-0.05kg/s, for example, 0.03kg/s, 0.04kg/s or 0.05kg/s, but not limited to the values listed, and other values not listed in the range of the values are also applicable.

Preferably, the temperature of the electroslag remelting reaction in step (C) is 1100-.

In the invention, the temperature of the electroslag remelting reaction in the step (C) specifically refers to the surface temperature of a molten salt slag pool.

Preferably, the gas of the third protective atmosphere comprises any one or a combination of at least two of nitrogen, helium or argon, typical but non-limiting combinations include a combination of nitrogen and helium, a combination of helium and argon, a combination of nitrogen and argon, or a combination of nitrogen, helium and argon, and further preferably argon.

In the invention, the third protective atmosphere can prevent the rare earth alloy from being oxidized in the electroslag remelting process.

In the present invention, the furnace mouth is protected by the third protective atmosphere, and the oxygen partial pressure is 0.005 to 0.01atm, for example, 0.005atm, 0.006atm, 0.007atm, 0.008atm, 0.009atm or 0.01atm, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.

As a preferred technical solution of the first aspect of the present invention, the method comprises the steps of:

(1) washing and drying the neodymium iron boron oil sludge material in sequence to obtain solid powder; the washing liquid used for washing is acetone, and the solid-liquid volume ratio is 1 (4-6); the drying temperature is 300-500 ℃, the drying time is 3-5h, and the drying is carried out in the argon protection; the neodymium iron boron oil sludge comprises any one or combination of at least two of linear cutting oil sludge, perforating oil sludge, double-sided grinding oil sludge, coreless grinding oil sludge or oil-based slicing oil sludge;

(2) firstly, mixing anhydrous calcium chloride powder with the solid powder obtained in the step (1), and keeping the temperature for 5-15 min; adding metal calcium particles, and keeping the temperature for 40-60 min; carrying out 900-1200 ℃ calcium thermal reduction reaction in argon protection in the whole process, and crushing to obtain primary alloy with the average grain diameter of less than or equal to 20 mm; the mass ratio of the anhydrous calcium chloride powder to the metal calcium particles to the solid powder obtained in the step (1) is (15-30): (3-7): 10;

(3) carrying out electroslag remelting treatment on the primary alloy obtained in the step (2), wherein the specific process is as follows;

(A) mixing the molten salt slag main agent and the molten salt slag auxiliary agent according to the mass ratio of (7-9) to 1 to obtain first molten salt slag; the main agent of the molten salt slag is CaF₂、CaCl₂And NdF₃The molten salt slag auxiliary agent comprises any one or a combination of at least two of KCl, KF, NaCl or NaF;

(B) carrying out slag melting treatment on the first molten salt slag obtained in the step (A) for 20-40min by adopting a graphite, molybdenum or tantalum electrode under the conditions of 3500-4500A current and 20-40V voltage to obtain second molten salt slag;

(C) and (3) mixing the primary alloy obtained in the step (2) and the second molten salt slag obtained in the step (B) according to the mass ratio of (35-40) to 1, and carrying out an electroslag remelting reaction at 1100-1300 ℃ in the argon protection to obtain the regenerated alloy.

In a second aspect, the present invention provides a recycled alloy prepared according to the method of the first aspect, wherein the recycled alloy has an oxygen content of 0.1 wt% or less, such as 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, or 0.1 wt%, but not limited to the recited values, and other values not recited within the recited values are also applicable.

Compared with the prior art, the invention has the beneficial effects that:

(1) the regenerated alloy obtained by the method provided by the invention has high purity: performing calcium thermal reduction treatment to obtain a primary alloy; residual rare earth impurities in the primary alloy are further removed through electroslag remelting treatment, so that the high-purity regenerated alloy with the oxygen content lower than 0.1 wt% is obtained;

(2) the method provided by the invention improves the processing efficiency, shortens the recovery path: according to the invention, by controlling the mixing order and mixing amount of each material in the calcium thermal reduction treatment, the reaction time is greatly reduced, and the treatment efficiency is improved; in addition, the steps of repeated cleaning and the like in the wet-method calcium removal process are not needed, and the recovery path is shorter;

(3) the method provided by the invention widens the range of processing objects: in view of the capability of removing impurities remarkably of electroslag remelting, the invention can treat more types of oil sludge on the basis of calcium thermal reduction.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments.

