A process for producing boron nickel by carbon thermal method using electric furnace

Abstract

The invention discloses a process for producing boron nickel by a carbon thermal method of a submerged arc furnace, comprising the following steps: S1, preparing the following raw materials by weight: 90-100 parts of nickel oxide, 100-110 parts of boric acid, 5-15 parts of petroleum coke, 75-85 parts of wood chips, and 1-5 parts of high-purity aluminum particles; S2, according to the weight parts described in S1, putting the boric acid, nickel oxide, wood chips and high-purity aluminum particles into a drying furnace, while the temperature is 180-200°C, and the petroleum coke and wood chips are used as combustion raw materials of the drying furnace; S3, drying the dried boric acid, nickel oxide, wood chips and high-purity aluminum particles. The pure aluminum particles are transferred to a rotary kiln for pre-reduction, and petroleum coke and wood chips are added to the high temperature zone of the rotary kiln, and the temperature is controlled between 780-830°C. After processing for 3-5 hours, a pre-reduction charge is obtained; S4, the pre-reduction charge is sent to a submersible thermal electric furnace for smelting at 1800°C for 10-24 hours; S5, and then refined at 1750°C for 30-60 minutes, and bottom oxygen is blown for 20-30 minutes through an oxygen blowing mechanism during refining; S6, after refining, it is naturally cooled for 30-60 minutes, and a casting operation is performed to obtain a boron-nickel alloy.

Description

Technical Field

[0001] The invention relates to the technical field of boron nickel production, and in particular to a process for producing boron nickel by a submerged arc furnace carbon thermal method. Background Art

[0002] Boron easily reacts with metal oxides under high temperature conditions to produce metal borides. These metal borides usually have special properties such as high hardness and high electrical conductivity, so boron is often added to metal alloys as a trace element. For example, typical nickel-based high-temperature alloys and cobalt-based high-temperature alloys are generally added with boron. Boron is used to refine grains, improve grain morphology, strengthen grain boundaries, etc., to improve the high-temperature properties of cast high-temperature alloys and increase high-temperature fracture strength. In addition, adding boron to non-ferrous alloys can improve their wear resistance and hardenability; adding boron to nickel-based magnetic materials can improve their high magnetic anisotropy; adding boron to copper alloys can improve their corrosion resistance and strength. However, the melting point of elemental boron is 2300℃ and its density is 2.35g / cm 3 When boron is directly added as a trace element in production, it is not conducive to the homogenization of the components and the element yield is low. Therefore, the addition of boron is generally done in the form of nickel-boron alloy.

[0003] In the prior art, nickel-boron alloys are mostly produced by thermal reduction, using nickel oxide and boron trioxide as raw materials, and thermally reducing aluminum and aluminum-magnesium alloys. The nickel-boron alloy prepared by this method contains a large amount of impurity elements, with an aluminum content of 3.5%, a magnesium content of 6.2%, and an iron content of 2.8%. The nickel-boron alloy prepared by this method meets the requirements when used as an element additive for steel alloys, but its impurity content cannot meet the use requirements when used as an element additive for casting nickel-based high-temperature alloys and cobalt-based high-temperature alloys. Summary of the invention

[0004] In order to solve the problems mentioned in the above background technology, the present invention provides a process for producing boron nickel by carbon thermal method using a submerged arc furnace.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] A process for producing boron nickel by a submerged arc furnace carbon thermal method comprises the following steps:

[0007] S1. Prepare the following raw materials by weight:

[0008] 90-100 parts of nickel oxide, 100-110 parts of boric acid, 5-15 parts of petroleum coke, 75-85 parts of wood chips, 1-5 parts of high-purity aluminum particles;

[0009] S2. Put boric acid, nickel oxide, wood chips and high-purity aluminum particles into a drying furnace according to the weight parts described in S1, and the temperature is 180-200° C. Petroleum coke and wood chips are used as combustion raw materials of the drying furnace;

[0010] S3, the dried boric acid, nickel oxide, wood chips and high-purity aluminum particles are transferred to a rotary kiln for pre-reduction, and petroleum coke and wood chips are added to the high temperature zone of the rotary kiln, and the temperature is controlled between 780-830°C, and the pre-reduction charge is obtained after processing for 3-5 hours;

[0011] S4, sending the pre-reduced charge to a submerged arc furnace for smelting at 1800°C for 10-24h;

[0012] S5, then refining at 1750°C for 30-60min, and at the same time, bottom oxygen blowing is performed for 20-30min through an oxygen blowing mechanism;

[0013] S6. After refining, the mixture is naturally cooled for 30-60 minutes and then cast to obtain a boron-nickel alloy.

