Method for producing high-quality nickel chloride from nickel carbonate raw material

Abstract

The invention discloses a method for producing high-quality nickel chloride from a nickel carbonate raw material, and relates to the technical field of nickel salt wet smelting. The method comprises the following specific steps: slurrying nickel carbonate and nickel chloride mother liquor, dissolving with hydrochloric acid under normal pressure, and then carrying out N235 extraction impurity removal, oil removal, lead removal, evaporation, crystallization, centrifugation, drying and other procedures to obtain high-quality nickel chloride. The high-quality nickel chloride product is obtained by controlling the temperature and pH of normal-pressure dissolution and controlling the extraction agent and the extraction flow ratio in the extraction and impurity removal process, Ni is larger than or equal to 24%, Co is smaller than or equal to 0.001%, Cu is smaller than or equal to 0.0001%, Fe is smaller than or equal to 0.001%, Pb is smaller than or equal to 0.0008%, Zn is smaller than or equal to 0.0001%, Ca is smaller than or equal to 0.026%, Mg is smaller than or equal to 0.02%, Na is smaller than or equal to 0.27%, water insoluble matter is smaller than or equal to 0.005%, and the product quality meets the requirements of GB / T 26522-2011 refined nickel chloride first-grade products. The method has the advantages of being short in technological process, high in leaching efficiency, short in time, easy to filter, low in energy consumption, convenient for industrial production and the like.

Description

Technical Field

[0001] The invention relates to the technical field of nickel salt hydrometallurgy, and in particular to a method for producing high-quality nickel chloride from a nickel carbonate raw material. Background Art

[0002] The statements in this section are merely intended to provide background information related to the technical solution of the present application to aid understanding, and they do not necessarily constitute prior art for the technical solution of the present application.

[0003] At present, the production of nickel chloride is mainly based on various mixed nickel concentrates with relatively low nickel content. However, the processing process of nickel concentrate is relatively long, the output is relatively low, and the supply of nickel concentrate raw materials is limited. Therefore, in order to solve the problem that the output of nickel chloride produced with nickel concentrate as raw material cannot be increased and to assist in the production transformation of nickel salts, it is necessary to select other nickel raw materials. Among them, the purchased BHP Billiton nickel carbonate material can be directly used to produce nickel chloride solution due to its high nickel content and low impurity content. At the same time, in order to further shorten the process of producing nickel chloride from nickel carbonate, it is necessary to further develop a short-process, low-energy consumption, high-quality production process using nickel carbonate.

[0004] Meanwhile, in the production process of nickel chloride, chemical precipitation is often used to remove iron, so that a certain amount of iron slag is generated during the production process and needs to be further processed. The disadvantage of this method is that the amount of slag is too large, and the filtration is difficult due to the high viscosity of the ferric hydroxide colloid, and the iron slag contains a large amount of nickel, so the iron slag needs to be further processed to recover the nickel therein. Therefore, it is also necessary to find a method for removing iron that reduces the generation of iron slag. Summary of the invention

[0005] In order to simplify the production process of nickel chloride and improve the yield, the present invention provides a method for producing high-quality nickel chloride from nickel carbonate raw material, comprising the following steps:

[0006] (1) Slurrying and dissolving the nickel carbonate raw material: taking a nickel chloride solution and adding water to prepare a nickel chloride mother liquor with a nickel content of 40-60 g / L, the nickel chloride mother liquor is used to slurry the nickel carbonate raw material, and the slurry liquid-to-solid ratio is (7-9):1, and then 8-9 mol / L hydrochloric acid is added under normal pressure to dissolve, and the temperature during the dissolution process is controlled to be greater than 80° C., and the endpoint pH value is controlled to be 3.0-4.0. After the dissolution is completed, the nickel chloride solution is filtered to obtain a nickel chloride solution and a filter residue, wherein the nickel chloride solution contains Ni≥170 g / L, and the filter residue contains Ni<6%, and the filter residue is returned to the nickel carbonate raw material slurrying and dissolving step;

[0007] (2) N235 extraction and iron removal: The nickel chloride solution is extracted and iron removed using N235 extractant, wherein the volume percentage of N235 in the N235 extractant is 15-17%, the extraction flow ratio is organic phase: aqueous phase (1.1-1.3):1, the reaction temperature is 40-50°C, and after four-stage oil removal, the iron-removed liquid is obtained. - Concentration ≥270g / L;

