WO2017024551A1 - Method and system for preparing carbonyl nickel powder with laterite-nickel ore - Google Patents

Method and system for preparing carbonyl nickel powder with laterite-nickel ore Download PDF

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WO2017024551A1
WO2017024551A1 PCT/CN2015/086746 CN2015086746W WO2017024551A1 WO 2017024551 A1 WO2017024551 A1 WO 2017024551A1 CN 2015086746 W CN2015086746 W CN 2015086746W WO 2017024551 A1 WO2017024551 A1 WO 2017024551A1
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Prior art keywords
nickel
carbonyl
carbon monoxide
iron powder
powder
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PCT/CN2015/086746
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French (fr)
Chinese (zh)
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吴道洪
王静静
宋文臣
李红科
曹志成
薛逊
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北京神雾环境能源科技集团股份有限公司
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Priority to PCT/CN2015/086746 priority Critical patent/WO2017024551A1/en
Publication of WO2017024551A1 publication Critical patent/WO2017024551A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/02—Carbonyls
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals

Definitions

  • the invention belongs to the technical field of metallurgy, in particular, the invention relates to a method and a system for preparing nickel carbonyl powder by using laterite nickel ore.
  • the most common method for smelting laterite nickel ore by fire method is the RKEF method.
  • the obtained product is a nickel-iron alloy, and the nickel-iron alloy can be used as a steelmaking raw material.
  • the smelting method consumes a large amount of energy.
  • the ferronickel plant is in a state of loss and production.
  • the wet smelting of laterite nickel ore involves environmental pollution problems such as waste liquid discharge. Therefore, it is necessary to carry out innovative research on the treatment process of laterite nickel ore and develop a new process for efficient use of laterite nickel ore.
  • the carbonyl refining process is the most advanced nickel purification process. It was invented by C. Langer and L. Mond in 1889. The principle is that nickel is a complex compound of nickel tetracarbonyl formed directly with CO under certain temperature and pressure conditions. Ni(CO) 4 , the carbonyl metal compound is unstable under normal pressure and rapidly decomposes into Ni and CO upon heating. The method has the advantages of simple process, low energy consumption and high nickel extraction rate.
  • Patent CN201310078977 discloses a method for producing nickel carbonyl powder by using nickel hydroxide having a nickel content of more than 39% as a raw material, and calcining to produce nickel oxide, and the oxide is reduced to elemental nickel in a hydrogen reduction furnace. Nickel and CO undergo a carbonylation synthesis reaction, which is then sent to a carbonyl decomposer to form a nickel carbonyl product.
  • the raw material nickel hydroxide used in the method is an industrial processed product, and does not directly exist in nature, and the method has a long process flow and high production cost, and the method has strict limits on the iron content of the raw material, and the iron content must be Less than 0.3%, otherwise it affects the purity of nickel powder.
  • an object of the present invention is to provide a method and system for preparing nickel carbonyl powder by using laterite nickel ore, which can effectively obtain high-purity nickel carbonyl powder by using low-cost laterite nickel ore, and has a simple process. Environmentally friendly.
  • the invention provides a method of preparing nickel carbonyl powder using laterite nickel ore, according to an embodiment of the invention, the method comprising:
  • the method for preparing nickel carbonyl powder by using laterite nickel ore according to the embodiment of the invention can effectively prepare high-purity nickel carbonyl powder by using low-cost laterite nickel ore, and the process is simple and environmentally friendly.
  • the method for preparing nickel carbonyl powder using laterite nickel ore according to the above embodiment of the present invention may further have the following additional technical features:
  • the method for preparing nickel carbonyl powder using laterite nickel ore further comprises: (7) contacting the first carbon monoxide returning step (4) with the nickel iron powder.
  • the method of preparing nickel carbonyl powder using laterite nickel ore further comprises: (8) returning the second carbon monoxide to step (4) to contact the nickel iron powder.
  • the carbon monoxide cycle utilization ratio can be further improved.
  • the sulfur content of the high sulfur coal is greater than 3 wt%.
  • the additive is at least one selected from the group consisting of a potassium salt, a sodium salt, a calcium salt, an alkali metal oxide, and an alkaline earth metal oxide.
  • the invention provides a system for preparing nickel carbonyl powder from laterite nickel ore, according to an embodiment of the invention, the system comprising:
  • a mixing pelletizing device having a laterite nickel ore inlet, a high sulfur coal inlet, an additive inlet, and a mixing pellet outlet, and is suitable for mixing a laterite nickel ore, a high sulfur coal, and an additive to obtain Mixed pellets;
  • a reduction smelting apparatus having a mixing pellet inlet and a metallized pellet outlet, the mixing pellet inlet being connected to the mixing pellet outlet, and adapted to perform the reduction smelting treatment of the mixing pellet In order to obtain metallized pellets;
  • a water quenching-grinding-magnetic separation device having a metallized pellet inlet, a nickel iron powder outlet, and a tailings outlet, the metallized pellet inlet and the metallized sphere
  • the group outlet is connected, and is suitable for performing water quenching-grinding-magnetic separation treatment on the metallized pellets to obtain nickel iron powder and tailings respectively;
  • An oxo synthesis apparatus having a carbon monoxide inlet, a nickel iron powder inlet, a gaseous mixture outlet, and an iron powder outlet, the nickel iron powder inlet being connected to the nickel iron powder outlet, and adapted to be the nickel iron powder Contacting with carbon monoxide to obtain a gaseous mixture containing nickel carbonyl, iron carbonyl and carbon monoxide, and iron powder;
  • a purification apparatus having a gaseous mixture inlet, a gaseous nickel carbonyl outlet, and a first carbon monoxide outlet, the gaseous mixture inlet being connected to the gaseous mixture outlet and adapted to contain the nickel carbonyl, carbonyl iron and carbon monoxide
  • the gaseous mixture is subjected to a purification treatment to obtain gaseous nickel carbonyl and first carbon monoxide, respectively;
  • a decomposition apparatus having a gaseous nickel carbonyl inlet, a nickel carbonyl powder outlet, and a second carbon monoxide outlet, the gaseous nickel carbonyl inlet being connected to the gaseous nickel carbonyl outlet, and adapted to decompose the gaseous nickel carbonyl In order to obtain nickel carbonyl powder and second carbon monoxide, respectively.
  • the system for preparing nickel carbonyl powder by using laterite nickel ore according to the embodiment of the present invention can effectively obtain high-purity nickel carbonyl powder by using low-cost laterite nickel ore, and the process is simple and environmentally friendly.
  • system for preparing nickel carbonyl powder using laterite nickel ore may further have the following additional technical features:
  • the reduction smelting apparatus is at least one selected from the group consisting of a rotary hearth furnace, a rotary kiln, and a tunnel kiln.
  • the first carbon monoxide outlet is connected to the carbon monoxide inlet and is adapted to return the first carbon monoxide to the oxo synthesis unit in contact with the nickel iron powder.
  • the second carbon monoxide outlet is connected to the carbon monoxide inlet and is adapted to return the second carbon monoxide to the oxo unit in contact with the nickel iron powder.
  • the carbon monoxide cycle utilization ratio can be further improved.
  • FIG. 1 is a schematic flow chart of a method for preparing nickel carbonyl powder by using laterite nickel ore according to an embodiment of the present invention
  • FIG. 2 is a schematic flow chart of a method for preparing nickel carbonyl powder by using laterite nickel ore according to still another embodiment of the present invention
  • FIG. 3 is a schematic flow chart of a method for preparing nickel carbonyl powder by using laterite nickel ore according to still another embodiment of the present invention
  • FIG. 4 is a schematic structural view of a system for preparing nickel carbonyl powder by using laterite nickel ore according to an embodiment of the present invention
  • FIG. 5 is a schematic structural view of a system for preparing nickel carbonyl powder by using laterite nickel ore according to still another embodiment of the present invention.
  • FIG. 6 is a schematic view showing the structure of a system for preparing nickel carbonyl powder using laterite nickel ore according to still another embodiment of the present invention.
  • first and second are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated.
  • features defining “first” or “second” may include at least one of the features, either explicitly or implicitly.
  • the meaning of "a plurality” is at least two, such as two, three, etc., unless specifically defined otherwise.
  • the terms “installation”, “connected”, “connected”, “fixed” and the like shall be understood broadly, and may be either a fixed connection or a detachable connection, unless explicitly stated and defined otherwise. , or integrated; can be mechanical or electrical connection; can be directly connected, or indirectly connected through an intermediate medium, can be the internal communication of two elements or the interaction of two elements, unless otherwise specified Limited.
  • the specific meanings of the above terms in the present invention can be understood on a case-by-case basis.
  • the first feature "on” or “under” the second feature may be a direct contact of the first and second features, or the first and second features may be indirectly through an intermediate medium, unless otherwise explicitly stated and defined. contact.
  • the first feature "above”, “above” and “above” the second feature may be that the first feature is directly above or above the second feature, or merely that the first feature level is higher than the second feature.
  • the first feature “below”, “below” and “below” the second feature may be that the first feature is directly below or obliquely below the second feature, or merely that the first feature level is less than the second feature.
  • the invention provides a method of preparing nickel carbonyl powder from laterite nickel ore.
  • the method comprises: (1) mixing a laterite nickel ore, a high sulfur coal, and an additive to obtain a mixed pellet; and (2) performing a reduction smelting treatment on the mixed pellet to Obtaining a metallized pellet; (3) subjecting the metallized pellet to water quenching-grinding-magnetic separation treatment to obtain nickel iron powder and tailings respectively; (4) contacting the nickel iron powder with carbon monoxide, To obtain a gaseous mixture containing nickel carbonyl, carbonyl iron and carbon monoxide and iron powder; (5) purifying the gaseous mixture containing nickel carbonyl, iron carbonyl and carbon monoxide to obtain gaseous nickel carbonyl and first carbon monoxide, respectively; (6) The gaseous nickel carbonyl is subjected to decomposition treatment to obtain nickel carbonyl powder and second carbon monoxide, respectively.
  • the laterite nickel ore is used as a raw material for preparing nickel carbonyl powder.
  • the grade of nickel in the laterite nickel ore is low, the high purity nickel carbonyl powder can be prepared by the method of the present invention, thereby broadening the source of the raw material.
  • the production cost of nickel carbonyl powder is reduced, and by using high sulfur coal as a reducing agent, not only the nickel iron oxide in the laterite nickel ore can be effectively reduced, but also the high activity high sulfur nickel iron powder can be obtained, because the nickel iron powder is Sulfur in Catalytic activation during the carbonylation synthesis reaction, so that it can react with carbon monoxide to react to form a carbonyl compound, and the carbonyl compound has a high synthesis rate.
  • the present invention is not in the synthesis process of the carbonyl compound.
  • Nickel-iron powder, and the nickel-iron powder obtained by the grinding magnetic separation treatment has a fine particle size, so that the contact area with carbon monoxide can be significantly increased, thereby further increasing the synthesis rate of the carbonyl compound, and using inexpensive high-sulfur coal as a reducing agent. Not only can the production cost be effectively reduced, but also sulfur can be used as a beneficial component in the synthesis process of the carbonyl compound, and no gaseous sulfur-containing substance is generated during the synthesis of the carbonyl compound, and air pollution is not caused.
  • the method comprises:
  • the laterite nickel ore, the high sulfur coal, and the additive are mixed and pelletized, whereby a mixed pellet can be obtained.
  • the inventors have found that the use of laterite nickel ore as a raw material for preparing nickel carbonyl powder, although the grade of nickel in the laterite nickel ore is relatively low, the high purity nickel carbonyl powder can be prepared by the method of the invention (the nickel content is higher than 99%).
  • the iron content in the obtained iron powder is as high as 60 to 85 wt%, and at the same time, by using high sulfur coal as a reducing agent, not only the nickel in the laterite nickel ore can be effectively reduced.
  • Iron oxide, and high-activity high-sulfur nickel-iron powder can be obtained, since the sulfur in the nickel-iron powder is catalytically activated during the carbonylation synthesis reaction, so that it can react with carbon monoxide to react to form a carbonyl compound, and The synthesis rate of the carbonyl compound is relatively high.
  • the invention does not need to add a catalyst in the synthesis process of the carbonyl compound, thereby shortening the process flow, and the high sulfur coal resource is abundant, but because it can cause serious sulfur It is difficult to obtain effective use of environmental problems such as pollution and acid rain, and the present invention uses high sulfur coal as a reducing agent, not only In order to effectively reduce the production cost, and high-sulfur coal does not need to be treated by desulfurization technology, it can be used as a beneficial component in the synthesis of carbonyl compounds, and no gaseous sulfur-containing substances are produced during the synthesis of carbonyl compounds. It will cause air pollution.
  • the mixing ratio of laterite nickel ore, high-sulfur coal and additives is not particularly limited, and those skilled in the art can select according to actual needs.
  • laterite nickel ore, high The sulfur coal and the additive may be mixed at a mass ratio of 100: (5 to 25) (3 to 15).