[0014] The present invention adds petroleum coke and wood chips into the high temperature zone of the rotary kiln, and selectively performs roasting pre-reduction in the rotary kiln to partially reduce nickel and boron oxides. In the rotary kiln in a reducing atmosphere, oxides such as nickel and boron can be reduced to metals or low-valent oxides, which can greatly reduce the smelting task in the electric furnace and improve the productivity of the furnace. The produced high-temperature roasted sand is directly added to the electric furnace through a high-level silo to provide heat and reduce smelting energy consumption.

[0015] Preferably, the nickel oxide has a content of 99%, contains nickel>65%, SiO2<6%, P<0.01%, and has a particle size<1mm; and the boric acid has a boric acid content of 99%.

[0016] Preferably, the petroleum coke has a carbon content of 96% and a particle size of 15 to 20 mm.

[0017] Preferably, the wood chips have a moisture content of less than 30% and a particle size of 20 to 30 mm.

[0018] Preferably, the method for preparing the high-purity aluminum particles comprises the following steps:

[0019] The crude aluminum particles are melted at a high temperature of 700-800°C. After melting for 5-8 hours, a composite refining agent is added and refined for 30-60 minutes to obtain high-purity aluminum liquid. After filtering, the high-purity aluminum particles are cast and cut.

[0020] Preferably, the composite refining agent is a compound of graphene, sodium hexafluoroaluminate, sodium hexametaphosphate, sodium hexafluorosilicate and sodium bisulfite, wherein the mass ratio of graphene, sodium hexafluoroaluminate, sodium hexametaphosphate, sodium hexafluorosilicate and sodium bisulfite is (3-5): (1-3): (1.5-2.0): (1-3): (0.5-1).

[0021] Since graphene has excellent thermal and electrical conductivity, it can promote the uniform distribution of heat in the aluminum liquid and help separate and remove impurities; sodium hexafluoroaluminate reacts chemically with the oxide inclusions in the aluminum liquid to generate easily separable compounds, which have a low density and can float to the surface of the aluminum liquid and be removed. Sodium hexametapolyphosphate is adsorbed on the surface of impurity particles to disperse them in the aluminum liquid, preventing impurities from agglomerating, while promoting the formation of crystal nuclei and refining the grain structure of aluminum. Sodium hexafluorosilicate reacts with hydrogen in the aluminum liquid to generate stable compounds, thereby reducing the hydrogen content in the aluminum liquid. The sulfur dioxide produced by the decomposition of sodium bisulfite can react with oxygen and sulfur in the aluminum liquid to generate corresponding oxides and sulfides, thereby achieving the purpose of deoxidation and desulfurization. Sodium hexafluoroaluminate reacts with aluminum oxide impurities to generate low-melting-point fluoroaluminates, which float to the surface of the aluminum liquid at high temperatures to form scum and be removed.

[0022] The composite refining agent of the present invention is prepared by compounding graphene, sodium hexafluoroaluminate, sodium hexametaphosphate, sodium hexafluorosilicate and sodium bisulfite. The components cooperate with each other to achieve a good synergistic effect.

[0023] Preferably, the graphene particle size is 6-12 μm and the number of layers is 8.

[0024] Preferably, the composite refining agent is added by loading the composite refining agent into a sprayer and spraying the refining agent into the aluminum liquid using an inert gas.

[0025] Preferably, the inert gas is pure nitrogen or pure argon, and its purity is greater than 99.99%.

[0026] ① Boric acid is dehydrated to generate boric anhydride; Boric acid is dehydrated at a high temperature above the melting point in an electric furnace:

[0027] 2H3BO3=B2O3+3H2O

[0028] ② Boric anhydride reduction:

[0029] 2 / 3B2O3+4 / 3Al=4 / 3B+2 / 3Al2O3

[0030] 1 / 3B2O3+C=2 / 3B+CO

[0031] ③NiO reduction:

[0032] NiO+C=Ni+CO

[0033] 3NiO+2Al=3Ni+Al2O3

[0034] ④Ni and B generate NiB:

[0035] Ni+B=NiB.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] 1. The present invention provides a process for producing boron nickel by a carbon thermal method in a mineral heat electric furnace. Since the alloy raw materials contain trace amounts of Mn, RE, etc., which can form refractory compounds, they act as non-spontaneous crystal nuclei during alloy crystallization, play a role in refining grains, and improve the strength and plasticity of the alloy. Al is refined by a composite refining agent, which can effectively remove hydrogen and floating oxide inclusions in the aluminum liquid. The prepared high-purity aluminum particles can be used as a deoxidizer to effectively remove oxygen elements in the raw materials and reduce the oxygen content in the alloy, thereby improving the purity and performance of the alloy.