[0008] (3) Lead removal with ion exchange resin: The de-ironized liquid is passed through an ion exchange resin for lead removal, and the lead-free liquid is obtained after four stages of oil removal;

[0009] (4) Post-treatment: evaporating, crystallizing, centrifuging and drying the lead-removed liquid to obtain a nickel chloride product, wherein the components of the nickel chloride product are: Ni ≥ 24%, Co ≤ 0.001%, Cu ≤ 0.0001%, Fe ≤ 0.001%, Pb ≤ 0.0008%, Zn ≤ 0.0001%, Ca ≤ 0.026%, Mg ≤ 0.02%, Na ≤ 0.27%, and water-insoluble matter ≤ 0.005%;

[0010] The four-stage oil removal process is respectively static oil removal, ultrasonic flotation oil removal and two-stage fiber ball oil removal.

[0011] Furthermore, in step (1), the typical composition of the nickel carbonate raw material is 45.09±0.2% nickel, 0.019±0.001% cobalt, 0.0075±0.0005% copper, 0.0025±0.0002% iron, 0.0088±0.0002% zinc, 0.055±0.002% calcium, and 0.027±0.002% magnesium.

[0012] Compared with the prior art, the beneficial technical effects of the present invention are:

[0013] (1) The above method is used to produce high-quality nickel chloride using BHP Billiton nickel carbonate raw material (nickel carbonate raw material with low impurities and high nickel content), and the iron is removed by extraction, thereby reducing the amount of iron slag produced by the chemical precipitation method, reducing the labor intensity of the operator, and improving the direct metal recovery rate. The quality of the nickel chloride product produced meets the requirements of GB / T26522-2011 for first-class refined nickel chloride.

[0014] (2) As Cl - As the concentration increases, almost all impurity metal ions in the nickel chloride solution are converted into [MeCl4] n-The complex anion exists, and the impurity metal can be effectively removed by N235 extraction. N235 is extracted in a hydrochloric acid system to improve the extraction capacity of N235, and the hydrochloric acid environment can also inhibit the generation of nickel chloride crystals. At the same time, the extraction O / A ratio and N235 ratio within the scope of the technical solution of the present invention are selected to make the removal rate of Co as high as 99.9%, and at the same time, Cu and Fe in the solution are further removed, thereby improving the quality of the nickel sulfate product, and at this time the removal rate of Ni is only about 4%, achieving the purpose of nickel-cobalt separation.

[0015] (3) This process method has a short process flow and low energy consumption, and the nickel chloride produced is of high quality, which can realize industrial mass production of nickel chloride. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 Production process flow chart of the present invention. DETAILED DESCRIPTION

[0017] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the method and process of the present application are described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0018] The method is specifically as follows: nickel chloride solution is added with water to prepare a nickel chloride mother liquor with a nickel content of 40-60 g / L, and nickel carbonate with typical composition (nickel 45.09±0.2%, cobalt 0.019±0.001%, copper 0.0075±0.0005%, iron 0.0025±0.0002%, zinc 0.0088±0.0002%, calcium 0.055±0.002%, magnesium 0.027±0.002%) is taken and put into a slurry tank together with the nickel chloride mother liquor for slurrying, and the slurry liquid-to-solid ratio is (7-9):1, and then enters the reaction tank. The tank is dissolved with 8-9 mol / L hydrochloric acid, the reaction temperature is controlled to be greater than 80°C, the pH of the reaction end point is 3.0-4.0, the dissolved slurry is discharged to the leaching intermediate tank for closed filtration, and the filter residue is returned to the reaction tank for dissolution after washing and filtration; then the nickel chloride solution is subjected to N235 extraction to remove iron, the content of N235 in the N235 extractant is controlled to be 15-17% (volume percentage), the extraction flow ratio O / A=(1.1-1.3):1, the reaction temperature is 40-50°C, and after extraction, a four-stage deoiling treatment is performed to obtain a deironing liquid, and Cl in the deironing liquid -Concentration ≥ 270g / L, of which the four-stage oil removal process is static oil removal, ultrasonic flotation oil removal and two-stage fiber ball oil removal. The four-stage oil removal operation process is: the raffinate passes through the outdoor clarification tank in turn for static oil removal, then passes through the No. 1 dissolved air flotation oil removal tank and the No. 2 dissolved air flotation oil removal tank for ultrasonic flotation oil removal, and then passes through the first oil removal column (filled with fiber balls), the first oil removal intermediate tank, the second oil removal column (filled with fiber balls), and the second oil removal intermediate tank for two-stage fiber ball oil removal to obtain the deoiled liquid. The oil discharged regularly from the outdoor clarification tank and the dissolved air flotation oil removal tank is sent to the waste oil tank for oil-water separation, the oil phase is passed to the load organic clarification tank for stripping and acid washing, and the water phase is passed to the wastewater tank. Subsequently, the iron-removed liquid is sent to an ion exchange resin for lead removal, and then undergoes four stages of oil removal, evaporation, crystallization, centrifugation, and drying to produce a nickel chloride product. The composition content of the nickel chloride product is: Ni ≥ 24%, Co ≤ 0.001%, Cu ≤ 0.0001%, Fe ≤ 0.001%, Pb ≤ 0.0008%, Zn ≤ 0.0001%, Ca ≤ 0.026%, Mg ≤ 0.02%, Na ≤ 0.27%, and water-insoluble matter ≤ 0.005%, which meets the requirements of GB / T 26522-2011 for first-class refined nickel chloride.

