Method for preparing nickel carbonyl and carbonyl iron by fluidized bed carbonylation process

Abstract

The invention discloses a method for preparing carbonyl nickel and carbonyl iron by using a fluidized bed carbonylation process, which solves the problems of low carbonylation efficiency and incapability of high-valued utilization of iron in part of raw materials, and specifically comprises the following steps: 1) pulverizing a material containing nickel and iron by using a vacuum gas atomization technology; 2) treating the ferronickel-containing material powder through a fluidized bed carbonylation kettle to obtain crude carbonyl ferronickel and carbonylation tailings; 3) treating the crude carbonyl ferronickel through a three-stage condensation process to obtain a carbonyl nickel solution, a carbonyl iron solution and a carbonyl nickel and carbonyl iron mixed solution; and (4) the nickel carbonyl liquid, the iron carbonyl liquid and the mixed liquid of the nickel carbonyl and the iron carbonyl are subjected to rectification and segmented decomposition processes to obtain a nickel product and an iron product, finally, development of the carbonylation metallurgical raw materials is achieved, and clean and efficient treatment of the raw materials containing the nickel and the iron is also achieved.

Description

Technical Field

[0001] The invention relates to the technical field of powder metallurgy and metal materials, and in particular to a method for preparing carbonyl nickel and carbonyl iron by treating nickel-iron-containing materials through a fluidized bed carbonylation process. Background Art

[0002] Carbonylation metallurgy technology belongs to the field of gas phase metallurgy. This technology mainly uses the reaction of metals and carbon monoxide (CO) at specific temperature and pressure to generate volatile metal carbonyl complexes. The metal carbonyl complexes have different boiling points, and the metal complexes are distilled and purified and then thermally decomposed to obtain products. Compared with traditional pyrometallurgy and hydrometallurgy, carbonylation metallurgy can more efficiently extract high-purity metals from complex ores or waste slags. The carbonylation process has a very high degree of selective separation of metals, which is very conducive to promoting the green development of the industry.

[0003] At present, the domestic carbonylation process production faces problems such as long production cycle; lengthy front-end processes such as raw material drying and reduction; insufficient material contact and low carbonylation efficiency due to the influence of the reactor and material agglomeration state. This scheme adopts the fluidized bed carbonylation process, which uses carbon monoxide gas in the fluidized bed reactor to suspend the material from bottom to top at a certain gas velocity. This method can greatly improve the carbonylation rate and efficiency.

[0004] The carbonylation process for treating nickel-iron raw materials is an efficient and environmentally friendly metallurgical technology. Through gas-solid reaction and staged distillation and decomposition, carbonyl nickel and carbonyl iron products can be produced respectively, thus preparing high-quality nickel products and realizing the resource utilization of iron.

[0005] Chinese patent CN114014373A discloses a process for producing carbonyl nickel powder and carbonyl iron powder from nickel-iron particles. Compared with the patented process, this process adopts a fluidized carbonyl synthesis reactor process to make the nickel-iron alloy into powder, and passes it through a fluidized bed carbonyl synthesis reactor to make the gas-solid reaction contact surface larger and the reaction efficiency higher; and this process uses three-stage condensation and segmented decomposition to produce high-purity carbonyl nickel and carbonyl iron products.