[0038] 2. The addition of high-purity aluminum particles in the present invention helps to refine the grain structure of the boron-nickel alloy, so that the alloy has higher strength and toughness, and an appropriate amount of pure aluminum can improve the hot working properties of the boron-nickel alloy, making it easier to perform subsequent processing and forming.

[0039] 3. The boron-nickel alloy produced by the present invention has low cost, is suitable for mass production, and has low content of impurities such as iron, sulfur, and phosphorus; at the same time, there is little dust in the production process, the process is highly controllable, the production environment can be improved, environmental protection is controllable, and there is little pollution to the external environment, and it has high social use value and application prospects. DETAILED DESCRIPTION

[0040] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0041] Unless otherwise specified, the raw materials used in the present invention are all conventional products purchased from the market.

[0042] The crude aluminum particles were purchased from Nangong Dinghong Metal Materials Co., Ltd. with a CAS number of 365-656.

[0043] Preparation Example 1

[0044] The preparation method of the high-purity aluminum particles comprises the following steps:

[0045] 100g of aluminum pellets are melted at a high temperature of 700℃. After melting for 5h, 10g of composite refining agent is added and refined for 30min to obtain high-purity aluminum liquid. After filtering, high-purity aluminum pellets are obtained by pouring and cutting. The composite refining agent is added by loading the composite refining agent into a jet machine and spraying the refining agent into the aluminum liquid using pure argon gas with a purity greater than 99.99%.

[0046] The composite refining agent is a compound of graphene, sodium hexafluoroaluminate, sodium hexametapolyphosphate, sodium hexafluorosilicate and sodium bisulfite, wherein the mass ratio of graphene, sodium hexafluoroaluminate, sodium hexametapolyphosphate, sodium hexafluorosilicate and sodium bisulfite is 3:1:1.5:1:1.

[0047] The graphene particle size is 6 μm and the number of layers is 8.

[0048] Preparation Example 2

[0049] The preparation method of the high-purity aluminum particles comprises the following steps:

[0050] 100g of aluminum pellets are melted at a high temperature of 750℃. After melting for 7h, 10g of composite refining agent is added and refined for 40min to obtain high-purity aluminum liquid. After filtering, high-purity aluminum pellets are obtained by pouring and cutting. The composite refining agent is added by loading the composite refining agent into a jet machine and spraying the refining agent into the aluminum liquid using pure argon gas with a purity greater than 99.99%.

[0051] The composite refining agent is a compound of graphene, sodium hexafluoroaluminate, sodium hexametapolyphosphate, sodium hexafluorosilicate and sodium bisulfite, wherein the mass ratio of graphene, sodium hexafluoroaluminate, sodium hexametapolyphosphate, sodium hexafluorosilicate and sodium bisulfite is 4:3:2:2:1.

[0052] The graphene particle size is 10 μm and the number of layers is 8.

[0053] Preparation Example 3

[0054] The preparation method of the high-purity aluminum particles comprises the following steps:

[0055] 100g of aluminum pellets are melted at a high temperature of 750℃. After melting for 7h, 10g of composite refining agent is added and refined for 40min to obtain high-purity aluminum liquid. After filtering, high-purity aluminum pellets are obtained by pouring and cutting. The composite refining agent is added by loading the composite refining agent into a jet machine and spraying the refining agent into the aluminum liquid using pure argon gas with a purity greater than 99.99%.

[0056] The composite refining agent is a compound of graphene, sodium hexafluoroaluminate, sodium hexametapolyphosphate, sodium hexafluorosilicate and sodium bisulfite, wherein the mass ratio of graphene, sodium hexafluoroaluminate, sodium hexametapolyphosphate, sodium hexafluorosilicate and sodium bisulfite is 4:3:2:2:1.

[0057] The graphene particle size is 10 μm and the number of layers is 8.

[0058] Example 1

[0059] A process for producing boron nickel by a submerged arc furnace carbon thermal method comprises the following steps:

[0060] S1. Prepare the following raw materials by weight:

[0061] 90 parts of nickel oxide, 100 parts of boric acid, 5 parts of petroleum coke, 75 parts of wood chips, and 1 part of high-purity aluminum particles prepared in Preparation Example 1;

[0062] The nickel oxide has a content of 99%, a nickel content of 70%, a SiO2 content of 5%, a P content of 0.005%, and a particle size of 0.8 mm; the boric acid has a boric acid content of 99%;

[0063] The petroleum coke has a carbon content of 96% and a particle size of 15 mm;

[0064] The wood chips contain 28% moisture and have a particle size of 20 mm.