  • the inventors have found that if the amount of high-sulfur coal added is too low, on the one hand, it affects the reduction effect of the metallized pellets, on the other hand, the low-sulfur content of the nickel-iron powder affects the activity of the nickel-iron powder, which is disadvantageous to the carbonyl group.
  • the synthesis reaction proceeds, and if the amount of high-sulfur coal added is too high, the technical specifications of the nickel-iron powder cannot be improved, and the high-sulfur coal resources are wasted and the production cost is increased.
  • the laterite nickel ore, the high-sulfur coal, and the additive are previously pulverized before the laterite nickel ore, the high-sulfur coal, and the additive are mixed.
  • the sulfur content in the high sulfur coal is not particularly limited, and those skilled in the art can select according to actual needs.
  • the sulfur content in the high sulfur coal can be high. Yu 3wt%.
  • the inventors have found that high-sulfur high-iron nickel iron powder can be prepared by using this type of high-sulfur coal, so that it can react with carbon monoxide to react to form a carbonyl compound, and the synthesis rate of the carbonyl compound is high, which is related to the prior art.
  • the present invention does not require the addition of a catalyst during the synthesis of the carbonyl compound, thereby shortening the process flow.
  • the specific type of the additive is not particularly limited, and those skilled in the art can select according to actual needs.
  • the additive may be selected from the group consisting of potassium salt, sodium salt and calcium. At least one of a salt, an alkali metal oxide, and an alkaline earth metal oxide. The inventors found that in the reduction process of laterite nickel ore, the additive can replace NiO from forsterite or fayalite to increase the activity of NiO, thereby significantly reducing the reduction smelting temperature and reducing the laterite nickel ore. The conditions are greatly improved and the reduction reaction is promoted.
  • the mixed pellets are subjected to a reduction smelting treatment, whereby metallized pellets can be obtained.
  • the conditions of the smelting process are not particularly limited, and those skilled in the art may select according to actual needs.
  • the reduction smelting process may be performed at 1000-1400 degrees Celsius for 20 minutes. The above is preferably carried out at 1200 to 1350 degrees Celsius for 30 to 60 minutes.
  • the inventors have found that under the smelting conditions, part of the iron oxide can be reduced to metallic iron, and at the same time, all the nickel oxide is reduced to metallic nickel, thereby obtaining a metallized pellet satisfying the process requirements, and neither affecting the nickel in the subsequent process. High recovery rate without causing energy waste.
  • the apparatus for reducing the smelting treatment is not particularly limited, and those skilled in the art may select according to actual needs.
  • the reduction smelting apparatus may be selected from a rotary hearth furnace. At least one of a rotary kiln and a tunnel kiln.
  • the above-mentioned obtained metallized pellets are subjected to water quenching-grinding-magnetic separation treatment, whereby nickel iron powder and tailings can be obtained.
  • the inventors have found that by subjecting the metallized pellets obtained in the reduction smelting process to water quenching treatment, the sulfur-containing substances can be uniformly dispersed in the metallized pellets, thereby obtaining a highly active nickel-iron powder having a loose structure, so that The nickel-iron powder forms a connected network structure inside, which facilitates the synthesis of the subsequent carbonyl compound, and the nickel-iron powder obtained by the grinding and magnetic separation treatment has a fine particle diameter, thereby significantly increasing the contact area with carbon monoxide, and further Compared with the prior art, the synthesis rate of the carbonyl compound is higher than that of the prior art, and the nickel-iron powder after the magnetic separation of the invention can meet the particle size requirement of the next nickel carbonyl synthesis reaction without secondary processing.
  • the water quen water quen
  • the nickel content in the nickel iron powder is not particularly limited, and those skilled in the art may select according to actual needs.
  • the nickel content in the nickel iron powder may be 5-15 wt. %.
  • the inventors have found that in order to obtain high-purity nickel carbonyl powder in the existing nickel carbonyl synthesis process, it is generally required to use a copper-nickel alloy or a high-purity nickel oxide containing more than 50% by weight of nickel, resulting in high raw material production cost and difficulty in procurement.
  • the invention has low threshold for nickel grade in nickel iron powder, and uses nickel iron powder with nickel content of only 5-15 wt% as synthetic raw material of nickel carbonyl powder. A high-purity nickel carbonyl powder is prepared, thereby significantly reducing the raw material cost while broadening the source of the nickel powder production raw material.
  • the sulfur content in the nickel iron powder is not particularly limited, and those skilled in the art may select according to actual needs.
  • the sulfur content in the nickel iron powder may be higher than 1 wt. % is preferably from 1 to 5% by weight. The inventors found that, within a certain range, the higher the sulfur content in the nickel-iron powder, the higher the activity of the nickel-iron powder, which is more favorable for the rapid progress of the nickel carbonyl synthesis reaction, and the nickel carbonyl synthesis rate is also higher, compared with the existing one.
  • the invention does not need to add an additional catalyst, thereby shortening the preparation process.
  • the sulphur content of the nickel-iron powder is too high, and on the one hand, the nickel-iron powder is caused.
  • the nickel-iron content is reduced at the same time, and on the other hand, the waste of high-sulfur coal resources is caused.
  • the particle size of the nickel iron powder is not particularly limited, and those skilled in the art can select according to actual needs.
  • the nickel iron powder has a particle size of less than 45 micrometers. More than 90% of the total mass. The inventors have found that the nickel-iron powder having a high particle size range has a high activity and a large contact area with carbon monoxide during the synthesis of nickel carbonyl, so that the synthesis rate of nickel carbonyl can be remarkably improved.
  • the nickel iron powder is brought into countercurrent contact with carbon monoxide, whereby a gaseous mixture containing nickel carbonyl, carbonyl iron and carbon monoxide and iron powder can be obtained.
  • the inventors have found that the use of highly active nickel iron powder in direct contact with carbon monoxide can react to form a carbonyl compound, and the synthesis rate of the carbonyl compound is relatively high.
  • the present invention does not require the addition of a catalyst during the synthesis of the carbonyl compound. , thus shortening the process flow.
  • the reaction conditions of the nickel iron powder and the carbon monoxide are not particularly limited, and those skilled in the art can select according to actual needs.
  • the nickel iron powder can be contacted with carbon monoxide at 110 ⁇ . It is carried out at 230 ° C and 2 to 10 MPa for 30 to 42 hours. Thereby, the synthesis rate of the carbonyl compound can be remarkably improved.
  • a gaseous mixture containing nickel carbonyl, iron carbonyl and carbon monoxide is subjected to purification treatment, whereby gaseous nickel carbonyl and first carbon monoxide can be obtained, respectively.
  • purification treatment whereby gaseous nickel carbonyl and first carbon monoxide can be obtained, respectively.
  • a gaseous mixture of nickel carbonyl, carbonyl iron and carbon monoxide is first condensed, and the nickel carbonyl and the carbonyl iron in the gaseous mixture are condensed into a liquid, and the carbon monoxide therein is present in the form of a gas, and then the resulting The liquid mixture containing nickel carbonyl and iron carbonyl is subjected to rectification treatment, whereby high purity gaseous nickel carbonyl can be isolated.
  • the specific operating conditions of the condensation and rectification employed may be selected by those skilled in the art according to actual needs.
  • the gaseous nickel carbonyl is subjected to decomposition treatment, whereby nickel powder and second carbon monoxide can be obtained, respectively.
  • the nickel carbonyl is unstable and can be rapidly decomposed into nickel and carbon monoxide when heated, thereby obtaining High purity nickel carbonyl powder. It should be noted that those skilled in the art can select the conditions of the decomposition process according to actual needs.
  • the method for preparing nickel carbonyl powder by using laterite nickel ore uses laterite nickel ore as a raw material for preparing nickel carbonyl powder. Although the grade of nickel in the laterite nickel ore is low, the method of the present invention can still be prepared high. Purity of nickel carbonyl powder, which can reduce the production cost of nickel carbonyl powder while broadening the source of raw materials, and at the same time, by using high sulfur coal as a reducing agent, not only can nickel iron oxide in the laterite nickel ore be effectively reduced, but also high activity can be obtained.
  • the high-sulfur nickel-iron powder because the sulfur in the nickel-iron powder plays a catalytic activation during the carbonylation synthesis reaction, so that it can react with carbon monoxide to react to form a carbonyl compound, and the carbonyl compound has a high synthesis rate.
  • the invention does not need to add a catalyst in the synthesis process of the carbonyl compound, thereby shortening the process flow, and secondly, by subjecting the metallized pellet obtained in the smelting process to water quenching treatment, the sulfur-containing substance can be uniformly dispersed in the process.
  • the obtained ferronickel powder has a fine particle diameter, thereby significantly increasing the contact area with carbon monoxide, thereby further increasing the synthesis rate of the carbonyl compound, and using inexpensive high-sulfur coal as a reducing agent, not only can effectively reduce the production cost, but also
  • the sulfur is applied as a beneficial component to the synthesis process of the carbonyl compound, and no gaseous sulfur-containing substance is generated during the synthesis of the carbonyl compound, and no air pollution is caused.
  • a method for preparing nickel carbonyl powder using laterite nickel ore according to an embodiment of the present invention further includes:
  • the first carbon monoxide obtained by purifying and separating S500 is returned to S400 to be in contact with the nickel iron powder, so that the carbon monoxide cycle utilization ratio can be remarkably improved.
  • a method for preparing nickel carbonyl powder using laterite nickel ore according to an embodiment of the present invention further includes:
  • the second carbon monoxide obtained by decomposing S600 is returned to S400 to be in contact with the nickel iron powder, so that the carbon monoxide cycle utilization ratio can be further improved.
  • the invention provides a system for preparing nickel carbonyl powder from laterite nickel ore.
  • the system comprises: a mixing pelletizing device having a laterite nickel ore inlet, a high sulfur coal inlet, an additive inlet, and a mixing pellet outlet, and is suitable for laterite nickel ore, high The sulfur coal and the additive are mixed and pelletized to obtain a mixed pellet; a reduction smelting apparatus having a mixed pellet inlet and a metallized pellet outlet, the mixed pellet inlet being connected to the mixed pellet outlet And suitable for performing the reduction smelting treatment of the mixed pellets to obtain a metallized pellet; a water quenching-grinding-magnetic separation device having a metallized pellet inlet, a nickel iron powder outlet and a tailings outlet, the metallized pellet inlet being connected to the metallized pellet outlet, and adapted to subject the metallized pellet to water quenching-grinding-magnetic separation treatment to obtain respectively Nickel iron powder
  • the laterite nickel ore is used as a raw material for preparing nickel carbonyl powder.
  • the grade of nickel in the laterite nickel ore is low, the high purity nickel carbonyl powder can be prepared by using the system of the present invention, thereby broadening the raw material source.
  • the production cost of nickel carbonyl powder is reduced, and by using high sulfur coal as a reducing agent, not only the nickel iron oxide in the laterite nickel ore can be effectively reduced, but also the high activity high sulfur nickel iron powder can be obtained, because the nickel iron powder is The sulfur is catalytically activated during the carbonylation synthesis reaction, so that it can react with carbon monoxide to react to form a carbonyl compound, and the carbonyl compound has a high synthesis rate.
  • the present invention is synthesized in a carbonyl compound.
  • the catalyst is not required to be added, thereby shortening the process flow, and secondly, by subjecting the metallized pellets obtained in the smelting process to water quenching treatment, the sulfur-containing substance can be uniformly dispersed in the metallized pellets, thereby obtaining a loose structure.
  • High-activity nickel-iron powder, and the nickel-iron powder obtained by the grinding magnetic separation treatment has a fine particle size, thereby In order to significantly increase the contact area with carbon monoxide, thereby further increasing the synthesis rate of carbonyl compounds, and using inexpensive high-sulfur coal as a reducing agent, not only can the production cost be effectively reduced, but also sulfur can be used as a beneficial component to the synthesis of carbonyl compounds. During the process, no gaseous sulfur compounds are produced during the synthesis of the carbonyl compound, and no air pollution is caused.
  • the system comprises:
  • hybrid pelletizing device 100 has a laterite nickel ore inlet 101, a high sulfur coal inlet 102, an additive inlet 103, and a mixing pellet outlet 104, and is suitable for laterite nickel ore, high
  • the sulfur coal and the additive are mixed and pelletized, so that a mixed pellet can be obtained.
  • the inventors have found that the use of laterite nickel ore as a raw material for preparing nickel carbonyl powder, although the grade of nickel in the laterite nickel ore is relatively low, the high purity nickel carbonyl powder can be prepared by the method of the invention (the nickel content is higher than 99%).
  • the iron content in the obtained iron powder is as high as 60 to 85 wt%, and at the same time, by using high sulfur coal as a reducing agent, not only the nickel in the laterite nickel ore can be effectively reduced.
  • Iron oxide, and high-activity high-sulfur nickel-iron powder can be obtained, since the sulfur in the nickel-iron powder is catalytically activated during the carbonylation synthesis reaction, so that it can react with carbon monoxide to react to form a carbonyl compound, and The synthesis rate of the carbonyl compound is relatively high.