[0006] Chinese patent CN105170989A discloses a method and system for preparing carbonyl nickel powder using nickel-iron alloy. Compared with the process, the raw material range of this application is wider and the raw material particle size is finer. In order to adapt to the fluidized bed carbonyl synthesis reactor, if the particle size is too coarse, fluidization will not be achieved, and if the particle size is too fine, fine particles will fly out. Therefore, this application obtains the most suitable particle size range through a large number of experiments, that is, the particle size is controlled within the range of 50-200μm and the particle size accounts for more than 75%. And the carbonylation process used in this application is a fluidization-carbonylation process, and the material is selected and carried out in a high-pressure fluidized bed carbonyl synthesis reactor. The equipment uses carbon monoxide gas to suspend the material from bottom to top at a certain gas velocity. This method can greatly improve the carbonylation rate and carbonylation efficiency. This process is an essentially different invention point. The condensation system in this process is a one-stage condensation system, while the present application adopts a three-stage condensation process. Due to the unstable nickel-iron ratio in the nickel-iron raw material, it is difficult to separate the mixed liquid of carbonyl nickel and carbonyl iron after only one stage of condensation. Since carbonyl nickel and carbonyl iron have different boiling points, the three-stage condensation process adopted in the present application can separate carbonyl nickel and carbonyl iron to a great extent in the condensation stage, and can also reduce the operating pressure of the subsequent distillation process. Summary of the invention

[0007] The purpose of the present invention is to provide a method for preparing carbonyl nickel and carbonyl iron by using a fluidized bed carbonylation process to address the problems of low efficiency of the carbonylation process for nickel-iron materials and the inability to realize high-value application of nickel and iron of some materials.

[0008] To achieve the above object, the present invention adopts the following technical solution: A method for preparing carbonyl nickel and carbonyl iron by using a fluidized bed carbonylation process, characterized in that it comprises the following steps: 1) Powdering nickel-iron materials by vacuum gas atomization technology; 2) Add the powdered material into a fluidized bed carbonylation reactor to carry out a fluidized carbonylation synthesis reaction to obtain crude carbonyl nickel iron and carbonylation tailings; wherein, in the fluidized bed carbonylation process, the pressure is controlled at 3-10 MPa, the temperature is controlled at 120°C-400°C, the CO gas flow rate is controlled at 1-4 m / s, and the reaction time is 8-24 h; 3) The crude carbonyl nickel iron is treated by a three-stage condensation process to obtain carbonyl nickel liquid, carbonyl iron liquid and carbonyl nickel and carbonyl iron mixed liquid; wherein the three-stage condensation temperatures are controlled at 85°C-180°C, 50°C-85°C and 5°C-50°C respectively; 4) The carbonyl nickel liquid, carbonyl iron liquid and the mixed liquid of carbonyl nickel and carbonyl iron are subjected to distillation and staged decomposition process to obtain nickel products and iron products. The distillation temperature is 45-51.6℃ at the top of the tower, 52.6-55℃ at the bottom of the tower, the working temperature of the reboiler temperature is: 52-75℃ at the shell side, the water cooler temperature is 30-51℃; the pressure of the bottom of the distillation tower is 0.05-0.07MPa. The decomposer temperature is 500-650℃ and the pressure is 0.1MPa.

[0009] In step 1), the nickel-iron material is a nickel-iron alloy which is an intermediate product of laterite ore, wherein the nickel grade is 8%-25% and the iron grade is 60%-82%. The particle size of the nickel-iron material powder prepared by vacuum gas atomization is controlled within the range of 50-200 μm, and the particle size accounts for more than 75%.

[0010] In step 2), the crude carbonyl nickel iron accounts for 1%-5% in the mixed gas, the nickel grade in the carbonyl tailings is 3%-8%, and the iron grade is 19%-23%.

[0011] Step 3) The purity of the carbonyl nickel liquid is greater than 96%, the purity of the carbonyl iron liquid is greater than 99.9%, and the carbonyl nickel and carbonyl iron mixed liquid contains 15%-30% carbonyl nickel and 70%-85% carbonyl iron.

[0012] In step 4), the grade of the final nickel product is greater than 98%, and the grade of the iron product is greater than 99.9%.