Example 1

The embodiment provides a recycled alloy prepared based on neodymium iron boron oil pug and a preparation method thereof, wherein the preparation method comprises the following steps:

(1) sequentially washing and stirring the neodymium-iron-boron wire cutting oil sludge material, standing for 10min for layering, carrying out suction filtration, drying, and cooling to room temperature to obtain solid powder; the washing liquid used for washing is acetone, and the solid-liquid volume ratio is 1: 5; the stirring is carried out by adopting an electric stirrer, the stirring speed is 450rpm, and the stirring time is 60 min; the suction filtration is carried out in a vacuum suction filter; the drying temperature is 400 ℃, the drying time is 4 hours, and the drying is carried out under the protection of argon; the solid powder has an oxygen content of 13.2 wt%, an iron content of 60 wt%, a rare earth content of 25.2 wt%, and the balance of other trace elements;

(2) mixing 4kg of anhydrous calcium chloride powder and 2kg of the solid powder obtained in the step (1) in a molybdenum crucible, heating the molybdenum crucible in a vacuum induction furnace, and keeping the temperature for 10 min; adding 900g of metal calcium particles, and keeping the temperature for 50 min; carrying out a calcium thermal reduction reaction at 1100 ℃ in argon protection in the whole process, and crushing to obtain a primary alloy with the average grain diameter of 15 mm; the mass ratio of the anhydrous calcium chloride powder to the metal calcium particles to the solid powder obtained in the step (1) is 20:4.5: 10; the oxygen content of the primary alloy is 0.2 wt%, the iron content is 65 wt%, the rare earth content is 30.2 wt%, and the balance is other trace elements;

(3) carrying out electroslag remelting treatment on the primary alloy obtained in the step (2) in a copper crystallizer, wherein the specific process is as follows;

(A) mixing a molten salt slag main agent and a molten salt slag auxiliary agent according to the mass ratio of 8:1 to obtain first molten salt slag; the main agent of the molten salt slag is 35gCaF₂、10gCaCl₂And 3g NdF₃The molten salt slag auxiliary agent is 6g of NaCl;

(B) carrying out slag melting treatment on the first molten salt slag obtained in the step (A) for 30min by adopting a graphite electrode under the conditions of current of 4000A and voltage of 30V to obtain second molten salt slag;

(C) adding the primary alloy obtained in the step (2) into the second molten salt slag obtained in the step (B) from the edge of the copper crystallizer at the speed of 0.04kg/s according to the mass ratio of 38:1, and carrying out electroslag remelting reaction at 1200 ℃ in the argon protection to obtain the recycled alloy.

The regenerated alloy obtained in this example had an oxygen content of 0.02 wt%, an iron content of 64.8 wt%, a rare earth content of 30 wt%, and the balance of other trace elements.

Example 2

The embodiment provides a recycled alloy prepared based on neodymium iron boron oil pug and a preparation method thereof, wherein the preparation method comprises the following steps:

(1) washing and stirring the neodymium iron boron punching oil sludge material in sequence, standing and layering for 8min, carrying out suction filtration, drying, and cooling to room temperature to obtain solid powder; the washing liquid used for washing is ethanol, and the solid-liquid volume ratio is 1: 4; the stirring is carried out by adopting an electric stirrer, the stirring speed is 400rpm, and the stirring time is 80 min; the suction filtration is carried out in a vacuum suction filter; the drying temperature is 300 ℃, the drying time is 5 hours, and the drying is carried out under the protection of nitrogen; the solid powder comprises 5.5 wt% of oxygen, 66.3 wt% of iron, 26.2 wt% of rare earth and the balance of other trace elements;