  • the invention does not need to add a catalyst in the synthesis process of the carbonyl compound, thereby shortening the process flow, and the high sulfur coal resource is abundant, but because it can cause serious sulfur It is difficult to obtain effective use of environmental problems such as pollution and acid rain, and the present invention uses high sulfur coal as a reducing agent, It can only effectively reduce the production cost, and high-sulfur coal does not need to be treated by desulfurization technology. Instead, sulfur can be used as a beneficial component in the synthesis of carbonyl compounds, and no gaseous sulfur-containing substances are produced during the synthesis of carbonyl compounds. Will not cause air pollution.
  • the mixing ratio of laterite nickel ore, high-sulfur coal and additives is not particularly limited, and those skilled in the art can select according to actual needs.
  • laterite nickel ore, high The sulfur coal and the additive may be mixed at a mass ratio of 100: (5 to 25) (3 to 15).
  • the inventors have found that if the amount of high-sulfur coal added is too low, on the one hand, it affects the reduction effect of the metallized pellets, on the other hand, the low-sulfur content of the nickel-iron powder affects the activity of the nickel-iron powder, which is disadvantageous to the carbonyl group.
  • the synthesis reaction proceeds, and if the amount of high-sulfur coal added is too high, the technical specifications of the nickel-iron powder cannot be improved, and the high-sulfur coal resources are wasted and the production cost is increased.
  • the laterite nickel ore, the high-sulfur coal, and the additive are previously pulverized before the laterite nickel ore, the high-sulfur coal, and the additive are mixed.
  • the sulfur content in the high sulfur coal is not particularly limited, and those skilled in the art can select according to actual needs.
  • the sulfur content in the high sulfur coal can be high. At 3wt%.
  • the inventors have found that high-sulfur high-iron nickel iron powder can be prepared by using this type of high-sulfur coal, so that it can react with carbon monoxide to react to form a carbonyl compound, and the synthesis rate of the carbonyl compound is high, which is related to the prior art.
  • the present invention does not require the addition of a catalyst during the synthesis of the carbonyl compound, thereby shortening the process flow.
  • the specific type of the additive is not particularly limited, and those skilled in the art can select according to actual needs.
  • the additive may be selected from the group consisting of potassium salt, sodium salt and calcium. At least one of a salt, an alkali metal oxide, and an alkaline earth metal oxide. The inventors found that in the reduction process of laterite nickel ore, the additive can replace NiO from forsterite or fayalite to increase the activity of NiO, thereby significantly reducing the reduction smelting temperature and reducing the laterite nickel ore. The conditions are greatly improved and the reduction reaction is promoted.
  • the reduction smelting apparatus 200 has a mixing pellet inlet 201 and a metallized pellet outlet 202, the mixing pellet inlet 201 and the mixing pellet outlet 104 are connected, and is suitable for mixing pellets A reduction smelting process is performed to obtain a metallized pellet.
  • the conditions of the smelting process are not particularly limited, and those skilled in the art may select according to actual needs.
  • the reduction smelting process may be performed at 1000-1400 degrees Celsius for 20 minutes. The above is preferably carried out at 1200 to 1350 degrees Celsius for 30 to 60 minutes.
  • the inventors have found that under the smelting conditions, part of the iron oxide can be reduced to metallic iron, and at the same time, all the nickel oxide is reduced to metallic nickel, thereby obtaining a metallized pellet satisfying the process requirements, and neither affecting the nickel in the subsequent process. High recovery rate without causing energy waste.
  • the reduction smelting apparatus is not particularly limited, and those skilled in the art may select according to actual needs.
  • the reduction smelting apparatus may be selected from a rotary hearth furnace and a rotary kiln. And at least one of the tunnel kiln.
  • the water quenching-grinding-magnetic separation device 300 has metallization a pellet inlet 301, a nickel iron powder outlet 302 and a tailings outlet 303, the metallized pellet inlet 301 is connected to the metallized pellet outlet 202, and is suitable for water quenching-grinding-magnetic separation of the obtained metallized pellets described above. Treatment, so that nickel iron powder and tailings can be obtained.
  • the inventors have found that by subjecting the metallized pellets obtained in the reduction smelting process to water quenching treatment, the sulfur-containing substances can be uniformly dispersed in the metallized pellets, thereby obtaining a highly active nickel-iron powder having a loose structure, so that The nickel-iron powder forms a connected network structure inside, which facilitates the synthesis of the subsequent carbonyl compound, and the nickel-iron powder obtained by the grinding and magnetic separation treatment has a fine particle diameter, thereby significantly increasing the contact area with carbon monoxide, and further Compared with the prior art, the synthesis rate of the carbonyl compound is higher than that of the prior art, and the nickel-iron powder after the magnetic separation of the invention can meet the particle size requirement of the next nickel carbonyl synthesis reaction without secondary processing.
  • the water quenching-grinding-magnetic separation device may be a combination device of a water quenching device, a grinding device, and a magnetic separation device.
  • the nickel content in the nickel iron powder is not particularly limited, and those skilled in the art may select according to actual needs.
  • the nickel content in the nickel iron powder may be 5-15 wt. %.
  • the inventors have found that in order to obtain high-purity nickel carbonyl powder in the existing nickel carbonyl synthesis process, it is generally required to use a copper-nickel alloy or a high-purity nickel oxide containing more than 50% by weight of nickel, resulting in high raw material production cost and difficulty in procurement.
  • the invention has low threshold for nickel grade in nickel iron powder, and nickel iron powder with nickel content of only 5-15 wt% is used as a synthetic raw material of carbonyl nickel powder, and high purity nickel carbonyl powder can be prepared, thereby broadening nickel carbonyl.
  • the source of raw materials for powder production also significantly reduces the cost of raw materials.
  • the sulfur content in the nickel iron powder is not particularly limited, and those skilled in the art may select according to actual needs.
  • the sulfur content in the nickel iron powder may be higher than 1 wt. % is preferably from 1 to 5% by weight. The inventors found that, within a certain range, the higher the sulfur content in the nickel-iron powder, the higher the activity of the nickel-iron powder, which is more favorable for the rapid progress of the nickel carbonyl synthesis reaction, and the nickel carbonyl synthesis rate is also higher, compared with the existing one.
  • the invention does not need to add an additional catalyst, thereby shortening the preparation process.
  • the sulphur content of the nickel-iron powder is too high, and on the one hand, the nickel-iron powder is caused.
  • the nickel-iron content is reduced at the same time, and on the other hand, the waste of high-sulfur coal resources is caused.
  • the particle size of the nickel iron powder is not particularly limited, and those skilled in the art can select according to actual needs.
  • the nickel iron powder has a particle size of less than 45 micrometers. More than 90% of the total mass. The inventors have found that the nickel-iron powder having a high particle size range has a high activity and a large contact area with carbon monoxide during the synthesis of nickel carbonyl, so that the synthesis rate of nickel carbonyl can be remarkably improved.
  • the oxo synthesis unit 400 has a carbon monoxide inlet 401, a nickel iron powder inlet 402, a gaseous mixture outlet 403 and an iron powder outlet 404, the nickel iron powder inlet 402 and the nickel iron powder outlet 302 being connected, It is also suitable for countercurrent contact of nickel iron powder with carbon monoxide, so that a gaseous mixture containing nickel carbonyl, iron carbonyl and carbon monoxide and iron powder can be obtained.
  • the inventors have found that the use of highly active nickel iron powder in direct contact with carbon monoxide can react to form a carbonyl compound, and the synthesis rate of the carbonyl compound is relatively high. Compared with the prior art, the present invention does not require the addition of a catalyst during the synthesis of the carbonyl compound. , thus shortening the process flow.
  • the reaction conditions of the nickel iron powder and the carbon monoxide are not particularly limited, and those skilled in the art can select according to actual needs.
  • the nickel iron powder can be contacted with carbon monoxide at 110 ⁇ . It is carried out at 230 ° C and 2 to 10 MPa for 30 to 42 hours. Thereby, the synthesis rate of the carbonyl compound can be remarkably improved.
  • purification apparatus 500 has a gaseous mixture inlet 501, a gaseous nickel carbonyl outlet 502, and a first carbon monoxide outlet 503, and a gaseous mixture inlet 501 is coupled to the gaseous mixture outlet 403 and is adapted to contain nickel carbonyl A gaseous mixture of carbonyl iron and carbon monoxide is purified to obtain gaseous nickel carbonyl and first carbon monoxide, respectively. Thereby, the purity of the subsequently obtained nickel carbonyl powder can be remarkably improved.
  • a gaseous mixture of nickel carbonyl, carbonyl iron and carbon monoxide is first condensed, and the nickel carbonyl and the carbonyl iron in the gaseous mixture are condensed into a liquid, and the carbon monoxide therein is present in the form of a gas, and then the resulting The liquid mixture containing nickel carbonyl and iron carbonyl is subjected to rectification treatment, whereby high purity gaseous nickel carbonyl can be isolated.
  • the specific operating conditions of the condensation and rectification employed may be selected by those skilled in the art according to actual needs.
  • the decomposition device 600 has a gaseous nickel carbonyl inlet 601, a nickel carbonyl powder outlet 602 and a second carbon monoxide outlet 603, the gaseous nickel carbonyl inlet 601 and the gaseous nickel carbonyl outlet 502 are connected, and is suitable for The gaseous nickel carbonyl is decomposed to obtain nickel carbonyl powder and second carbon monoxide, respectively.
  • the nickel carbonyl is unstable and can be rapidly decomposed into nickel and carbon monoxide upon heating, so that high-purity nickel carbonyl powder can be obtained. It should be noted that those skilled in the art can select the conditions of the decomposition process according to actual needs.
  • the system for preparing nickel carbonyl powder by using laterite nickel ore uses laterite nickel ore as a raw material for preparing nickel carbonyl powder. Although the grade of nickel in the laterite nickel ore is low, the system of the present invention can still be prepared high. Purity of nickel carbonyl powder, which can reduce the production cost of nickel carbonyl powder while broadening the source of raw materials, and at the same time, by using high sulfur coal as a reducing agent, not only can nickel iron oxide in the laterite nickel ore be effectively reduced, but also high activity can be obtained.
  • the high-sulfur nickel-iron powder because the sulfur in the nickel-iron powder plays a catalytic activation during the carbonylation synthesis reaction, so that it can react with carbon monoxide to react to form a carbonyl compound, and the carbonyl compound has a high synthesis rate.
  • the invention does not need to add a catalyst in the synthesis process of the carbonyl compound, thereby shortening the process flow, and secondly, by subjecting the metallized pellet obtained in the smelting process to water quenching treatment, the sulfur-containing substance can be uniformly dispersed in the process.
  • the obtained ferronickel powder has a fine particle diameter, thereby significantly increasing the contact area with carbon monoxide, thereby further increasing the synthesis rate of the carbonyl compound, and using inexpensive high-sulfur coal as a reducing agent, not only can effectively reduce the production cost, but also
  • the sulfur is applied as a beneficial component to the synthesis process of the carbonyl compound, and no gaseous sulfur-containing substance is generated during the synthesis of the carbonyl compound, and no air pollution is caused.
  • a first carbon monoxide outlet 503 is connected to a carbon monoxide inlet 401, and The first carbon monoxide suitable for separating the purification device 500 is returned to the oxo synthesis unit 400 in contact with the nickel iron powder, so that the carbon monoxide cycle utilization ratio can be remarkably improved.
  • the second carbon monoxide outlet 603 is connected to the carbon monoxide inlet 401, and is adapted to return the second carbon monoxide decomposed by the decomposition device 600 to the oxo synthesis device 400 for contact with the nickel iron powder, thereby further improving Carbon monoxide cycle utilization.
  • the laterite nickel ore with a nickel content of 1.56wt% is blended with high-sulfur coal with a sulfur content of 4% and mixed with an industrial alkali to form a ball and dried.
  • the laterite nickel ore, high-sulfur coal and industrial alkali are mass-produced according to the mass ratio. 100:17:5% mixing, the dried mixed pellets were placed in a rotary hearth furnace for smelting, the smelting conditions were 1300 ° C, time 35 min, and the reduced metallized pellets were treated by a water quenching-grinding-magnetic separation device.
  • a nickel iron powder having a nickel content of 6.5 wt%, an iron content of 68.6 wt%, and an S content of 2.0 wt% is obtained.
  • the average particle size of the product is 25 ⁇ m.
  • the nickel iron powder is fed into the oxo unit and reacted with CO in a countercurrent contact to form a carbonyl group.
  • the carbonyl compound is sent to a rectification column for rectification to obtain a high-purity gaseous nickel carbonyl.
  • the gaseous nickel carbonyl is sent to a decomposition device for decomposition to obtain a nickel carbonyl powder having a nickel content of 99.5 wt%, and iron selected by an iron powder re-election device.
  • the iron content in the powder is 73wt .
  • the laterite nickel ore with a nickel content of 1.75wt% is blended with high-sulfur coal and limestone with a sulfur content of 7%, and then ball is prepared and dried.