[0065] S2. Put boric acid, nickel oxide, wood chips and high-purity aluminum particles into a drying furnace according to the weight parts described in S1, and the temperature is 180° C. Petroleum coke and wood chips are used as combustion raw materials of the drying furnace;

[0066] S3, the dried boric acid, nickel oxide, wood chips and high-purity aluminum particles are transferred to a rotary kiln for pre-reduction, and petroleum coke and wood chips are added to the high temperature zone of the rotary kiln, and the temperature is controlled between 780°C, and the pre-reduction charge is obtained after processing for 3 hours;

[0067] S4, sending the pre-reduced charge to a submerged arc furnace for smelting at 1800°C for 10 hours;

[0068] S5, then refining at 1750°C for 30 minutes, and at the same time, bottom oxygen blowing is performed for 25 minutes through an oxygen blowing mechanism;

[0069] S6. After refining, the mixture is naturally cooled for 35 minutes and then cast to obtain a boron-nickel alloy.

[0070] Example 2

[0071] A process for producing boron nickel by a submerged arc furnace carbon thermal method comprises the following steps:

[0072] S1. Prepare the following raw materials by weight:

[0073] 90 parts of nickel oxide, 100 parts of boric acid, 5 parts of petroleum coke, 75 parts of wood chips, and 1 part of high-purity aluminum particles prepared in Preparation Example 2;

[0074] The nickel oxide has a content of 99%, a nickel content of 70%, a SiO2 content of 5%, a P content of 0.005%, and a particle size of 0.8 mm; the boric acid has a boric acid content of 99%;

[0075] The petroleum coke has a carbon content of 96% and a particle size of 15 mm;

[0076] The wood chips contain 25% moisture and have a particle size of 20 mm.

[0077] S2. Put boric acid, nickel oxide, wood chips and high-purity aluminum particles into a drying furnace according to the weight parts described in S1, and the temperature is 190° C. Petroleum coke and wood chips are used as combustion raw materials of the drying furnace;

[0078] S3, the dried boric acid, nickel oxide, wood chips and high-purity aluminum particles are transferred to a rotary kiln for pre-reduction, and petroleum coke and wood chips are added to the high temperature zone of the rotary kiln, and the temperature is controlled between 800°C, and the pre-reduction charge is obtained after 4 hours of treatment;

[0079] S4, sending the pre-reduced charge to a submerged arc furnace for smelting at 1800°C for 20 hours;

[0080] S5, then refining at 1750°C for 45 minutes, and at the same time, bottom oxygen blowing is performed for 25 minutes through an oxygen blowing mechanism;

[0081] S6. After refining, the mixture is naturally cooled for 45 minutes and then cast to obtain a boron-nickel alloy.

[0082] Example 3

[0083] A process for producing boron nickel by a submerged arc furnace carbon thermal method comprises the following steps:

[0084] S1. Prepare the following raw materials by weight:

[0085] 90 parts of nickel oxide, 100 parts of boric acid, 5 parts of petroleum coke, 75 parts of wood chips, and 1 part of high-purity aluminum particles prepared in Preparation Example 3;

[0086] The nickel oxide has a content of 99%, a nickel content of 70%, a SiO2 content of 5%, a P content of 0.005%, and a particle size of 0.8 mm; the boric acid has a boric acid content of 99%;

[0087] The petroleum coke has a carbon content of 96% and a particle size of 15 mm;

[0088] The wood chips contain 25% moisture and have a particle size of 20 mm.

[0089] S2. Put boric acid, nickel oxide, wood chips and high-purity aluminum particles into a drying furnace according to the weight parts described in S1, and the temperature is 200° C. Petroleum coke and wood chips are used as combustion raw materials of the drying furnace;

[0090] S3, the dried boric acid, nickel oxide, wood chips and high-purity aluminum particles are transferred to a rotary kiln for pre-reduction, and petroleum coke and wood chips are added to the high temperature zone of the rotary kiln, and the temperature is controlled between 830°C, and the pre-reduction charge is obtained after processing for 5 hours;

[0091] S4, sending the pre-reduced charge to a submerged arc furnace for smelting at 1800°C for 24 hours;

[0092] S5, then refining at 1750°C for 60 minutes, and at the same time, bottom oxygen blowing is performed for 30 minutes through an oxygen blowing mechanism;

[0093] S6. After refining, the mixture is naturally cooled for 60 minutes and then cast to obtain a boron-nickel alloy.

[0094] Example 4

[0095] A process for producing boron nickel by a submerged arc furnace carbon thermal method comprises the following steps:

[0096] S1. Prepare the following raw materials by weight:

[0097] 95 parts of nickel oxide, 105 parts of boric acid, 10 parts of petroleum coke, 80 parts of wood chips, and 3 parts of high-purity aluminum particles prepared in Preparation Example 1;

[0098] The nickel oxide has a content of 99%, a nickel content of 75%, a SiO2 content of 4.5%, a P content of 0.005%, and a particle size of 0.75 mm; the boric acid has a boric acid content of 99%;

[0099] The petroleum coke has a carbon content of 96% and a particle size of 15 mm;

[0100] The wood chips contain 28% moisture and have a particle size of 20 mm.