(2) mixing 3kg of anhydrous sodium chloride powder and 2kg of solid powder obtained in the step (1) in a molybdenum crucible, heating the molybdenum crucible in a vacuum induction furnace, and keeping the temperature for 5 min; then 600g of metal calcium particles are added, and the temperature is kept for 40 min; carrying out a calcium thermal reduction reaction at 1200 ℃ in the nitrogen protection in the whole process, and crushing to obtain a primary alloy with the average grain diameter of 10 mm; the mass ratio of the anhydrous sodium chloride powder to the metal calcium particles to the solid powder obtained in the step (1) is 15:3: 10; the oxygen content of the primary alloy is 0.15 wt%, the iron content is 67 wt%, the rare earth content is 30.8 wt%, and the balance is other trace elements;

(3) carrying out electroslag remelting treatment on the primary alloy obtained in the step (2) in a copper crystallizer, wherein the specific process is as follows;

(A) mixing a molten salt slag main agent and a molten salt slag auxiliary agent according to the mass ratio of 7:1 to obtain first molten salt slag; the main agent of the molten salt slag is 25gCaF₂、5gCaCl₂And 5g NdF₃The molten salt slag adjuvant is 5g of KCl;

(B) carrying out slag melting treatment on the first molten salt slag obtained in the step (A) for 40min by adopting a molybdenum electrode under the conditions of 3500A current and 40V voltage to obtain second molten salt slag;

(C) adding the primary alloy obtained in the step (2) into the second molten salt slag obtained in the step (B) from the edge of the copper crystallizer at the speed of 0.04kg/s according to the mass ratio of 35:1, and carrying out electroslag remelting reaction at 1100 ℃ in the argon protection to obtain the recycled alloy.

The regenerated alloy obtained in this example had an oxygen content of 0.05 wt%, an iron content of 66.8 wt%, a rare earth content of 30.5 wt%, and the balance other trace elements.

Example 3

The embodiment provides a recycled alloy prepared based on neodymium iron boron oil pug and a preparation method thereof, wherein the preparation method comprises the following steps:

(1) washing and stirring the neodymium iron boron double-sided grinding oil sludge in sequence, standing for 12min for layering, filtering, drying, and cooling to room temperature to obtain solid powder; the washing liquid used for washing is acetic acid, and the solid-liquid volume ratio is 1: 6; the stirring is carried out by adopting an electric stirrer, the stirring speed is 500rpm, and the stirring time is 40 min; the suction filtration is carried out in a vacuum suction filter; the drying temperature is 500 ℃, the drying time is 3 hours, and the drying is carried out in the protection of helium; the solid powder has an oxygen content of 7.82 wt%, an iron content of 64.5 wt%, a rare earth content of 25.4 wt%, and the balance of other trace elements;

(2) mixing 6kg of anhydrous potassium chloride powder and 2kg of solid powder obtained in the step (1) in a molybdenum crucible, heating the molybdenum crucible in a vacuum induction furnace, and keeping the temperature for 15 min; then adding 1.4kg of metal calcium particles, and keeping the temperature for 60 min; carrying out a calcium thermal reduction reaction at 900 ℃ in helium protection in the whole process, and crushing to obtain a primary alloy with the average grain diameter of 20 mm; the mass ratio of the anhydrous potassium chloride powder to the metal calcium particles to the solid powder obtained in the step (1) is 30:7: 10; the oxygen content of the primary alloy is 0.17 wt%, the iron content is 66.3 wt%, the rare earth content is 29.5 wt%, and the balance is other trace elements;

(3) carrying out electroslag remelting treatment on the primary alloy obtained in the step (2) in a copper crystallizer, wherein the specific process is as follows;

(A) mixing a molten salt slag main agent and a molten salt slag auxiliary agent according to the mass ratio of 9:1 to obtain first molten salt slag; the main agent of the molten salt slag is 25gCaF₂、10gCaCl₂And 10g NdF₃The molten salt slag adjuvant is 5g NaF;

(B) carrying out slag melting treatment on the first molten salt slag obtained in the step (A) for 20min by adopting a tantalum electrode under the conditions of 4500A current and 20V voltage to obtain second molten salt slag;

(C) adding the primary alloy obtained in the step (2) into the second molten salt slag obtained in the step (B) from the edge of the copper crystallizer at the speed of 0.04kg/s according to the mass ratio of 40:1, and carrying out electroslag remelting reaction at 1300 ℃ in the argon protection to obtain the recycled alloy.