[0019] Example 1

[0020] like Figure 1 As shown, a method for producing high-quality nickel chloride from nickel carbonate raw materials comprises the following steps:

[0021] S1: Take nickel carbonate with typical composition: nickel 45.09%, cobalt 0.019%, copper 0.0075%, iron 0.0025%, zinc 0.0088%, calcium 0.055%, magnesium 0.027%, and put it into a slurry tank together with nickel chloride mother liquor for slurrying, with a slurry liquid-solid ratio of 7:1, and then put it into a reaction tank for dissolution with 8.5-9mol / L hydrochloric acid, control the reaction temperature to 85°C, and the reaction end point pH is 3.5 , the dissolved ore pulp is discharged to the leaching intermediate tank for closed filtration, and the filter residue is washed and filtered and then returned to the reaction tank for dissolution; the composition of the filtered nickel chloride solution is: nickel 178.97g / L, cobalt 0.083g / L, copper 0.014g / L, iron 0.020g / L, lead 0.011g / L, calcium 0.058g / L, magnesium 0.091g / L, sodium 0.32g / L, sulfate 3.96g / L, and the filter residue contains 4.5% nickel. The nickel chloride solution is subjected to N235 extraction to remove iron, and the volume ratio of N235 extractant is controlled to be 16% N235 and 84% solvent, the extraction flow ratio O / A=1.2:1, the reaction temperature is 45℃, and the iron-removed liquid is obtained by four-stage deoiling treatment after extraction. The Cl in the iron-removed liquid -The concentration is 270g / L, and the other components are: nickel 171.23g / L, cobalt 0.003g / L, copper 0.002g / L, iron 0.002g / L, lead 0.015g / L, calcium 0.034g / L, magnesium 0.078g / L, sodium 0.27g / L. The de-ironized liquid is then sent to the ion exchange resin for lead removal, and then the nickel chloride product is produced after four stages of oil removal, evaporation, crystallization, centrifugation, and drying. The components in the nickel chloride product are: Ni 24.08%, Co 0.0006%, Cu 0.0001%, Fe 0.00096%, Pb 0.00068%, Zn 0.0001%, Ca 0.024%, Mg 0.017%, Na 0.024%, and water insoluble matter 0.0047%.

[0022] Example 2

[0023] like Figure 1 As shown, a method for producing high-quality nickel chloride from nickel carbonate raw materials comprises the following steps:

[0024] S1: Take nickel carbonate with typical composition: 45.07% nickel, 0.018% cobalt, 0.0075% copper, 0.0026% iron, 0.0088% zinc, 0.055% calcium, 0.029% magnesium, and mix it with nickel chloride mother liquor into a slurry tank for slurrying, with a slurry liquid-solid ratio of 8.5:1, and then enter the reaction tank for dissolution with 8.0-8.5 mol / L hydrochloric acid, control the reaction temperature at 90°C, and the reaction end point pH is 4 .0, the dissolved ore pulp is discharged to the leaching intermediate tank for closed filtration, and the filter residue is washed and filtered and then returned to the reaction tank for dissolution; the composition of the nickel chloride solution after filtration is: nickel 175.51g / L, cobalt 0.079g / L, copper 0.0072g / L, iron 0.0025g / L, lead 0.01g / L, calcium 0.059g / L, magnesium 0.088g / L, sodium 0.31g / L, sulfate 3.87g / L, and the filter residue contains 4.8% nickel. The nickel chloride solution is subjected to N235 extraction to remove iron, and the volume ratio of N235 extractant is controlled to be 15% N235 and 85% solvent, the extraction flow ratio O / A=1.1:1, the reaction temperature is 50℃, and after extraction, it is subjected to four-stage deoiling treatment to obtain the deironing liquid, and the Cl in the deironing liquid -The concentration is 280g / L, and the other components are: nickel 168.78g / L, cobalt 0.003g / L, copper 0.002g / L, iron 0.002g / L, lead 0.009g / L, calcium 0.042g / L, magnesium 0.086g / L, sodium 0.32g / L. The de-ironized liquid is then sent to the ion exchange resin for lead removal, and then the nickel chloride product is produced after four stages of oil removal, evaporation, crystallization, centrifugation, and drying. The components in the nickel chloride product are: Ni 24.01%, Co 0.001%, Cu 0.0001%, Fe 0.00099%, Pb 0.00068%, Zn0.0001%, Ca 0.017%, Mg 0.017%, Na 0.027%, and water insoluble matter 0.0046%.

[0025] Example 3

[0026] like Figure 1 As shown, a method for producing high-quality nickel chloride from nickel carbonate raw materials comprises the following steps:

[0027] S1: Take nickel carbonate with typical composition: nickel 45.10%, cobalt 0.020%, copper 0.0074%, iron 0.0026%, zinc 0.0088%, calcium 0.055%, magnesium 0.027%, and put it into a slurry tank together with nickel chloride mother liquor for slurrying, with a slurry liquid-solid ratio of 9:1, and then put it into a reaction tank for dissolution with 8.2-8.7 mol / L hydrochloric acid, control the reaction temperature to 87°C, and the reaction end point pH is 3 .0, the dissolved ore pulp is discharged to the leaching intermediate tank for closed filtration, and the filter residue is washed and filtered and then returned to the reaction tank for dissolution; the composition of the filtered nickel chloride solution is: nickel 179.28g / L, cobalt 0.085g / L, copper 0.015g / L, iron 0.020g / L, lead 0.012g / L, calcium 0.059g / L, magnesium 0.09g / L, sodium 0.32g / L, sulfate 3.98g / L, and the filter residue contains 4.2% nickel. The nickel chloride solution is subjected to N235 extraction to remove iron, and the volume ratio of N235 extractant is controlled to be 17% N235 and 83% solvent, the extraction flow ratio O / A=1.3:1, the reaction temperature is 40℃, and after extraction, it is subjected to four-stage deoiling treatment to obtain the iron-removed liquid, and the Cl in the iron-removed liquid -The concentration is 270g / L, and the other components are: nickel 171.23g / L, cobalt 0.003g / L, copper 0.002g / L, iron 0.002g / L, lead 0.015g / L, calcium 0.034g / L, magnesium 0.078g / L, sodium 0.30g / L. The de-ironized liquid is then sent to the ion exchange resin for lead removal, and then the nickel chloride product is produced after four stages of oil removal, evaporation, crystallization, centrifugation, and drying. The components in the nickel chloride product are: Ni 24.05%, Co 0.0008%, Cu 0.0001%, Fe 0.00096%, Pb 0.00072%, Zn 0.0001%, Ca 0.024%, Mg0.019%, Na 0.026%, and water insoluble matter 0.0047%.

[0028] Comparative Example 1

[0029] A method for producing high-quality nickel chloride from a nickel carbonate raw material comprises the following steps:

[0030] S1: Take nickel carbonate with typical composition: 45.09% nickel, 0.019% cobalt, 0.0075% copper, 0.0025% iron, 0.0088% zinc, 0.055% calcium, 0.027% magnesium, and put it into a slurry tank together with nickel chloride mother liquor for slurrying, with a slurry liquid-solid ratio of 5:1, and then put it into a reaction tank for dissolution with 5mol / L hydrochloric acid, control the reaction temperature to 80°C, and the reaction end point pH to 5.0, The dissolved ore pulp is discharged to the leaching intermediate tank for closed filtration, and the filter residue is washed and filtered and then returned to the reaction tank for dissolution; the composition of the filtered nickel chloride solution is: nickel 161.78g / L, cobalt 0.079g / L, copper 0.013g / L, iron 0.020g / L, lead 0.015g / L, calcium 0.054g / L, magnesium 0.091g / L, sodium 0.03g / L, sulfate 4.52g / L, and the filter residue contains 4.8% nickel. The nickel chloride solution is subjected to N235 extraction to remove iron, and the volume ratio of N235 extractant is controlled to be 20% N235 and 80% solvent, the extraction flow ratio O / A=0.8:1, the reaction temperature is 40°C, and after extraction, it is subjected to four-stage deoiling treatment to obtain the deironized liquid, and the Cl in the deironized liquid -The concentration is 230g / L, and the other components are: nickel 153.43g / L, cobalt 0.0041g / L, copper 0.0035g / L, iron 0.0037g / L, lead 0.014g / L, calcium 0.034g / L, magnesium 0.082g / L, sodium 0.29g / L. The de-ironized liquid is then sent to the ion exchange resin for lead removal, and then the nickel chloride product is produced after four stages of oil removal, evaporation, crystallization, centrifugation, and drying. The components in the nickel chloride product are: Ni22.51%, Co 0.0007%, Cu0.00015%, Fe 0.0011%, Pb 0.00069%, Zn 0.0002%, Ca0.028%, Mg 0.019%, Na 0.026%, and water insoluble matter 0.0058%.

[0031] According to the above embodiments, it can be seen that when the reaction conditions, especially the dissolution pH, the extractant concentration, the extraction flow ratio, etc. are controlled within the scope of the present invention, a high-quality nickel chloride product Ni ≥ 24%, Co ≤ 0.001%, Cu ≤ 0.0005%, Fe ≤ 0.001%, Pb ≤ 0.002%, Zn ≤ 0.0002%, Ca ≤ 0.04%, Mg ≤ 0.16%, Na ≤ 0.24%, and water-insoluble matter ≤ 0.005% can be obtained, and the product quality meets the requirements of the first-class refined nickel chloride in GB / T 26522-2011.

Claims

1. A method for producing high-quality nickel chloride from nickel carbonate raw material, characterized in that: The method comprises the following steps: (1) Slurry dissolution of nickel carbonate raw material: prepare a nickel chloride mother liquor with a nickel content of 40-60 g / L, use the nickel chloride mother liquor to slurry the nickel carbonate raw material, the slurry liquid-to-solid ratio is (7-9):1, then add 8-9 mol / L hydrochloric acid under normal pressure to dissolve, the dissolution process temperature is controlled to be greater than 80° C., the endpoint pH value is controlled to be 3.0-4.0, and after the dissolution is completed, filter to obtain a nickel chloride solution and a filter residue, wherein the nickel chloride solution contains nickel ≥170 g / L, and the filter residue contains nickel <6%. The filter residue is returned to the nickel carbonate raw material slurry dissolution step; (2) N235 extraction and iron removal: The nickel chloride solution is extracted and iron removed using N235 extractant, wherein the volume percentage of N235 in the N235 extractant is 15-17%, the extraction flow ratio is organic phase: aqueous phase (1.1-1.3):1, the reaction temperature is 40-50°C, and after four-stage oil removal, an iron-removed liquid is obtained. The iron-removed liquid contains Cl - Concentration ≥270g / L; (3) Lead removal with ion exchange resin: The de-ironized liquid is subjected to lead removal with ion exchange resin, and the lead-free liquid is obtained after four-stage oil removal; (4) Post-treatment: evaporating, crystallizing, centrifuging and drying the lead-free solution to obtain a nickel chloride product, wherein the components of the nickel chloride product are: Ni ≥ 24%, Co ≤ 0.001%, Cu ≤ 0.0001%, Fe ≤ 0.001%, Pb ≤ 0.0008%, Zn ≤ 0.0001%, Ca ≤ 0.026%, Mg ≤ 0.02%, Na ≤ 0.27%, and water-insoluble matter ≤ 0.005%; The four-stage oil removal process is respectively static oil removal, ultrasonic flotation oil removal and two-stage fiber ball oil removal.

2. The method for producing high-quality nickel chloride from a nickel carbonate raw material according to claim 1, characterized in that: In step (1), the typical composition of the nickel carbonate raw material is nickel 45.09±0.2%, cobalt 0.019±0.001%, copper 0.0075±0.0005%, iron 0.0025±0.0002%, zinc 0.0088±0.0002%, calcium 0.055±0.002%, and magnesium 0.027±0.002%.

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