[0101] S2. Put boric acid, nickel oxide, wood chips and high-purity aluminum particles into a drying furnace according to the weight parts described in S1, and the temperature is 180° C. Petroleum coke and wood chips are used as combustion raw materials of the drying furnace;

[0102] S3, the dried boric acid, nickel oxide, wood chips and high-purity aluminum particles are transferred to a rotary kiln for pre-reduction, and petroleum coke and wood chips are added to the high temperature zone of the rotary kiln, and the temperature is controlled between 780°C, and the pre-reduction charge is obtained after processing for 3 hours;

[0103] S4, sending the pre-reduced charge to a submerged arc furnace for smelting at 1800°C for 10 hours;

[0104] S5, then refining at 1750°C for 30 minutes, and at the same time, bottom oxygen blowing is performed for 25 minutes through an oxygen blowing mechanism;

[0105] S6. After refining, the mixture is naturally cooled for 35 minutes and then cast to obtain a boron-nickel alloy.

[0106] Example 5

[0107] A process for producing boron nickel by a submerged arc furnace carbon thermal method comprises the following steps:

[0108] S1. Prepare the following raw materials by weight:

[0109] 95 parts of nickel oxide, 105 parts of boric acid, 10 parts of petroleum coke, 80 parts of wood chips, and 3 parts of high-purity aluminum particles prepared in Preparation Example 2;

[0110] The nickel oxide has a content of 99%, a nickel content of 75%, a SiO2 content of 4.5%, a P content of 0.005%, and a particle size of 0.75 mm; the boric acid has a boric acid content of 99%;

[0111] The petroleum coke has a carbon content of 96% and a particle size of 15 mm;

[0112] The wood chips contain 28% moisture and have a particle size of 20 mm.

[0113] S2. Put boric acid, nickel oxide, wood chips and high-purity aluminum particles into a drying furnace according to the weight parts described in S1, and the temperature is 190° C. Petroleum coke and wood chips are used as combustion raw materials of the drying furnace;

[0114] S3, the dried boric acid, nickel oxide, wood chips and high-purity aluminum particles are transferred to a rotary kiln for pre-reduction, and petroleum coke and wood chips are added to the high temperature zone of the rotary kiln, and the temperature is controlled between 800°C, and the pre-reduction charge is obtained after 4 hours of treatment;

[0115] S4, sending the pre-reduced charge to a submerged arc furnace for smelting at 1800°C for 20 hours;

[0116] S5, then refining at 1750°C for 45 minutes, and at the same time, bottom oxygen blowing is performed for 25 minutes through an oxygen blowing mechanism;

[0117] S6. After refining, the mixture is naturally cooled for 45 minutes and then cast to obtain a boron-nickel alloy.

[0118] Example 6

[0119] A process for producing boron nickel by a submerged arc furnace carbon thermal method comprises the following steps:

[0120] S1. Prepare the following raw materials by weight:

[0121] 95 parts of nickel oxide, 105 parts of boric acid, 10 parts of petroleum coke, 80 parts of wood chips, and 3 parts of high-purity aluminum particles prepared in Preparation Example 3;

[0122] The nickel oxide has a content of 99%, a nickel content of 75%, a SiO2 content of 4.5%, a P content of 0.005%, and a particle size of 0.75 mm; the boric acid has a boric acid content of 99%;

[0123] The petroleum coke has a carbon content of 96% and a particle size of 15 mm;

[0124] The wood chips contain 28% moisture and have a particle size of 20 mm.

[0125] S2. Put boric acid, nickel oxide, wood chips and high-purity aluminum particles into a drying furnace according to the weight parts described in S1, and the temperature is 200° C. Petroleum coke and wood chips are used as combustion raw materials of the drying furnace;

[0126] S3, the dried boric acid, nickel oxide, wood chips and high-purity aluminum particles are transferred to a rotary kiln for pre-reduction, and petroleum coke and wood chips are added to the high temperature zone of the rotary kiln, and the temperature is controlled between 830°C, and the pre-reduction charge is obtained after processing for 5 hours;

[0127] S4, sending the pre-reduced charge to a submerged arc furnace for smelting at 1800°C for 24 hours;

[0128] S5, then refining at 1750°C for 60 minutes, and at the same time, bottom oxygen blowing is performed for 30 minutes through an oxygen blowing mechanism;

[0129] S6. After refining, the mixture is naturally cooled for 60 minutes and then cast to obtain a boron-nickel alloy.