The regenerated alloy obtained in this example had an oxygen content of 0.07 wt%, an iron content of 66 wt%, a rare earth content of 29.8 wt%, and the balance of other trace elements.

Example 4

The embodiment provides a recycled alloy prepared based on neodymium iron boron oil pug and a preparation method thereof, wherein the preparation method is implemented by changing the mixing sequence of the step (2) into: 6kg of anhydrous potassium chloride powder, 1.4kg of metal calcium particles and 2kg of the solid powder obtained in the step (1) are mixed in a molybdenum crucible at one time, the molybdenum crucible is placed in a vacuum induction furnace for heating, and the temperature is kept for 75min, and the rest conditions are the same as those in the example 1, so that the details are not repeated.

The regenerated alloy obtained in this example had an oxygen content of 0.09 wt%, an iron content of 67.5 wt%, a rare earth content of 32.5 wt%, and the balance other trace elements.

Compared with the example 1, the step (2) in the present embodiment is performed by mixing materials in one step instead of mixing materials in steps, which is not beneficial to further removing residual rare earth impurities in the primary alloy, thereby reducing the purity of the regenerated alloy, but the oxygen content can still be kept below 0.1 wt%.

Example 5

This embodiment provides a recycled alloy prepared based on a neodymium iron boron oil slurry and a preparation method thereof, in the preparation method, except that the mass ratio of the anhydrous calcium chloride powder and the metallic calcium particles in step (2) to the solid powder obtained in step (1) is changed to 2:1:2, that is, the mass of the anhydrous calcium chloride powder is 2kg, the mass of the metallic calcium particles is 1kg, and the mass of the solid powder is 2kg, the other conditions are the same as those in example 1, and thus, details are not described herein.

The regenerated alloy obtained in this example had an oxygen content of 0.1 wt%, an iron content of 68.4 wt%, a rare earth content of 33.1 wt%, and the balance of other trace elements.

Compared with the example 1, the step (2) in the embodiment changes the mass ratio of the three materials to 2:1:2 instead of (15-30): 3-7):10, which is not beneficial to further removing the residual rare earth impurities in the primary alloy, thereby reducing the purity of the regenerated alloy, but the oxygen content can still be maintained at 0.1 wt%.

Example 6

This embodiment provides a recycled alloy prepared based on neodymium iron boron oil sludge and a preparation method thereof, in the preparation method, except that the mass ratio of the anhydrous calcium chloride powder and the metallic calcium particles in step (2) to the solid powder obtained in step (1) is changed to 10:1:5, that is, the mass of the anhydrous calcium chloride powder is 4kg, the mass of the metallic calcium particles is 400g, and the mass of the solid powder is 2kg, the other conditions are the same as those in embodiment 1, and thus, details are not described herein.

The regenerated alloy obtained in this example had an oxygen content of 0.09 wt%, an iron content of 67.1 wt%, a rare earth content of 30.4 wt%, and the balance other trace elements.

Compared with the example 1, the step (2) in the embodiment changes the mass ratio of the three materials to 10:1:5 instead of (15-30): 3-7):10, which is not beneficial to further removing residual rare earth impurities in the primary alloy, thereby reducing the purity of the regenerated alloy, but the oxygen content can still be kept below 0.1 wt%.

Example 7

The embodiment provides a recycled alloy prepared based on neodymium iron boron oil sludge and a preparation method thereof, wherein the preparation method is the same as that of embodiment 1 except that the average particle size of the primary alloy after the crushing treatment in the step (2) is changed to 22mm, and therefore, the details are not repeated herein.

The regenerated alloy obtained in this example had an oxygen content of 0.08 wt%, an iron content of 65.1 wt%, a rare earth content of 30.1 wt%, and the balance of other trace elements.

Compared with the embodiment 1, in the embodiment, the average grain size of the primary alloy after the crushing treatment is changed to be more than 20mm in the step (2), which is not beneficial to the alloy to smoothly pass through the molten salt slag bath in the electroslag remelting process, so that the impurity phase in the primary alloy can not be sufficiently removed, the purity of the regenerated alloy is further reduced, and the oxygen content can still be kept below 0.1 wt%.