[0013] Compared with the prior art, the present invention has the following beneficial effects: 1. Make nickel-iron materials into powder to increase the surface area and the efficiency of gas-solid reaction; 2. The nickel-iron material powder is carbonylated in a fluidized bed carbonylation reactor to further improve the efficiency of the carbonylation reaction; 3. The crude carbonyl nickel iron produced can be refined to prepare carbonyl nickel and carbonyl iron products through three-stage condensation and segmented decomposition. That is, high-quality nickel and iron products are prepared, and high-value utilization of iron is achieved. The expansion of carbonyl metallurgical raw materials is achieved, and the use of nickel iron raw materials is transformed. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 It is a process flow chart of the present invention. DETAILED DESCRIPTION

[0015] Example 1 See also Figure 1 A method for preparing carbonyl nickel and carbonyl iron by using a fluidized bed carbonylation process, wherein the key steps of the treatment process include: 1) The nickel-iron alloy (nickel grade 12%, iron grade 75%) of the intermediate product of laterite ore is powdered by vacuum gas atomization technology, and the particle size of the powder in the range of 50-200μm accounts for 78%; 2) The nickel-iron alloy powder is processed by a fluidized carbonyl synthesis reactor to obtain crude nickel-iron carbonyl and carbonyl tailings; the fluidized bed pressure is 3MPa, the temperature is 150°C, the CO gas flow rate is 3.3m / s, and the reaction time is 24h; 3) treating the crude carbonyl nickel iron through a three-stage condensation process to obtain carbonyl nickel liquid, carbonyl iron liquid and a mixture of carbonyl nickel and carbonyl iron; the temperatures are 90° C., 70° C. and 45° C. respectively; 4) The carbonyl nickel liquid, carbonyl iron liquid and the mixed liquid of carbonyl nickel and carbonyl iron are subjected to distillation and staged decomposition process to obtain nickel products and iron products. The distillation temperature is 48°C at the top of the tower, 53°C at the bottom of the tower, the working temperature of the reboiler temperature is 58°C at the shell side, and the water cooler temperature is 35°C. The pressure of the bottom of the distillation tower is 0.05MPa. The decomposer temperature is 500°C and the pressure is 0.1MPa. The final nickel product grade is greater than 98%, and the iron product grade is greater than 99.9%.

[0016] Example 2 Ginseng Figure 1 A method for preparing carbonyl nickel and carbonyl iron by using a fluidized bed carbonylation process, wherein the key steps of the treatment process include: 1) The water-quenched alloy (nickel grade 20%, iron grade 80%) was powdered by vacuum gas atomization technology, and the particle size of the powder in the range of 50-200μm accounted for 86%; 2) The water-quenched alloy powder was treated by a fluidized carbonylation synthesis reactor to obtain crude carbonyl nickel iron and carbonylation tailings; the fluidized bed pressure was 8MPa, the temperature was 180°C, the CO gas flow rate was 1.4m / s, and the reaction time was 8h; 3) treating the crude carbonyl nickel iron through a three-stage condensation process to obtain carbonyl nickel liquid, carbonyl iron liquid and a mixture of carbonyl nickel and carbonyl iron; the temperatures are 150° C., 70° C. and 45° C. respectively; 4) The carbonyl nickel liquid, carbonyl iron liquid and the mixed liquid of carbonyl nickel and carbonyl iron are subjected to distillation and segmented decomposition process to obtain nickel products and iron products. The distillation temperature is 45°C at the top of the tower, 52.5°C at the bottom of the tower, the working temperature of the reboiler temperature is 60°C at the shell side, and the water cooler temperature is 35°C. The pressure of the bottom of the distillation tower is 0.07MPa. The decomposer temperature is 550°C and the pressure is 0.1MPa. The final nickel product grade is greater than 98%, and the iron product grade is greater than 99.9%.