  • the laterite nickel ore, high-sulfur coal and limestone are in a mass ratio of 100:
  • the mixture was mixed at 12:10, and the dried pellets were placed in a rotary hearth furnace for smelting.
  • the smelting conditions were 1280 ° C for 45 min.
  • the reduced metallized pellets were treated with a water quenching-grinding-magnetic separation device to obtain nickel content.
  • the nickel iron powder is sent into the oxo unit and reacted with CO in a countercurrent contact to form a carbonyl containing reaction to form nickel carbonyl and carbonyl.
  • the gaseous mixture of iron, the carbonylation conditions are: pressure 3MPa, temperature 130 ° C, time 42h, CO gas concentration 90%, synthesis rate 95%
  • the gaseous mixture containing nickel carbonyl and carbonyl iron is sent to the condenser to condense into a liquid carbonyl compound, Then, it is sent to the rectification column for rectification to obtain high-purity gaseous nickel carbonyl.
  • the gaseous nickel carbonyl is sent to a decomposition device for decomposition to obtain nickel carbonyl powder having a nickel content of 99.5 wt%, and iron content in the iron powder selected by the iron powder re-election device. 77% by weight .

Abstract

Provided is a method and system for preparing a carbonyl nickel powder using laterite-nickel ore. The method comprises: (1) mixing and pelletizing laterite-nickel ore, high-sulphur coal, and additives to obtain pellets; (2) reducing the pellets; (3) subjecting the reduced metallized pellets to water quenching-ore grinding-magnetic separation treatments to obtain a nickel iron powder and tailings; and (4) bringing the nickel iron powder into contact with carbon monoxide for reaction, and then performing purification and decomposition treatments so as to obtain the carbonyl nickel powder, with the carbon monoxide being recycled, wherein the use of the high-sulphur coal results in a highly active nickel iron powder, it is not necessary to add any catalyst in the process of producing the carbonyl nickel powder, and the synthesis efficiency is high.

Description

利用红土镍矿制备羰基镍粉的方法和***Method and system for preparing nickel carbonyl powder from laterite nickel ore 技术领域Technical field
本发明属于冶金技术领域，具体而言，本发明涉及一种利用红土镍矿制备羰基镍粉的方法和***。The invention belongs to the technical field of metallurgy, in particular, the invention relates to a method and a system for preparing nickel carbonyl powder by using laterite nickel ore.
背景技术Background technique
随着硫化镍矿的枯竭，红土镍矿的开发日益受到重视。当前工业生产中，火法冶炼红土镍矿最常用的方法是RKEF法，得到的产品为镍铁合金，镍铁合金可以作为炼钢原料使用。该冶炼方法能耗大，在当前的市场镍价条件下，镍铁厂处于亏损停产状态。而湿法冶炼红土镍矿则涉及废液排放等环境污染问题。因此，有必要对红土镍矿处理工艺进行创新性研究，开发一种高效利用红土镍矿的新工艺。With the depletion of nickel sulphide ore, the development of laterite nickel ore has received increasing attention. In the current industrial production, the most common method for smelting laterite nickel ore by fire method is the RKEF method. The obtained product is a nickel-iron alloy, and the nickel-iron alloy can be used as a steelmaking raw material. The smelting method consumes a large amount of energy. Under the current market nickel price conditions, the ferronickel plant is in a state of loss and production. The wet smelting of laterite nickel ore involves environmental pollution problems such as waste liquid discharge. Therefore, it is necessary to carry out innovative research on the treatment process of laterite nickel ore and develop a new process for efficient use of laterite nickel ore.
羰基法精炼镍工艺是最先进的镍提纯工艺，是C.Langer和L.Mond于1889年发明的，原理是镍在一定的温度、压力条件下直接与CO在形成的配位化合物四羰基镍Ni(CO)4，该羰基金属化合物在常压下不稳定，加热时迅速分解成Ni和CO，该方法具有工艺简单、能耗低、镍提取率高等优点。The carbonyl refining process is the most advanced nickel purification process. It was invented by C. Langer and L. Mond in 1889. The principle is that nickel is a complex compound of nickel tetracarbonyl formed directly with CO under certain temperature and pressure conditions. Ni(CO) 4 , the carbonyl metal compound is unstable under normal pressure and rapidly decomposes into Ni and CO upon heating. The method has the advantages of simple process, low energy consumption and high nickel extraction rate.
专利CN201310078977公开了一种生产羰基镍粉的方法，该方法以镍含量大于39％的氢氧化镍为原料，经焙烧后生产镍的氧化物，氧化物在氢气还原炉内还原成单质镍，单质镍与CO发生羰化合成反应，再输送至羰基分解器生成羰基镍产品。然而该方法使用的原料氢氧化镍是工业加工产品，并不直接赋存于自然界中，并且该方法的工艺流程长，生产成本高，同时该方法对原料的铁含量有严格限制，铁含量必须小于0.3％，否则影响镍粉的纯度。Patent CN201310078977 discloses a method for producing nickel carbonyl powder by using nickel hydroxide having a nickel content of more than 39% as a raw material, and calcining to produce nickel oxide, and the oxide is reduced to elemental nickel in a hydrogen reduction furnace. Nickel and CO undergo a carbonylation synthesis reaction, which is then sent to a carbonyl decomposer to form a nickel carbonyl product. However, the raw material nickel hydroxide used in the method is an industrial processed product, and does not directly exist in nature, and the method has a long process flow and high production cost, and the method has strict limits on the iron content of the raw material, and the iron content must be Less than 0.3%, otherwise it affects the purity of nickel powder.
因此，现有的制备镍粉的技术有待进一步改进。Therefore, the existing technology for preparing nickel powder needs to be further improved.
发明内容Summary of the invention
本发明旨在至少在一定程度上解决相关技术中的技术问题之一。为此，本发明的一个目的在于提出一种利用红土镍矿制备羰基镍粉的方法和***，该方法可以有效利用价格低廉的红土镍矿制备得到高纯度的羰基镍粉，并且工艺流程简单、环境友好。The present invention aims to solve at least one of the technical problems in the related art to some extent. To this end, an object of the present invention is to provide a method and system for preparing nickel carbonyl powder by using laterite nickel ore, which can effectively obtain high-purity nickel carbonyl powder by using low-cost laterite nickel ore, and has a simple process. Environmentally friendly.
在本发明的一个方面，本发明提出了一种利用红土镍矿制备羰基镍粉的方法，根据本发明实施例的，该方法包括：In one aspect of the invention, the invention provides a method of preparing nickel carbonyl powder using laterite nickel ore, according to an embodiment of the invention, the method comprising:
(1)将红土镍矿、高硫煤和添加剂进行混合造球，以便得到混合球团；(1) mixing red earth nickel ore, high sulfur coal and additives to obtain a mixed pellet;
(2)将所述混合球团进行还原冶炼处理，以便得到金属化球团；(2) subjecting the mixed pellets to reduction smelting treatment to obtain metallized pellets;
(3)将所述金属化球团进行水淬-磨矿-磁选处理，以便分别得到镍铁粉和尾矿； (3) subjecting the metallized pellets to water quenching-grinding-magnetic separation treatment to obtain nickel iron powder and tailings, respectively;
(4)将所述镍铁粉与一氧化碳接触，以便得到含有羰基镍、羰基铁和一氧化碳的气态混合物以及铁粉；(4) contacting the nickel iron powder with carbon monoxide to obtain a gaseous mixture containing nickel carbonyl, iron carbonyl and carbon monoxide, and iron powder;
(5)将所述含有羰基镍、羰基铁和一氧化碳的气态混合物进行提纯处理，以便分别得到气态羰基镍和第一一氧化碳；以及(5) purifying the gaseous mixture containing nickel carbonyl, carbonyl iron and carbon monoxide to obtain gaseous nickel carbonyl and first carbon monoxide, respectively;
(6)将所述气态羰基镍进行分解处理，以便分别得到羰基镍粉和第二一氧化碳。(6) The gaseous nickel carbonyl is subjected to decomposition treatment to obtain nickel carbonyl powder and second carbon monoxide, respectively.
由此，根据本发明实施例的利用红土镍矿制备羰基镍粉的方法可以有效利用价格低廉的红土镍矿制备得到高纯度的羰基镍粉，并且工艺流程简单、环境友好。Therefore, the method for preparing nickel carbonyl powder by using laterite nickel ore according to the embodiment of the invention can effectively prepare high-purity nickel carbonyl powder by using low-cost laterite nickel ore, and the process is simple and environmentally friendly.
另外，根据本发明上述实施例的利用红土镍矿制备羰基镍粉的方法还可以具有如下附加的技术特征：In addition, the method for preparing nickel carbonyl powder using laterite nickel ore according to the above embodiment of the present invention may further have the following additional technical features:
在本发明的一些实施例中，所述利用红土镍矿制备羰基镍粉的方法进一步包括：(7)将所述第一一氧化碳返回步骤(4)与所述镍铁粉接触。由此，可以显著提高一氧化碳循环利用率。In some embodiments of the present invention, the method for preparing nickel carbonyl powder using laterite nickel ore further comprises: (7) contacting the first carbon monoxide returning step (4) with the nickel iron powder. Thereby, the carbon monoxide cycle utilization ratio can be remarkably improved.
在本发明的一些实施例中，所述利用红土镍矿制备羰基镍粉的方法进一步包括：(8)将所述第二一氧化碳返回至步骤(4)与所述镍铁粉接触。由此，可以进一步提高一氧化碳循环利用率。In some embodiments of the present invention, the method of preparing nickel carbonyl powder using laterite nickel ore further comprises: (8) returning the second carbon monoxide to step (4) to contact the nickel iron powder. Thereby, the carbon monoxide cycle utilization ratio can be further improved.
在本发明的一些实施例中，在步骤(1)中，所述高硫煤中硫含量高于3wt％。由此，不仅可以降低还原剂成本，而且可以显著简化后续羰基合成工艺流程。In some embodiments of the invention, in step (1), the sulfur content of the high sulfur coal is greater than 3 wt%. Thereby, not only the cost of the reducing agent can be reduced, but also the subsequent oxo process flow can be significantly simplified.
在本发明的一些实施例中，在步骤(1)中，所述添加剂为选自钾盐、钠盐、钙盐、碱金属氧化物和碱土金属氧化物中的至少一种。In some embodiments of the present invention, in the step (1), the additive is at least one selected from the group consisting of a potassium salt, a sodium salt, a calcium salt, an alkali metal oxide, and an alkaline earth metal oxide.
在本发明的另一个方面，本发明提出了一种利用红土镍矿制备羰基镍粉的***，根据本发明的实施例，该***包括：In another aspect of the invention, the invention provides a system for preparing nickel carbonyl powder from laterite nickel ore, according to an embodiment of the invention, the system comprising:
混合造球装置，所述混合造球装置具有红土镍矿入口、高硫煤入口、添加剂入口和混合球团出口，且适于将红土镍矿、高硫煤和添加剂进行混合造球，以便得到混合球团；a mixing pelletizing device having a laterite nickel ore inlet, a high sulfur coal inlet, an additive inlet, and a mixing pellet outlet, and is suitable for mixing a laterite nickel ore, a high sulfur coal, and an additive to obtain Mixed pellets;
还原冶炼装置，所述还原冶炼装置具有混合球团入口和金属化球团出口，所述混合球团入口和所述混合球团出口相连，且适于将所述混合球团进行还原冶炼处理，以便得到金属化球团；a reduction smelting apparatus having a mixing pellet inlet and a metallized pellet outlet, the mixing pellet inlet being connected to the mixing pellet outlet, and adapted to perform the reduction smelting treatment of the mixing pellet In order to obtain metallized pellets;
水淬-磨矿-磁选装置，所述水淬-磨矿-磁选装置具有金属化球团入口、镍铁粉出口和尾矿出口，所述金属化球团入口与所述金属化球团出口相连，且适于将所述金属化球团进行水淬-磨矿-磁选处理，以便分别得到镍铁粉和尾矿；a water quenching-grinding-magnetic separation device having a metallized pellet inlet, a nickel iron powder outlet, and a tailings outlet, the metallized pellet inlet and the metallized sphere The group outlet is connected, and is suitable for performing water quenching-grinding-magnetic separation treatment on the metallized pellets to obtain nickel iron powder and tailings respectively;
羰基合成装置，所述羰基合成装置具有一氧化碳入口、镍铁粉入口、气态混合物出口和铁粉出口，所述镍铁粉入口和所述镍铁粉出口相连，且适于将所述镍铁粉与一氧化碳接触，以便得到含有羰基镍、羰基铁和一氧化碳的气态混合物以及铁粉； An oxo synthesis apparatus having a carbon monoxide inlet, a nickel iron powder inlet, a gaseous mixture outlet, and an iron powder outlet, the nickel iron powder inlet being connected to the nickel iron powder outlet, and adapted to be the nickel iron powder Contacting with carbon monoxide to obtain a gaseous mixture containing nickel carbonyl, iron carbonyl and carbon monoxide, and iron powder;
提纯装置，所述提纯装置具有气态混合物入口、气态羰基镍出口和第一一氧化碳出口，所述气态混合物入口与所述气态混合物出口相连，且适于将所述含有羰基镍、羰基铁和一氧化碳的气态混合物进行提纯处理，以便分别得到气态羰基镍和第一一氧化碳；以及a purification apparatus having a gaseous mixture inlet, a gaseous nickel carbonyl outlet, and a first carbon monoxide outlet, the gaseous mixture inlet being connected to the gaseous mixture outlet and adapted to contain the nickel carbonyl, carbonyl iron and carbon monoxide The gaseous mixture is subjected to a purification treatment to obtain gaseous nickel carbonyl and first carbon monoxide, respectively;
分解装置，所述分解装置具有气态羰基镍入口、羰基镍粉出口和第二一氧化碳出口，所述气态羰基镍入口和所述气态羰基镍出口相连，且适于将所述气态羰基镍进行分解处理，以便分别得到羰基镍粉和第二一氧化碳。a decomposition apparatus having a gaseous nickel carbonyl inlet, a nickel carbonyl powder outlet, and a second carbon monoxide outlet, the gaseous nickel carbonyl inlet being connected to the gaseous nickel carbonyl outlet, and adapted to decompose the gaseous nickel carbonyl In order to obtain nickel carbonyl powder and second carbon monoxide, respectively.