[0130] Example 7

[0131] A process for producing boron nickel by a submerged arc furnace carbon thermal method comprises the following steps:

[0132] S1. Prepare the following raw materials by weight:

[0133] 100 parts of nickel oxide, 110 parts of boric acid, 15 parts of petroleum coke, 85 parts of wood chips, and 5 parts of high-purity aluminum particles prepared in Preparation Example 1;

[0134] The nickel oxide has a content of 99%, a nickel content of 70%, a SiO2 content of 5%, a P content of 0.005%, and a particle size of 0.8 mm; the boric acid has a boric acid content of 99%;

[0135] The petroleum coke has a carbon content of 96% and a particle size of 15 mm;

[0136] The wood chips contain 25% moisture and have a particle size of 20 mm.

[0137] S2. Put boric acid, nickel oxide, wood chips and high-purity aluminum particles into a drying furnace according to the weight parts described in S1, and the temperature is 200° C. Petroleum coke and wood chips are used as combustion raw materials of the drying furnace;

[0138] S3, the dried boric acid, nickel oxide, wood chips and high-purity aluminum particles are transferred to a rotary kiln for pre-reduction, and petroleum coke and wood chips are added to the high temperature zone of the rotary kiln, and the temperature is controlled between 830°C, and the pre-reduction charge is obtained after processing for 5 hours;

[0139] S4, sending the pre-reduced charge to a submerged arc furnace for smelting at 1800°C for 24 hours;

[0140] S5, then refining at 1750°C for 60 minutes, and at the same time, bottom oxygen blowing is performed for 30 minutes through an oxygen blowing mechanism;

[0141] S6. After refining, the mixture is naturally cooled for 60 minutes and then cast to obtain a boron-nickel alloy.

[0142] Example 8

[0143] A process for producing boron nickel by a submerged arc furnace carbon thermal method comprises the following steps:

[0144] S1. Prepare the following raw materials by weight:

[0145] 100 parts of nickel oxide, 110 parts of boric acid, 15 parts of petroleum coke, 85 parts of wood chips, and 5 parts of high-purity aluminum particles prepared in Preparation Example 2;

[0146] The nickel oxide has a content of 99%, a nickel content of 70%, a SiO2 content of 5%, a P content of 0.005%, and a particle size of 0.8 mm; the boric acid has a boric acid content of 99%;

[0147] The petroleum coke has a carbon content of 96% and a particle size of 15 mm;

[0148] The wood chips contain 25% moisture and have a particle size of 20 mm.

[0149] S2. Put boric acid, nickel oxide, wood chips and high-purity aluminum particles into a drying furnace according to the weight parts described in S1, and the temperature is 190° C. Petroleum coke and wood chips are used as combustion raw materials of the drying furnace;

[0150] S3, the dried boric acid, nickel oxide, wood chips and high-purity aluminum particles are transferred to a rotary kiln for pre-reduction, and petroleum coke and wood chips are added to the high temperature zone of the rotary kiln, and the temperature is controlled between 800°C, and the pre-reduction charge is obtained after 4 hours of treatment;

[0151] S4, sending the pre-reduced charge to a submerged arc furnace for smelting at 1800°C for 20 hours;

[0152] S5, then refining at 1750°C for 45 minutes, and at the same time, bottom oxygen blowing is performed for 25 minutes through an oxygen blowing mechanism;

[0153] S6. After refining, the mixture is naturally cooled for 45 minutes and then cast to obtain a boron-nickel alloy.

[0154] Example 9

[0155] A process for producing boron nickel by a submerged arc furnace carbon thermal method comprises the following steps:

[0156] S1. Prepare the following raw materials by weight:

[0157] 100 parts of nickel oxide, 110 parts of boric acid, 15 parts of petroleum coke, 85 parts of wood chips, and 5 parts of high-purity aluminum particles prepared in Preparation Example 3;

[0158] The nickel oxide has a content of 99%, a nickel content of 70%, a SiO2 content of 5%, a P content of 0.005%, and a particle size of 0.8 mm; the boric acid has a boric acid content of 99%;

[0159] The petroleum coke has a carbon content of 96% and a particle size of 15 mm;

[0160] The wood chips contain 25% moisture and have a particle size of 20 mm.

[0161] S2. Put boric acid, nickel oxide, wood chips and high-purity aluminum particles into a drying furnace according to the weight parts described in S1, and the temperature is 180° C. Petroleum coke and wood chips are used as combustion raw materials of the drying furnace;

[0162] S3, the dried boric acid, nickel oxide, wood chips and high-purity aluminum particles are transferred to a rotary kiln for pre-reduction, and petroleum coke and wood chips are added to the high temperature zone of the rotary kiln, and the temperature is controlled between 780°C, and the pre-reduction charge is obtained after processing for 5 hours;

[0163] S4, sending the pre-reduced charge to a submerged arc furnace for smelting at 1800°C for 20 hours;

[0164] S5, then refining at 1750°C for 35 minutes, and at the same time, bottom oxygen blowing is performed for 30 minutes through an oxygen blowing mechanism;

[0165] S6. After refining, the mixture is naturally cooled for 30 minutes and then cast to obtain a boron-nickel alloy.