Example 8

The embodiment provides a recycled alloy prepared based on neodymium iron boron oil sludge and a preparation method thereof, wherein the preparation method is characterized in that the molten salt slag main agent in the step (A) is changed into 48gCaF₂The rest of the conditions are the same as those in example 1, and therefore, the description thereof is omitted.

The regenerated alloy obtained in this example had an oxygen content of 0.07 wt%, an iron content of 64.2 wt%, a rare earth content of 31.5 wt%, and the balance of other trace elements.

Example 9

This embodiment provides based on preparation of neodymium iron boron oil mud materialThe preparation method is characterized in that the molten salt slag main agent in the step (A) is changed into 48gCaCl₂The rest of the conditions are the same as those in example 1, and therefore, the description thereof is omitted.

The regenerated alloy obtained in this example had an oxygen content of 0.06 wt%, an iron content of 66.3 wt%, a rare earth content of 32.7 wt%, and the balance of other trace elements.

Example 10

The embodiment provides a recycled alloy prepared based on neodymium iron boron oil pug and a preparation method thereof, wherein the preparation method is characterized in that the molten salt slag main agent in the step (A) is changed into 48g NdF₃The rest of the conditions are the same as those in example 1, and therefore, the description thereof is omitted.

The regenerated alloy obtained in this example had an oxygen content of 0.07 wt%, an iron content of 65.4 wt%, a rare earth content of 31.9 wt%, and the balance of other trace elements.

Comparative example 1

The comparative example provides a recycled alloy prepared based on neodymium iron boron oil sludge and a preparation method thereof, and the preparation method comprises the following steps:

(1) sequentially washing and stirring the neodymium-iron-boron wire cutting oil sludge material, standing for 10min for layering, carrying out suction filtration, drying, and cooling to room temperature to obtain solid powder; the washing liquid used for washing is acetone, and the solid-liquid volume ratio is 1: 5; the stirring is carried out by adopting an electric stirrer, the stirring speed is 450rpm, and the stirring time is 60 min; the suction filtration is carried out in a vacuum suction filter; the drying temperature is 400 ℃, the drying time is 4 hours, and the drying is carried out under the protection of argon; the solid powder has an oxygen content of 13.2 wt%, an iron content of 60 wt%, a rare earth content of 25.2 wt%, and the balance of other trace elements;

(2) mixing 4kg of anhydrous calcium chloride powder and 2kg of the solid powder obtained in the step (1) in a molybdenum crucible, heating the molybdenum crucible in a vacuum induction furnace, and keeping the temperature for 10 min; adding 900g of metal calcium particles, and keeping the temperature for 50 min; carrying out a calcium thermal reduction reaction at 1100 ℃ in argon protection in the whole process, and cooling to room temperature to obtain a regenerated alloy; the mass ratio of the anhydrous calcium chloride powder to the metal calcium particles to the solid powder obtained in the step (1) is 20:4.5: 10.

The regenerated alloy obtained in the comparative example has an oxygen content of 0.2 wt%, an iron content of 65 wt%, a rare earth content of 30.2 wt%, and the balance of other trace elements.

Compared with the example 1, the comparative example removes the electroslag remelting treatment, the oxygen content of the obtained regenerated alloy is more than 0.1 wt%, the residual rare earth impurities in the alloy cannot be further removed, the application range is limited, and a larger improvement space is provided.

Therefore, the purity of the regenerated alloy obtained by the method is high; obtaining a primary alloy through calcium thermal reduction treatment, and further removing residual rare earth impurities in the primary alloy through electroslag remelting treatment, thereby obtaining a high-purity regenerated alloy with the oxygen content lower than 0.1 wt%; the method improves the processing efficiency and shortens the recovery path; by controlling the mixing order and mixing amount of each material in the calcium thermal reduction treatment, the reaction time is greatly reduced, and the treatment efficiency is improved; in addition, the steps of repeated cleaning and the like in the wet-method calcium removal process are not needed, and the recovery path is shorter; the range of processing objects is widened; in view of the obvious impurity removing capacity of electroslag remelting, the method can treat more types of oil sludge on the basis of calcium thermal reduction, and has wide application prospect.

The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.