由此，根据本发明实施例的利用红土镍矿制备羰基镍粉的***可以有效利用价格低廉的红土镍矿制备得到高纯度的羰基镍粉，并且工艺流程简单、环境友好。Therefore, the system for preparing nickel carbonyl powder by using laterite nickel ore according to the embodiment of the present invention can effectively obtain high-purity nickel carbonyl powder by using low-cost laterite nickel ore, and the process is simple and environmentally friendly.
另外，根据本发明上述实施例的利用红土镍矿制备羰基镍粉的***还可以具有如下附加的技术特征：Further, the system for preparing nickel carbonyl powder using laterite nickel ore according to the above embodiment of the present invention may further have the following additional technical features:
在本发明的一些实施例中，所述还原冶炼装置为选自转底炉、回转窑和隧道窑中的至少一种。由此，可以将氧化镍全部还原成金属镍，同时将部分铁氧化物还原成金属铁。In some embodiments of the invention, the reduction smelting apparatus is at least one selected from the group consisting of a rotary hearth furnace, a rotary kiln, and a tunnel kiln. Thereby, all of the nickel oxide can be reduced to metallic nickel while a part of the iron oxide is reduced to metallic iron.
在本发明的一些实施例中，所述第一一氧化碳出口与所述一氧化碳入口相连，且适于将所述第一一氧化碳返回所述羰基合成装置与所述镍铁粉接触。由此，可以显著提高一氧化碳循环利用率。In some embodiments of the invention, the first carbon monoxide outlet is connected to the carbon monoxide inlet and is adapted to return the first carbon monoxide to the oxo synthesis unit in contact with the nickel iron powder. Thereby, the carbon monoxide cycle utilization ratio can be remarkably improved.
在本发明的一些实施例中，所述第二一氧化碳出口与所述一氧化碳入口相连，且适于将所述第二一氧化碳返回所述羰基合成装置与所述镍铁粉接触。由此，可以进一步提高一氧化碳循环利用率。In some embodiments of the invention, the second carbon monoxide outlet is connected to the carbon monoxide inlet and is adapted to return the second carbon monoxide to the oxo unit in contact with the nickel iron powder. Thereby, the carbon monoxide cycle utilization ratio can be further improved.
本发明的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本发明的实践了解到。The additional aspects and advantages of the invention will be set forth in part in the description which follows.
附图说明DRAWINGS
本发明的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：The above and/or additional aspects and advantages of the present invention will become apparent and readily understood from
图1是根据本发明一个实施例的利用红土镍矿制备羰基镍粉的方法流程示意图；1 is a schematic flow chart of a method for preparing nickel carbonyl powder by using laterite nickel ore according to an embodiment of the present invention;
图2是根据本发明再一个实施例的利用红土镍矿制备羰基镍粉的方法流程示意图；2 is a schematic flow chart of a method for preparing nickel carbonyl powder by using laterite nickel ore according to still another embodiment of the present invention;
图3是根据本发明又一个实施例的利用红土镍矿制备羰基镍粉的方法流程示意图；3 is a schematic flow chart of a method for preparing nickel carbonyl powder by using laterite nickel ore according to still another embodiment of the present invention;
图4是根据本发明一个实施例的利用红土镍矿制备羰基镍粉的***结构示意图；4 is a schematic structural view of a system for preparing nickel carbonyl powder by using laterite nickel ore according to an embodiment of the present invention;
图5是根据本发明再一个实施例的利用红土镍矿制备羰基镍粉的***结构示意图；5 is a schematic structural view of a system for preparing nickel carbonyl powder by using laterite nickel ore according to still another embodiment of the present invention;
图6是根据本发明又一个实施例的利用红土镍矿制备羰基镍粉的***结构示意图。6 is a schematic view showing the structure of a system for preparing nickel carbonyl powder using laterite nickel ore according to still another embodiment of the present invention.
发明详细描述Detailed description of the invention
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同 或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本发明，而不能理解为对本发明的限制。Embodiments of the invention are described in detail below, examples of which are illustrated in the accompanying drawings in which the same Or similar reference numerals indicate the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the drawings are intended to be illustrative of the invention and are not to be construed as limiting.
在本发明的描述中，需要理解的是，术语“中心”、“纵向”、“横向”、“长度”、“宽度”、“厚度”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”、“顺时针”、“逆时针”、“轴向”、“径向”、“周向”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", " Rear, Left, Right, Vertical, Horizontal, Top, Bottom, Inner, Out, Clockwise, Counterclockwise, Axial The orientation or positional relationship of the "radial", "circumferential" and the like is based on the orientation or positional relationship shown in the drawings, and is merely for the convenience of describing the present invention and simplifying the description, and does not indicate or imply the indicated device or The elements must have a particular orientation, are constructed and operated in a particular orientation and are therefore not to be construed as limiting.
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。在本发明的描述中，“多个”的含义是至少两个，例如两个，三个等，除非另有明确具体的限定。Moreover, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, features defining "first" or "second" may include at least one of the features, either explicitly or implicitly. In the description of the present invention, the meaning of "a plurality" is at least two, such as two, three, etc., unless specifically defined otherwise.
在本发明中，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”、“固定”等术语应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或成一体；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通或两个元件的相互作用关系，除非另有明确的限定。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本发明中的具体含义。In the present invention, the terms "installation", "connected", "connected", "fixed" and the like shall be understood broadly, and may be either a fixed connection or a detachable connection, unless explicitly stated and defined otherwise. , or integrated; can be mechanical or electrical connection; can be directly connected, or indirectly connected through an intermediate medium, can be the internal communication of two elements or the interaction of two elements, unless otherwise specified Limited. For those skilled in the art, the specific meanings of the above terms in the present invention can be understood on a case-by-case basis.
在本发明中，除非另有明确的规定和限定，第一特征在第二特征“上”或“下”可以是第一和第二特征直接接触，或第一和第二特征通过中间媒介间接接触。而且，第一特征在第二特征“之上”、“上方”和“上面”可是第一特征在第二特征正上方或斜上方，或仅仅表示第一特征水平高度高于第二特征。第一特征在第二特征“之下”、“下方”和“下面”可以是第一特征在第二特征正下方或斜下方，或仅仅表示第一特征水平高度小于第二特征。In the present invention, the first feature "on" or "under" the second feature may be a direct contact of the first and second features, or the first and second features may be indirectly through an intermediate medium, unless otherwise explicitly stated and defined. contact. Moreover, the first feature "above", "above" and "above" the second feature may be that the first feature is directly above or above the second feature, or merely that the first feature level is higher than the second feature. The first feature "below", "below" and "below" the second feature may be that the first feature is directly below or obliquely below the second feature, or merely that the first feature level is less than the second feature.
在本发明的一个方面，本发明提出了一种利用红土镍矿制备羰基镍粉的方法。根据本发明的实施例，该方法包括：(1)将红土镍矿、高硫煤和添加剂进行混合造球，以便得到混合球团；(2)将所述混合球团进行还原冶炼处理，以便得到金属化球团；(3)将所述金属化球团进行水淬-磨矿-磁选处理，以便分别得到镍铁粉和尾矿；(4)将所述镍铁粉与一氧化碳接触，以便得到含有羰基镍、羰基铁和一氧化碳的气态混合物以及铁粉；(5)将所述含有羰基镍、羰基铁和一氧化碳的气态混合物进行提纯处理，以便分别得到气态羰基镍和第一一氧化碳；以及(6)将所述气态羰基镍进行分解处理，以便分别得到羰基镍粉和第二一氧化碳。发明人发现，采用红土镍矿作为制备羰基镍粉的原料，虽然红土镍矿中镍的品位较低，但是采用本发明的方法仍可以制备得到高纯度的羰基镍粉，从而在拓宽原料来源的同时降低羰基镍粉的生产成本，同时通过采用高硫煤作为还原剂，不仅可以有效还原红土镍矿中的镍铁氧化物，而且可以得到高活性的高硫镍铁粉，由于镍铁粉中的硫在 羰化合成反应过程中起催化活化作用，从而使其与一氧化碳直接接触即可反应生成羰基化合物，并且羰基化合物合成率较高，与现有技术相比，本发明在羰基化合物合成过程中并不需要加入催化剂，从而缩短了工艺流程，其次通过对冶炼过程所得金属化球团进行水淬处理，可以有助于含硫物均匀分散在金属化球团中，从而可以得到具有疏松结构的高活性镍铁粉，并且经过磨矿磁选处理所得镍铁粉具有较细的粒径，从而可以显著提高与一氧化碳的接触面积，进而进一步提高羰基化合物合成率，另外采用廉价的高硫煤作为还原剂，不仅可以有效降低生产成本，而且可以使得其中的硫作为有益成分被应用到羰基化合物合成过程中，且在羰基化合物合成过程中不产生气态含硫物，不会造成大气污染。In one aspect of the invention, the invention provides a method of preparing nickel carbonyl powder from laterite nickel ore. According to an embodiment of the present invention, the method comprises: (1) mixing a laterite nickel ore, a high sulfur coal, and an additive to obtain a mixed pellet; and (2) performing a reduction smelting treatment on the mixed pellet to Obtaining a metallized pellet; (3) subjecting the metallized pellet to water quenching-grinding-magnetic separation treatment to obtain nickel iron powder and tailings respectively; (4) contacting the nickel iron powder with carbon monoxide, To obtain a gaseous mixture containing nickel carbonyl, carbonyl iron and carbon monoxide and iron powder; (5) purifying the gaseous mixture containing nickel carbonyl, iron carbonyl and carbon monoxide to obtain gaseous nickel carbonyl and first carbon monoxide, respectively; (6) The gaseous nickel carbonyl is subjected to decomposition treatment to obtain nickel carbonyl powder and second carbon monoxide, respectively. The inventors have found that the laterite nickel ore is used as a raw material for preparing nickel carbonyl powder. Although the grade of nickel in the laterite nickel ore is low, the high purity nickel carbonyl powder can be prepared by the method of the present invention, thereby broadening the source of the raw material. At the same time, the production cost of nickel carbonyl powder is reduced, and by using high sulfur coal as a reducing agent, not only the nickel iron oxide in the laterite nickel ore can be effectively reduced, but also the high activity high sulfur nickel iron powder can be obtained, because the nickel iron powder is Sulfur in Catalytic activation during the carbonylation synthesis reaction, so that it can react with carbon monoxide to react to form a carbonyl compound, and the carbonyl compound has a high synthesis rate. Compared with the prior art, the present invention is not in the synthesis process of the carbonyl compound. It is necessary to add a catalyst, thereby shortening the process flow, and secondly, by subjecting the metallized pellets obtained in the smelting process to water quenching treatment, the sulfur-containing substance can be uniformly dispersed in the metallized pellets, thereby obtaining high activity with a loose structure. Nickel-iron powder, and the nickel-iron powder obtained by the grinding magnetic separation treatment has a fine particle size, so that the contact area with carbon monoxide can be significantly increased, thereby further increasing the synthesis rate of the carbonyl compound, and using inexpensive high-sulfur coal as a reducing agent. Not only can the production cost be effectively reduced, but also sulfur can be used as a beneficial component in the synthesis process of the carbonyl compound, and no gaseous sulfur-containing substance is generated during the synthesis of the carbonyl compound, and air pollution is not caused.