[0166] Comparative Example 1

[0167] A process for producing boron nickel by a submerged arc furnace carbon thermal method comprises the following steps:

[0168] S1. Prepare the following raw materials by weight:

[0169] 100 parts of nickel oxide, 110 parts of boric acid, 15 parts of petroleum coke, 85 parts of wood chips, and 5 parts of ordinary commercially available aluminum particles were purchased from Nangong Dinghong Metal Materials Co., Ltd. with a CAS number of 365-656.

[0170] The nickel oxide has a content of 99%, a nickel content of 70%, a SiO2 content of 5%, a P content of 0.005%, and a particle size of 0.8 mm; the boric acid has a boric acid content of 99%;

[0171] The petroleum coke has a carbon content of 96% and a particle size of 15 mm;

[0172] The wood chips contain 25% moisture and have a particle size of 20 mm.

[0173] S2. Put boric acid, nickel oxide, wood chips and common commercially available aluminum particles into a drying furnace according to the weight parts described in S1, and the temperature is 200° C. Petroleum coke and wood chips are used as combustion raw materials of the drying furnace;

[0174] S3, the dried boric acid, nickel oxide, wood chips and common commercially available aluminum particles are transferred to a rotary kiln for pre-reduction, and petroleum coke and wood chips are added to the high temperature zone of the rotary kiln, and the temperature is controlled between 830°C, and the pre-reduction charge is obtained after treatment for 5 hours;

[0175] S4, sending the pre-reduced charge to a submerged arc furnace for smelting at 1800°C for 24 hours;

[0176] S5, then refining at 1750°C for 60 minutes, and at the same time, bottom oxygen blowing is performed for 30 minutes through an oxygen blowing mechanism;

[0177] S6. After refining, the mixture is naturally cooled for 60 minutes and then cast to obtain a boron-nickel alloy.

[0178] Comparative Example 2

[0179] The difference between this comparative example and Example 1 is:

[0180] The composite refining agent is a compound of sodium hexafluoroaluminate, sodium hexametapolyphosphate, sodium hexafluorosilicate and sodium bisulfite, wherein the mass ratio of sodium hexafluoroaluminate, sodium hexametapolyphosphate, sodium hexafluorosilicate and sodium bisulfite is 1:1.5:1:1.

[0181] Comparative Example 3

[0182] The difference between this comparative example and Example 1 is:

[0183] The composite refining agent is a compound of graphene, sodium hexafluoroaluminate, sodium hexametapolyphosphate, sodium hexafluorosilicate and sodium bisulfite, wherein the mass ratio of graphene, sodium hexafluoroaluminate, sodium hexametapolyphosphate, sodium hexafluorosilicate and sodium bisulfite is 1:5:5:5:3.

[0184] The graphene particle size is 6 μm and the number of layers is 8.

[0185] Comparative Example 4

[0186] The difference between this comparative example and Example 1 is:

[0187] The composite refining agent is a compound of graphene, sodium hexafluoroaluminate, sodium hexametapolyphosphate, sodium hexafluorosilicate and sodium bisulfite, wherein the mass ratio of graphene, sodium hexafluoroaluminate, sodium hexametapolyphosphate, sodium hexafluorosilicate and sodium bisulfite is 10:1:1:1:1.

[0188] The graphene particle size is 6 μm and the number of layers is 8.

[0189] The boron-nickel alloys prepared in Examples 1-9 and Comparative Examples 1-4 were analyzed for element content, with the remainder being Ni, as shown in Table 1 below:

[0190] Table 1

[0191] Analytical ingredients (%) Analytical ingredients (%) Analytical ingredients (%) Analytical ingredients (%) Analytical ingredients (%) Analytical ingredients (%) Analytical ingredients (%) Detection items B Si P Al Fe C S Example 1 21.57 0.45 0.020 0.97 1.23 0.250 0.003 Example 2 21.45 0.46 0.028 0.95 1.22 0.265 0.003 Example 3 21.35 0.47 0.026 0.96 1.21 0.245 0.004 Example 4 21.56 0.48 0.025 0.98 1.22 0.256 0.003 Example 5 21.48 0.46 0.028 0.95 1.22 0.265 0.004 Example 6 21.46 0.47 0.029 0.98 1.21 0.249 0.003 Example 7 21.45 0.46 0.028 0.95 1.22 0.265 0.003 Example 8 21.35 0.47 0.026 0.96 1.21 0.248 0.004 Example 9 21.57 0.49 0.028 0.96 1.21 0.252 0.004 Comparative Example 1 18.68 0.98 0.056 1.85 3.5 0.353 0.008 Comparative Example 2 20.68 0.68 0.042 1.25 3.1 0.312 0.007 Comparative Example 3 20.18 0.59 0.038 1.05 2.8 0.289 0.006 Comparative Example 4 19.88 0.56 0.036 1.02 2.7 0.286 0.006