[0017] Example 3 Ginseng Figure 1 A method for preparing carbonyl nickel and carbonyl iron by using a fluidized bed carbonylation process, wherein the key steps of the treatment process include: 1) The recovered nickel-containing secondary resources (nickel grade 10%, iron grade 62%) are powdered through vacuum gas atomization technology, and the particle size of the powder in the range of 50-200μm accounts for 82%; 2) The raw material powder is processed through a fluidized carbonyl synthesis reactor to obtain crude carbonyl nickel iron and carbonyl tailings; the fluidized bed pressure is 6MPa, the temperature is 330°C, the CO gas flow rate is 3.3m / s, and the reaction time is 16h; 3) treating the crude carbonyl nickel iron through a three-stage condensation process to obtain carbonyl nickel liquid, carbonyl iron liquid and a mixture of carbonyl nickel and carbonyl iron; the temperatures are 170° C., 70° C. and 45° C. respectively; 4) The carbonyl nickel liquid, carbonyl iron liquid and the carbonyl nickel and carbonyl iron mixed liquid are subjected to distillation and segmented decomposition processes to obtain a final nickel product with a grade greater than 98% and an iron product with a grade greater than 99.9%. The distillation temperature is 50°C at the top of the tower, 53°C at the bottom of the tower, and the working temperature of the reboiler temperature is 75°C at the shell side and 51°C at the water cooler. The pressure of the distillation tower bottom is 0.05MPa. The decomposer temperature is 650°C and the pressure is 0.1MPa.

Claims

1. A method for preparing carbonyl nickel and carbonyl iron by using a fluidized bed carbonylation process, characterized in that: The following steps are involved: 1) Powdering nickel-iron materials by vacuum gas atomization technology; 2) Add the powdered material into a fluidized bed carbonylation reactor to carry out a fluidized carbonylation synthesis reaction to obtain crude carbonyl nickel iron and carbonylation tailings; wherein, in the fluidized bed carbonylation process, the pressure is controlled at 3-10 MPa, the temperature is controlled at 120°C-400°C, the CO gas flow rate is controlled at 1-4 m / s, and the reaction time is 8-24 h; 3) The crude carbonyl nickel iron is treated by a three-stage condensation process to obtain carbonyl nickel liquid, carbonyl iron liquid and carbonyl nickel and carbonyl iron mixed liquid; wherein the three-stage condensation temperatures are controlled at 85°C-180°C, 50°C-85°C and 5°C-50°C respectively; 4) The carbonyl nickel liquid, the carbonyl iron liquid and the carbonyl nickel and carbonyl iron mixed liquid are subjected to distillation and staged decomposition processes to obtain nickel products and iron products; wherein the distillation temperature is 45-51.6°C at the top of the tower and 52.6-55°C at the bottom of the tower; the reboiler temperature working temperature: 52-75°C at the shell side and 30-51°C at the water cooler; the distillation tower bottom pressure is 0.05-0.07MPa; the decomposer temperature is 500-650°C and the pressure is 0.1MPa.

2. The method for preparing carbonyl nickel and carbonyl iron by fluidized bed carbonylation process according to claim 1, characterized in that: In step 1), the nickel-iron material is a nickel-iron alloy which is an intermediate product of laterite ore, wherein the nickel grade is 8%-25%, the iron grade is 60%-82%, and the powder particle size of the nickel-iron material prepared by vacuum gas atomization is controlled within the range of 50-200 μm, and the particle size accounts for more than 75%.

3. The method for preparing carbonyl nickel and carbonyl iron by fluidized bed carbonylation process according to claim 1, characterized in that: In step 2), crude carbonyl nickel iron accounts for 1%-5% in the mixed gas, the nickel grade in the carbonyl tailings is 3%-8%, and the iron grade is 19%-23%.

4. The method for preparing carbonyl nickel and carbonyl iron by using fluidized bed carbonylation process according to claim 1, characterized in that: In step 3), the purity of the carbonyl nickel liquid is greater than 96%, the purity of the carbonyl iron liquid is greater than 99.9%, and the carbonyl nickel and carbonyl iron mixed liquid contains 15%-30% carbonyl nickel and 70%-85% carbonyl iron.

5. The method for preparing carbonyl nickel and carbonyl iron by fluidized bed carbonylation process according to claim 1, characterized in that: In step 4), the grade of the final nickel product is greater than 98%, and the grade of the iron product is greater than 99.9%.

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