下面参考图1-3对本发明实施例的利用红土镍矿制备羰基镍粉的方法进行详细描述。根据本发明的实施例，该方法包括：A method for preparing carbonyl nickel powder using laterite nickel ore according to an embodiment of the present invention will be described in detail below with reference to Figs. According to an embodiment of the invention, the method comprises:
S100：将红土镍矿、高硫煤和添加剂进行混合造球S100: Mixing laterite nickel ore, high-sulfur coal and additives
根据本发明的实施例，将红土镍矿、高硫煤和添加剂进行混合造球，从而可以得到混合球团。发明人发现，采用红土镍矿作为制备羰基镍粉的原料，虽然红土镍矿中镍的品位较低，但是采用本发明的方法仍可以制备得到高纯度的羰基镍粉(镍含量高于99％以上)，从而在拓宽原料来源的同时降低羰基镍粉的生产成本，并且所得铁粉中铁含量高达60～85wt％，同时通过采用高硫煤作为还原剂，不仅可以有效还原红土镍矿中的镍铁氧化物，而且可以得到高活性的高硫镍铁粉，由于镍铁粉中的硫在羰化合成反应过程中起催化活化作用，从而使其与一氧化碳直接接触即可反应生成羰基化合物，并且羰基化合物合成率较高，与现有技术相比，本发明在羰基化合物合成过程中并不需要加入催化剂，从而缩短了工艺流程，另外高硫煤资源储量丰富，但由于其会引发严重的硫污染和酸雨等环境问题而难以得到有效的利用，而本发明采用高硫煤作为还原剂，不仅可以有效降低生产成本，而且高硫煤不需要经过脱硫技术处理，反而可以使得其中的硫作为有益成分被应用到羰基化合物合成过程中，且在羰基化合物合成过程中不产生气态含硫物，不会造成大气污染。According to an embodiment of the present invention, the laterite nickel ore, the high sulfur coal, and the additive are mixed and pelletized, whereby a mixed pellet can be obtained. The inventors have found that the use of laterite nickel ore as a raw material for preparing nickel carbonyl powder, although the grade of nickel in the laterite nickel ore is relatively low, the high purity nickel carbonyl powder can be prepared by the method of the invention (the nickel content is higher than 99%). The above), thereby reducing the production cost of the nickel carbonyl powder while broadening the source of the raw material, and the iron content in the obtained iron powder is as high as 60 to 85 wt%, and at the same time, by using high sulfur coal as a reducing agent, not only the nickel in the laterite nickel ore can be effectively reduced. Iron oxide, and high-activity high-sulfur nickel-iron powder can be obtained, since the sulfur in the nickel-iron powder is catalytically activated during the carbonylation synthesis reaction, so that it can react with carbon monoxide to react to form a carbonyl compound, and The synthesis rate of the carbonyl compound is relatively high. Compared with the prior art, the invention does not need to add a catalyst in the synthesis process of the carbonyl compound, thereby shortening the process flow, and the high sulfur coal resource is abundant, but because it can cause serious sulfur It is difficult to obtain effective use of environmental problems such as pollution and acid rain, and the present invention uses high sulfur coal as a reducing agent, not only In order to effectively reduce the production cost, and high-sulfur coal does not need to be treated by desulfurization technology, it can be used as a beneficial component in the synthesis of carbonyl compounds, and no gaseous sulfur-containing substances are produced during the synthesis of carbonyl compounds. It will cause air pollution.
根据本发明的一个实施例，红土镍矿、高硫煤和添加剂的混合比例并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，红土镍矿、高硫煤和添加剂可以按照质量比为100：(5～25)(3～15)进行混合。发明人发现，若高硫煤的添加量过低，则一方面影响金属化球团的还原效果，另一方面，会导致镍铁粉的硫含量低而影响镍铁粉的活性，不利于羰基合成反应进行，而若高硫煤的添加量过高，并不能提高镍铁粉技术指标，且会造成高硫煤资源浪费，提高生产成本。该步骤中，具体的，在将红土镍矿、高硫煤和添加剂混合之前，预先对红土镍矿、高硫煤和添加剂进行粉碎。According to an embodiment of the present invention, the mixing ratio of laterite nickel ore, high-sulfur coal and additives is not particularly limited, and those skilled in the art can select according to actual needs. According to a specific embodiment of the present invention, laterite nickel ore, high The sulfur coal and the additive may be mixed at a mass ratio of 100: (5 to 25) (3 to 15). The inventors have found that if the amount of high-sulfur coal added is too low, on the one hand, it affects the reduction effect of the metallized pellets, on the other hand, the low-sulfur content of the nickel-iron powder affects the activity of the nickel-iron powder, which is disadvantageous to the carbonyl group. The synthesis reaction proceeds, and if the amount of high-sulfur coal added is too high, the technical specifications of the nickel-iron powder cannot be improved, and the high-sulfur coal resources are wasted and the production cost is increased. In this step, specifically, the laterite nickel ore, the high-sulfur coal, and the additive are previously pulverized before the laterite nickel ore, the high-sulfur coal, and the additive are mixed.
根据本发明的再一个实施例，高硫煤的中的硫含量并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，高硫煤中硫含量可以高于 3wt％。发明人发现，采用该类型的高硫煤可以制备得到高活性的高硫镍铁粉，从而使其与一氧化碳直接接触即可反应生成羰基化合物，并且羰基化合物合成率较高，与现有技术相比，本发明在羰基化合物合成过程中并不需要加入催化剂，从而缩短了工艺流程。According to still another embodiment of the present invention, the sulfur content in the high sulfur coal is not particularly limited, and those skilled in the art can select according to actual needs. According to a specific embodiment of the present invention, the sulfur content in the high sulfur coal can be high. Yu 3wt%. The inventors have found that high-sulfur high-iron nickel iron powder can be prepared by using this type of high-sulfur coal, so that it can react with carbon monoxide to react to form a carbonyl compound, and the synthesis rate of the carbonyl compound is high, which is related to the prior art. In contrast, the present invention does not require the addition of a catalyst during the synthesis of the carbonyl compound, thereby shortening the process flow.
根据本发明的又一个实施例，添加剂的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，添加剂可以为选自钾盐、钠盐、钙盐、碱金属氧化物和碱土金属氧化物中的至少一种。发明人发现，在红土镍矿的还原过程中，该类添加剂能从镁橄榄石或铁橄榄石中置换出NiO，以提高NiO的活度，从而显著降低还原冶炼温度，使得红土镍矿的还原条件大为改善，促进还原反应进行。According to still another embodiment of the present invention, the specific type of the additive is not particularly limited, and those skilled in the art can select according to actual needs. According to a specific embodiment of the present invention, the additive may be selected from the group consisting of potassium salt, sodium salt and calcium. At least one of a salt, an alkali metal oxide, and an alkaline earth metal oxide. The inventors found that in the reduction process of laterite nickel ore, the additive can replace NiO from forsterite or fayalite to increase the activity of NiO, thereby significantly reducing the reduction smelting temperature and reducing the laterite nickel ore. The conditions are greatly improved and the reduction reaction is promoted.
S200：将混合球团进行还原冶炼处理S200: The mixing pellet is subjected to reduction smelting treatment
根据本发明的实施例，将混合球团进行还原冶炼处理，从而可以得到金属化球团。根据本发明的一个实施例，冶炼处理的条件并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，还原冶炼处理可以在1000～1400摄氏度下进行20分钟以上，优选在1200～1350摄氏度下进行30～60分钟。发明人发现，该冶炼条件下可以将部分铁氧化物还原成金属铁，同时，将氧化镍全部还原成金属镍，从而得到满足工艺要求的金属化球团，并且既不影响后续工艺中镍的高回收率，又不造成能源浪费。According to an embodiment of the present invention, the mixed pellets are subjected to a reduction smelting treatment, whereby metallized pellets can be obtained. According to an embodiment of the present invention, the conditions of the smelting process are not particularly limited, and those skilled in the art may select according to actual needs. According to a specific embodiment of the present invention, the reduction smelting process may be performed at 1000-1400 degrees Celsius for 20 minutes. The above is preferably carried out at 1200 to 1350 degrees Celsius for 30 to 60 minutes. The inventors have found that under the smelting conditions, part of the iron oxide can be reduced to metallic iron, and at the same time, all the nickel oxide is reduced to metallic nickel, thereby obtaining a metallized pellet satisfying the process requirements, and neither affecting the nickel in the subsequent process. High recovery rate without causing energy waste.
根据本发明的再一个实施例，还原冶炼处理的装置并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，还原冶炼装置可以为选自转底炉、回转窑和隧道窑中的至少一种。According to still another embodiment of the present invention, the apparatus for reducing the smelting treatment is not particularly limited, and those skilled in the art may select according to actual needs. According to a specific embodiment of the present invention, the reduction smelting apparatus may be selected from a rotary hearth furnace. At least one of a rotary kiln and a tunnel kiln.
S300：将金属化球团进行水淬-磨矿-磁选处理S300: Water quenching-grinding-magnetic separation treatment of metallized pellets
根据本发明的实施例，将上述所得金属化球团进行水淬-磨矿-磁选处理，从而可以得到镍铁粉和尾矿。发明人发现，通过对还原冶炼过程所得金属化球团进行水淬处理，可以有助于含硫物均匀分散在金属化球团中，从而可以得到具有疏松结构的高活性镍铁粉，使得在镍铁粉内部形成连通的网状结构，进而利于后续羰基化合物的合成，并且经过磨矿、磁选处理所得镍铁粉具有较细的粒径，从而可以显著提高与一氧化碳的接触面积，进而进一步提高羰基化合物合成率，较现有技术采用雾化制粒相比，本发明采用磨矿磁选后的镍铁粉不需要进行二次加工即可满足下一步羰基镍合成反应的粒度要求。具体的，水淬-磨矿-磁选处理可以是采用水淬装置、磨矿装置和磁选装置的联用装置进行的。According to an embodiment of the present invention, the above-mentioned obtained metallized pellets are subjected to water quenching-grinding-magnetic separation treatment, whereby nickel iron powder and tailings can be obtained. The inventors have found that by subjecting the metallized pellets obtained in the reduction smelting process to water quenching treatment, the sulfur-containing substances can be uniformly dispersed in the metallized pellets, thereby obtaining a highly active nickel-iron powder having a loose structure, so that The nickel-iron powder forms a connected network structure inside, which facilitates the synthesis of the subsequent carbonyl compound, and the nickel-iron powder obtained by the grinding and magnetic separation treatment has a fine particle diameter, thereby significantly increasing the contact area with carbon monoxide, and further Compared with the prior art, the synthesis rate of the carbonyl compound is higher than that of the prior art, and the nickel-iron powder after the magnetic separation of the invention can meet the particle size requirement of the next nickel carbonyl synthesis reaction without secondary processing. Specifically, the water quenching-grinding-magnetic separation treatment may be performed by a combination of a water quenching device, a grinding device, and a magnetic separation device.
根据本发明的一个实施例，镍铁粉中镍含量并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，镍铁粉中镍含量可以为5～15wt％。发明人发现，现有羰基镍合成工艺中为了得到高纯度的羰基镍粉，通常需要采用含镍量超过50wt％的铜镍合金或高纯氧化镍，导致原料生产成本较高，不易采购，而本发明对镍铁粉中镍品位要求门槛较低，采用镍含量仅为5～15wt％的镍铁粉作为羰基镍粉的合成原料，可以 制备得到高纯度的羰基镍粉，从而在拓宽镍粉生产原料来源的同时显著降低原料成本。According to an embodiment of the present invention, the nickel content in the nickel iron powder is not particularly limited, and those skilled in the art may select according to actual needs. According to a specific embodiment of the present invention, the nickel content in the nickel iron powder may be 5-15 wt. %. The inventors have found that in order to obtain high-purity nickel carbonyl powder in the existing nickel carbonyl synthesis process, it is generally required to use a copper-nickel alloy or a high-purity nickel oxide containing more than 50% by weight of nickel, resulting in high raw material production cost and difficulty in procurement. The invention has low threshold for nickel grade in nickel iron powder, and uses nickel iron powder with nickel content of only 5-15 wt% as synthetic raw material of nickel carbonyl powder. A high-purity nickel carbonyl powder is prepared, thereby significantly reducing the raw material cost while broadening the source of the nickel powder production raw material.
根据本发明的再一个实施例，镍铁粉中硫含量并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，镍铁粉中硫含量可以高于1wt％，优选为1～5wt％。发明人发现，在一定范围内，镍铁粉中硫含量越高，使得镍铁粉活性越高，从而越有利于羰基镍合成反应的快速进行，并且羰基镍合成率也较高，较现有技术在羰基镍合成步骤中加入含硫物作为催化剂相比，本发明并不需要额外加入催化剂，从而缩短了制备工艺流程，然而镍铁粉含硫量过高，一方面会导致镍铁粉中镍铁含量同时降低，另一方面会造成高硫煤资源的浪费。According to still another embodiment of the present invention, the sulfur content in the nickel iron powder is not particularly limited, and those skilled in the art may select according to actual needs. According to a specific embodiment of the present invention, the sulfur content in the nickel iron powder may be higher than 1 wt. % is preferably from 1 to 5% by weight. The inventors found that, within a certain range, the higher the sulfur content in the nickel-iron powder, the higher the activity of the nickel-iron powder, which is more favorable for the rapid progress of the nickel carbonyl synthesis reaction, and the nickel carbonyl synthesis rate is also higher, compared with the existing one. Compared with the method of adding sulfur-containing substance as a catalyst in the nickel carbonyl synthesis step, the invention does not need to add an additional catalyst, thereby shortening the preparation process. However, the sulphur content of the nickel-iron powder is too high, and on the one hand, the nickel-iron powder is caused. The nickel-iron content is reduced at the same time, and on the other hand, the waste of high-sulfur coal resources is caused.