[0192] The mechanical properties of the boron-nickel alloys prepared in Examples 1-9 of the present invention and Comparative Example 1 were tested respectively, and the specific results are shown in Table 2 below:

[0193] The bending strength of composite reinforced cemented carbide was tested by three-point bending method;

[0194] The fracture toughness of composite reinforced cemented carbide was tested by indentation method;

[0195] Table 2

[0196] Test items Flexural strength (MPa) Fracture toughness (MPa·m1 / 2) Example 1 1750 17.5 Example 2 1745 17.2 Example 3 1746 17.4 Example 4 1742 16.9 Example 5 1748 17.1 Example 6 1741 17.0 Example 7 1739 16.9 Example 8 1742 17.2 Example 9 1745 17.3 Comparative Example 1 1225 10.5 Comparative Example 2 1465 13.8 Comparative Example 3 1528 14.7 Comparative Example 4 1535 14.6

[0197] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A process for producing boron nickel by carbon thermal method in a submerged arc furnace, characterized in that: The following steps are involved: S1. Prepare the following raw materials by weight: 90-100 parts of nickel oxide, 100-110 parts of boric acid, 5-15 parts of petroleum coke, 75-85 parts of wood chips, 1-5 parts of high-purity aluminum particles; S2. Put boric acid, nickel oxide, wood chips and high-purity aluminum particles into a drying furnace according to the weight parts described in S1, and the temperature is 180-200° C. Petroleum coke and wood chips are used as combustion raw materials of the drying furnace; S3, the dried boric acid, nickel oxide, wood chips and high-purity aluminum particles are transferred to a rotary kiln for pre-reduction, and petroleum coke and wood chips are added to the high temperature zone of the rotary kiln, and the temperature is controlled between 780-830°C, and the pre-reduction charge is obtained after processing for 3-5 hours; S4, sending the pre-reduced charge to a submerged arc furnace for smelting at 1800°C for 10-24h; S5, then refining at 1750°C for 30-60min, while performing bottom oxygen blowing for 20-30min through an oxygen blowing mechanism; S6. After refining, the alloy is naturally cooled for 30-60 minutes and then cast to obtain a boron-nickel alloy. The preparation method of the high-purity aluminum particles comprises the following steps: The crude aluminum particles are melted at a high temperature of 700-800°C. After melting for 5-8 hours, a composite refining agent is added and refined for 30-60 minutes to obtain high-purity aluminum liquid. After filtering, the high-purity aluminum particles are cast and cut. The composite refining agent is a compound of graphene, sodium hexafluoroaluminate, sodium hexametapolyphosphate, sodium hexafluorosilicate and sodium bisulfite, wherein the mass ratio of graphene, sodium hexafluoroaluminate, sodium hexametapolyphosphate, sodium hexafluorosilicate and sodium bisulfite is 3-5:1-3:1.5-2.0:1-3:0.5-1.

2. The process for producing boron nickel by carbon thermal method using a submerged arc furnace according to claim 1, characterized in that: The nickel oxide has a content of 99%, contains nickel>65%, SiO2<6%, P<0.01%, and has a particle size<1mm; the boric acid has a boric acid content of 99%.

3. The process for producing boron nickel by carbon thermal method using a submerged arc furnace according to claim 1, characterized in that: The petroleum coke has a carbon content of 96% and a particle size of 15 to 20 mm.

4. The process for producing boron nickel by carbon thermal method using a submerged arc furnace according to claim 1, characterized in that: The wood chips contain less than 30% moisture and have a particle size of 20 to 30 mm.

5. The process for producing boron nickel by carbon thermal method using a submerged arc furnace according to claim 1, characterized in that: The graphene particle size is 6-12 μm, and the number of layers is 8.

6. The process for producing boron nickel by carbon thermal method using a submerged arc furnace according to claim 1, characterized in that: The composite refining agent is added in a manner of loading the composite refining agent into a sprayer and spraying the refining agent into the aluminum liquid using an inert gas.

7. The process for producing boron nickel by carbon thermal method using a submerged arc furnace according to claim 6, characterized in that: The inert gas is pure nitrogen or pure argon, and its purity is greater than 99.99%.