根据本发明的又一个实施例，镍铁粉粒度并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，镍铁粉粒度小于45微米的占镍铁粉总质量的90％以上。发明人发现，该粒径范围的镍铁粉活性较高，且在羰基镍合成过程中与一氧化碳接触面积较大，从而可以显著提高羰基镍的合成率。According to still another embodiment of the present invention, the particle size of the nickel iron powder is not particularly limited, and those skilled in the art can select according to actual needs. According to a specific embodiment of the present invention, the nickel iron powder has a particle size of less than 45 micrometers. More than 90% of the total mass. The inventors have found that the nickel-iron powder having a high particle size range has a high activity and a large contact area with carbon monoxide during the synthesis of nickel carbonyl, so that the synthesis rate of nickel carbonyl can be remarkably improved.
S400：将镍铁粉与一氧化碳接触S400: contacting nickel iron powder with carbon monoxide
根据本发明的实施例，将镍铁粉与一氧化碳逆流接触，从而可以得到含有羰基镍、羰基铁和一氧化碳的气态混合物以及铁粉。发明人发现，采用高活性的镍铁粉与一氧化碳直接接触即可反应生成羰基化合物，并且羰基化合物合成率较高，与现有技术相比，本发明在羰基化合物合成过程中并不需要加入催化剂，从而缩短了工艺流程。According to an embodiment of the present invention, the nickel iron powder is brought into countercurrent contact with carbon monoxide, whereby a gaseous mixture containing nickel carbonyl, carbonyl iron and carbon monoxide and iron powder can be obtained. The inventors have found that the use of highly active nickel iron powder in direct contact with carbon monoxide can react to form a carbonyl compound, and the synthesis rate of the carbonyl compound is relatively high. Compared with the prior art, the present invention does not require the addition of a catalyst during the synthesis of the carbonyl compound. , thus shortening the process flow.
根据本发明的一个实施例，镍铁粉与一氧化碳反应条件并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，镍铁粉与一氧化碳接触可以在110～230摄氏度和2～10MPa的条件下进行30～42小时。由此，可以显著提高羰基化合物的合成率。According to an embodiment of the present invention, the reaction conditions of the nickel iron powder and the carbon monoxide are not particularly limited, and those skilled in the art can select according to actual needs. According to a specific embodiment of the present invention, the nickel iron powder can be contacted with carbon monoxide at 110~. It is carried out at 230 ° C and 2 to 10 MPa for 30 to 42 hours. Thereby, the synthesis rate of the carbonyl compound can be remarkably improved.
S500：将含有羰基镍、羰基铁和一氧化碳的气态混合物进行提纯处理S500: purifying a gaseous mixture containing nickel carbonyl, iron carbonyl and carbon monoxide
根据本发明的实施例，将含有羰基镍、羰基铁和一氧化碳的气态混合物进行提纯处理，从而可以分别得到气态羰基镍和第一一氧化碳。由此，可以显著提高后续所得羰基镍粉的纯度。该步骤中，具体的，首先将羰基镍、羰基铁和一氧化碳的气态混合物进行冷凝处理，气态混合物中的羰基镍和羰基铁冷凝变为液体，而其中的一氧化碳则以气体形式存在，然后对所得含有羰基镍和羰基铁的液态混合物进行精馏处理，从而可以分离得到高纯度的气态羰基镍。需要说明的是，本领域技术人员可以根据实际需要对所采用冷凝和精馏的具体操作条件进行选择。According to an embodiment of the present invention, a gaseous mixture containing nickel carbonyl, iron carbonyl and carbon monoxide is subjected to purification treatment, whereby gaseous nickel carbonyl and first carbon monoxide can be obtained, respectively. Thereby, the purity of the subsequently obtained nickel carbonyl powder can be remarkably improved. In this step, specifically, a gaseous mixture of nickel carbonyl, carbonyl iron and carbon monoxide is first condensed, and the nickel carbonyl and the carbonyl iron in the gaseous mixture are condensed into a liquid, and the carbon monoxide therein is present in the form of a gas, and then the resulting The liquid mixture containing nickel carbonyl and iron carbonyl is subjected to rectification treatment, whereby high purity gaseous nickel carbonyl can be isolated. It should be noted that the specific operating conditions of the condensation and rectification employed may be selected by those skilled in the art according to actual needs.
S600：将气态羰基镍进行分解处理S600: Decomposition of gaseous nickel carbonyl
根据本发明的实施例，将气态羰基镍进行分解处理，从而可以分别得到镍粉和第二一氧化碳。具体的，羰基镍不稳定，在加热时可以迅速分解为镍和一氧化碳，从而可以得到 高纯度的羰基镍粉。需要说明的是，本领域技术人员可以根据实际需要对分解处理的条件进行选择。According to an embodiment of the present invention, the gaseous nickel carbonyl is subjected to decomposition treatment, whereby nickel powder and second carbon monoxide can be obtained, respectively. Specifically, the nickel carbonyl is unstable and can be rapidly decomposed into nickel and carbon monoxide when heated, thereby obtaining High purity nickel carbonyl powder. It should be noted that those skilled in the art can select the conditions of the decomposition process according to actual needs.
根据本发明实施例的利用红土镍矿制备羰基镍粉的方法采用红土镍矿作为制备羰基镍粉的原料，虽然红土镍矿中镍的品位较低，但是采用本发明的方法仍可以制备得到高纯度的羰基镍粉，从而在拓宽原料来源的同时降低羰基镍粉的生产成本，同时通过采用高硫煤作为还原剂，不仅可以有效还原红土镍矿中的镍铁氧化物，而且可以得到高活性的高硫镍铁粉，由于镍铁粉中的硫在羰化合成反应过程中起催化活化作用，从而使其与一氧化碳直接接触即可反应生成羰基化合物，并且羰基化合物合成率较高，与现有技术相比，本发明在羰基化合物合成过程中并不需要加入催化剂，从而缩短了工艺流程，其次通过对冶炼过程所得金属化球团进行水淬处理，可以有助于含硫物均匀分散在金属化球团中，从而可以得到具有疏松结构的高活性镍铁粉，并且经过磨矿磁选处理所得镍铁粉具有较细的粒径，从而可以显著提高与一氧化碳的接触面积，进而进一步提高羰基化合物合成率，另外采用廉价的高硫煤作为还原剂，不仅可以有效降低生产成本，而且可以使得其中的硫作为有益成分被应用到羰基化合物合成过程中，且在羰基化合物合成过程中不产生气态含硫物，不会造成大气污染。The method for preparing nickel carbonyl powder by using laterite nickel ore according to an embodiment of the present invention uses laterite nickel ore as a raw material for preparing nickel carbonyl powder. Although the grade of nickel in the laterite nickel ore is low, the method of the present invention can still be prepared high. Purity of nickel carbonyl powder, which can reduce the production cost of nickel carbonyl powder while broadening the source of raw materials, and at the same time, by using high sulfur coal as a reducing agent, not only can nickel iron oxide in the laterite nickel ore be effectively reduced, but also high activity can be obtained. The high-sulfur nickel-iron powder, because the sulfur in the nickel-iron powder plays a catalytic activation during the carbonylation synthesis reaction, so that it can react with carbon monoxide to react to form a carbonyl compound, and the carbonyl compound has a high synthesis rate. Compared with the prior art, the invention does not need to add a catalyst in the synthesis process of the carbonyl compound, thereby shortening the process flow, and secondly, by subjecting the metallized pellet obtained in the smelting process to water quenching treatment, the sulfur-containing substance can be uniformly dispersed in the process. Metallized pellets, thereby obtaining a highly active nickel-iron powder having a loose structure and being subjected to grinding The obtained ferronickel powder has a fine particle diameter, thereby significantly increasing the contact area with carbon monoxide, thereby further increasing the synthesis rate of the carbonyl compound, and using inexpensive high-sulfur coal as a reducing agent, not only can effectively reduce the production cost, but also The sulfur is applied as a beneficial component to the synthesis process of the carbonyl compound, and no gaseous sulfur-containing substance is generated during the synthesis of the carbonyl compound, and no air pollution is caused.
参考图2，根据本发明实施例的利用红土镍矿制备羰基镍粉的方法进一步包括：Referring to FIG. 2, a method for preparing nickel carbonyl powder using laterite nickel ore according to an embodiment of the present invention further includes:
S700：将第一一氧化碳返回S400与镍铁粉接触S700: returning the first carbon monoxide back to S400 and contacting with the nickel iron powder
根据本发明的实施例，将S500提纯分离所得第一一氧化碳返回至S400与镍铁粉接触，从而可以显著提高一氧化碳循环利用率。According to an embodiment of the present invention, the first carbon monoxide obtained by purifying and separating S500 is returned to S400 to be in contact with the nickel iron powder, so that the carbon monoxide cycle utilization ratio can be remarkably improved.
参考图3，根据本发明实施例的利用红土镍矿制备羰基镍粉的方法进一步包括：Referring to FIG. 3, a method for preparing nickel carbonyl powder using laterite nickel ore according to an embodiment of the present invention further includes:
S800：将第二一氧化碳返回S400与镍铁粉接触S800: returning the second carbon monoxide back to S400 and contacting the nickel iron powder
根据本发明的实施例，将S600分解所得第二一氧化碳返回至S400与镍铁粉接触，从而可以进一步提高一氧化碳循环利用率。According to an embodiment of the present invention, the second carbon monoxide obtained by decomposing S600 is returned to S400 to be in contact with the nickel iron powder, so that the carbon monoxide cycle utilization ratio can be further improved.
在本发明的另一个方面，本发明提出了一种利用红土镍矿制备羰基镍粉的***。根据本发明的实施例，该***包括：混合造球装置，所述混合造球装置具有红土镍矿入口、高硫煤入口、添加剂入口和混合球团出口，且适于将红土镍矿、高硫煤和添加剂进行混合造球，以便得到混合球团；还原冶炼装置，所述还原冶炼装置具有混合球团入口和金属化球团出口，所述混合球团入口和所述混合球团出口相连，且适于将所述混合球团进行还原冶炼处理，以便得到金属化球团；水淬-磨矿-磁选装置，所述水淬-磨矿-磁选装置具有金属化球团入口、镍铁粉出口和尾矿出口，所述金属化球团入口与所述金属化球团出口相连，且适于将所述金属化球团进行水淬-磨矿-磁选处理，以便分别得到镍铁粉和尾矿；羰基合成装置，所述羰基合成装置具有一氧化碳入口、镍铁粉入口、气态混合物出口和铁粉出口，所 述镍铁粉入口和所述镍铁粉出口相连，且适于将所述镍铁粉与一氧化碳接触，以便得到含有羰基镍、羰基铁和一氧化碳的气态混合物以及铁粉；提纯装置，所述提纯装置具有气态混合物入口、气态羰基镍出口和第一一氧化碳出口，所述气态混合物入口与所述气态混合物出口相连，且适于将所述含有羰基镍、羰基铁和一氧化碳的气态混合物进行提纯处理，以便分别得到气态羰基镍和第一一氧化碳；以及分解装置，所述分解装置具有气态羰基镍入口、羰基镍粉出口和第二一氧化碳出口，所述气态羰基镍入口和所述气态羰基镍出口相连，且适于将所述气态羰基镍进行分解处理，以便分别得到羰基镍粉和第二一氧化碳。发明人发现，采用红土镍矿作为制备羰基镍粉的原料，虽然红土镍矿中镍的品位较低，但是采用本发明的***仍可以制备得到高纯度的羰基镍粉，从而在拓宽原料来源的同时降低羰基镍粉的生产成本，同时通过采用高硫煤作为还原剂，不仅可以有效还原红土镍矿中的镍铁氧化物，而且可以得到高活性的高硫镍铁粉，由于镍铁粉中的硫在羰化合成反应过程中起催化活化作用，从而使其与一氧化碳直接接触即可反应生成羰基化合物，并且羰基化合物合成率较高，与现有技术相比，本发明在羰基化合物合成过程中并不需要加入催化剂，从而缩短了工艺流程，其次通过对冶炼过程所得金属化球团进行水淬处理，可以有助于含硫物均匀分散在金属化球团中，从而可以得到具有疏松结构的高活性镍铁粉，并且经过磨矿磁选处理所得镍铁粉具有较细的粒径，从而可以显著提高与一氧化碳的接触面积，进而进一步提高羰基化合物合成率，另外采用廉价的高硫煤作为还原剂，不仅可以有效降低生产成本，而且可以使得其中的硫作为有益成分被应用到羰基化合物合成过程中，且在羰基化合物合成过程中不产生气态含硫物，不会造成大气污染。In another aspect of the invention, the invention provides a system for preparing nickel carbonyl powder from laterite nickel ore. According to an embodiment of the invention, the system comprises: a mixing pelletizing device having a laterite nickel ore inlet, a high sulfur coal inlet, an additive inlet, and a mixing pellet outlet, and is suitable for laterite nickel ore, high The sulfur coal and the additive are mixed and pelletized to obtain a mixed pellet; a reduction smelting apparatus having a mixed pellet inlet and a metallized pellet outlet, the mixed pellet inlet being connected to the mixed pellet outlet And suitable for performing the reduction smelting treatment of the mixed pellets to obtain a metallized pellet; a water quenching-grinding-magnetic separation device having a metallized pellet inlet, a nickel iron powder outlet and a tailings outlet, the metallized pellet inlet being connected to the metallized pellet outlet, and adapted to subject the metallized pellet to water quenching-grinding-magnetic separation treatment to obtain respectively Nickel iron powder and tailings; a oxo synthesis unit having a carbon monoxide inlet, a nickel iron powder inlet, a gaseous mixture outlet, and an iron powder outlet, The nickel iron powder inlet is connected to the nickel iron powder outlet, and is adapted to contact the nickel iron powder with carbon monoxide to obtain a gaseous mixture containing nickel carbonyl, carbonyl iron and carbon monoxide and iron powder; and a purification device for purifying The apparatus has a gaseous mixture inlet, a gaseous nickel carbonyl outlet, and a first carbon monoxide outlet, the gaseous mixture inlet being coupled to the gaseous mixture outlet, and adapted to purify the gaseous mixture comprising nickel carbonyl, carbonyl iron, and carbon monoxide, To obtain a gaseous nickel carbonyl and a first carbon monoxide, respectively; and a decomposition device having a gaseous nickel carbonyl inlet, a nickel carbonyl powder outlet, and a second carbon monoxide outlet, the gaseous nickel carbonyl inlet being connected to the gaseous nickel carbonyl outlet, And suitable for decomposing the gaseous nickel carbonyl to obtain nickel carbonyl powder and second carbon monoxide, respectively. The inventors have found that the laterite nickel ore is used as a raw material for preparing nickel carbonyl powder. Although the grade of nickel in the laterite nickel ore is low, the high purity nickel carbonyl powder can be prepared by using the system of the present invention, thereby broadening the raw material source. At the same time, the production cost of nickel carbonyl powder is reduced, and by using high sulfur coal as a reducing agent, not only the nickel iron oxide in the laterite nickel ore can be effectively reduced, but also the high activity high sulfur nickel iron powder can be obtained, because the nickel iron powder is The sulfur is catalytically activated during the carbonylation synthesis reaction, so that it can react with carbon monoxide to react to form a carbonyl compound, and the carbonyl compound has a high synthesis rate. Compared with the prior art, the present invention is synthesized in a carbonyl compound. The catalyst is not required to be added, thereby shortening the process flow, and secondly, by subjecting the metallized pellets obtained in the smelting process to water quenching treatment, the sulfur-containing substance can be uniformly dispersed in the metallized pellets, thereby obtaining a loose structure. High-activity nickel-iron powder, and the nickel-iron powder obtained by the grinding magnetic separation treatment has a fine particle size, thereby In order to significantly increase the contact area with carbon monoxide, thereby further increasing the synthesis rate of carbonyl compounds, and using inexpensive high-sulfur coal as a reducing agent, not only can the production cost be effectively reduced, but also sulfur can be used as a beneficial component to the synthesis of carbonyl compounds. During the process, no gaseous sulfur compounds are produced during the synthesis of the carbonyl compound, and no air pollution is caused.
下面参考图4-6对本发明实施例的利用红土镍矿制备羰基镍粉的***进行详细描述。根据本发明的实施例，该***包括：A system for preparing carbonyl nickel powder using laterite nickel ore according to an embodiment of the present invention will now be described in detail with reference to Figs. 4-6. According to an embodiment of the invention, the system comprises:
混合造球装置100：根据本发明的实施例，混合造球装置100具有红土镍矿入口101、高硫煤入口102、添加剂入口103和混合球团出口104，且适于将红土镍矿、高硫煤和添加剂进行混合造球，从而可以得到混合球团。发明人发现，采用红土镍矿作为制备羰基镍粉的原料，虽然红土镍矿中镍的品位较低，但是采用本发明的方法仍可以制备得到高纯度的羰基镍粉(镍含量高于99％以上)，从而在拓宽原料来源的同时降低羰基镍粉的生产成本，并且所得铁粉中铁含量高达60～85wt％，同时通过采用高硫煤作为还原剂，不仅可以有效还原红土镍矿中的镍铁氧化物，而且可以得到高活性的高硫镍铁粉，由于镍铁粉中的硫在羰化合成反应过程中起催化活化作用，从而使其与一氧化碳直接接触即可反应生成羰基化合物，并且羰基化合物合成率较高，与现有技术相比，本发明在羰基化合物合成过程中并不需要加入催化剂，从而缩短了工艺流程，另外高硫煤资源储量丰富，但由于其会引发严重的硫污染和酸雨等环境问题而难以得到有效的利用，而本发明采用高硫煤作为还原剂，不 仅可以有效降低生产成本，而且高硫煤不需要经过脱硫技术处理，反而可以使得其中的硫作为有益成分被应用到羰基化合物合成过程中，且在羰基化合物合成过程中不产生气态含硫物，不会造成大气污染。Mixed pelletizing device 100: According to an embodiment of the invention, hybrid pelletizing device 100 has a laterite nickel ore inlet 101, a high sulfur coal inlet 102, an additive inlet 103, and a mixing pellet outlet 104, and is suitable for laterite nickel ore, high The sulfur coal and the additive are mixed and pelletized, so that a mixed pellet can be obtained. The inventors have found that the use of laterite nickel ore as a raw material for preparing nickel carbonyl powder, although the grade of nickel in the laterite nickel ore is relatively low, the high purity nickel carbonyl powder can be prepared by the method of the invention (the nickel content is higher than 99%). The above), thereby reducing the production cost of the nickel carbonyl powder while broadening the source of the raw material, and the iron content in the obtained iron powder is as high as 60 to 85 wt%, and at the same time, by using high sulfur coal as a reducing agent, not only the nickel in the laterite nickel ore can be effectively reduced. Iron oxide, and high-activity high-sulfur nickel-iron powder can be obtained, since the sulfur in the nickel-iron powder is catalytically activated during the carbonylation synthesis reaction, so that it can react with carbon monoxide to react to form a carbonyl compound, and The synthesis rate of the carbonyl compound is relatively high. Compared with the prior art, the invention does not need to add a catalyst in the synthesis process of the carbonyl compound, thereby shortening the process flow, and the high sulfur coal resource is abundant, but because it can cause serious sulfur It is difficult to obtain effective use of environmental problems such as pollution and acid rain, and the present invention uses high sulfur coal as a reducing agent, It can only effectively reduce the production cost, and high-sulfur coal does not need to be treated by desulfurization technology. Instead, sulfur can be used as a beneficial component in the synthesis of carbonyl compounds, and no gaseous sulfur-containing substances are produced during the synthesis of carbonyl compounds. Will not cause air pollution.
根据本发明的一个实施例，红土镍矿、高硫煤和添加剂的混合比例并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，红土镍矿、高硫煤和添加剂可以按照质量比为100：(5～25)(3～15)进行混合。发明人发现，若高硫煤的添加量过低，则一方面影响金属化球团的还原效果，另一方面，会导致镍铁粉的硫含量低而影响镍铁粉的活性，不利于羰基合成反应进行，而若高硫煤的添加量过高，并不能提高镍铁粉技术指标，且会造成高硫煤资源浪费，提高生产成本。该步骤中，具体的，在将红土镍矿、高硫煤和添加剂混合之前，预先对红土镍矿、高硫煤和添加剂进行粉碎。According to an embodiment of the present invention, the mixing ratio of laterite nickel ore, high-sulfur coal and additives is not particularly limited, and those skilled in the art can select according to actual needs. According to a specific embodiment of the present invention, laterite nickel ore, high The sulfur coal and the additive may be mixed at a mass ratio of 100: (5 to 25) (3 to 15). The inventors have found that if the amount of high-sulfur coal added is too low, on the one hand, it affects the reduction effect of the metallized pellets, on the other hand, the low-sulfur content of the nickel-iron powder affects the activity of the nickel-iron powder, which is disadvantageous to the carbonyl group. The synthesis reaction proceeds, and if the amount of high-sulfur coal added is too high, the technical specifications of the nickel-iron powder cannot be improved, and the high-sulfur coal resources are wasted and the production cost is increased. In this step, specifically, the laterite nickel ore, the high-sulfur coal, and the additive are previously pulverized before the laterite nickel ore, the high-sulfur coal, and the additive are mixed.
根据本发明的再一个实施例，高硫煤的中的硫含量并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，高硫煤中硫含量可以高于3wt％。发明人发现，采用该类型的高硫煤可以制备得到高活性的高硫镍铁粉，从而使其与一氧化碳直接接触即可反应生成羰基化合物，并且羰基化合物合成率较高，与现有技术相比，本发明在羰基化合物合成过程中并不需要加入催化剂，从而缩短了工艺流程。According to still another embodiment of the present invention, the sulfur content in the high sulfur coal is not particularly limited, and those skilled in the art can select according to actual needs. According to a specific embodiment of the present invention, the sulfur content in the high sulfur coal can be high. At 3wt%. The inventors have found that high-sulfur high-iron nickel iron powder can be prepared by using this type of high-sulfur coal, so that it can react with carbon monoxide to react to form a carbonyl compound, and the synthesis rate of the carbonyl compound is high, which is related to the prior art. In contrast, the present invention does not require the addition of a catalyst during the synthesis of the carbonyl compound, thereby shortening the process flow.
根据本发明的又一个实施例，添加剂的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，添加剂可以为选自钾盐、钠盐、钙盐、碱金属氧化物和碱土金属氧化物中的至少一种。发明人发现，在红土镍矿的还原过程中，该类添加剂能从镁橄榄石或铁橄榄石中置换出NiO，以提高NiO的活度，从而显著降低还原冶炼温度，使得红土镍矿的还原条件大为改善，促进还原反应进行。According to still another embodiment of the present invention, the specific type of the additive is not particularly limited, and those skilled in the art can select according to actual needs. According to a specific embodiment of the present invention, the additive may be selected from the group consisting of potassium salt, sodium salt and calcium. At least one of a salt, an alkali metal oxide, and an alkaline earth metal oxide. The inventors found that in the reduction process of laterite nickel ore, the additive can replace NiO from forsterite or fayalite to increase the activity of NiO, thereby significantly reducing the reduction smelting temperature and reducing the laterite nickel ore. The conditions are greatly improved and the reduction reaction is promoted.
还原冶炼装置200：根据本发明的实施例，还原冶炼装置200具有混合球团入口201和金属化球团出口202，混合球团入口201和混合球团出口104相连，且适于将混合球团进行还原冶炼处理，从而可以得到金属化球团。Reduction smelting apparatus 200: According to an embodiment of the invention, the reduction smelting apparatus 200 has a mixing pellet inlet 201 and a metallized pellet outlet 202, the mixing pellet inlet 201 and the mixing pellet outlet 104 are connected, and is suitable for mixing pellets A reduction smelting process is performed to obtain a metallized pellet.
根据本发明的一个实施例，冶炼处理的条件并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，还原冶炼处理可以在1000～1400摄氏度下进行20分钟以上，优选在1200～1350摄氏度下进行30～60分钟。发明人发现，该冶炼条件下可以将部分铁氧化物还原成金属铁，同时，将氧化镍全部还原成金属镍，从而得到满足工艺要求的金属化球团，并且既不影响后续工艺中镍的高回收率，又不造成能源浪费。According to an embodiment of the present invention, the conditions of the smelting process are not particularly limited, and those skilled in the art may select according to actual needs. According to a specific embodiment of the present invention, the reduction smelting process may be performed at 1000-1400 degrees Celsius for 20 minutes. The above is preferably carried out at 1200 to 1350 degrees Celsius for 30 to 60 minutes. The inventors have found that under the smelting conditions, part of the iron oxide can be reduced to metallic iron, and at the same time, all the nickel oxide is reduced to metallic nickel, thereby obtaining a metallized pellet satisfying the process requirements, and neither affecting the nickel in the subsequent process. High recovery rate without causing energy waste.
根据本发明的再一个实施例，还原冶炼装置并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，还原冶炼装置可以为选自转底炉、回转窑和隧道窑中的至少一种。According to still another embodiment of the present invention, the reduction smelting apparatus is not particularly limited, and those skilled in the art may select according to actual needs. According to a specific embodiment of the present invention, the reduction smelting apparatus may be selected from a rotary hearth furnace and a rotary kiln. And at least one of the tunnel kiln.
水淬-磨矿-磁选装置300：根据本发明的实施例，水淬-磨矿-磁选装置300具有金属化 球团入口301、镍铁粉出口302和尾矿出口303，金属化球团入口301与金属化球团出口202相连，且适于将上述所得金属化球团进行水淬-磨矿-磁选处理，从而可以得到镍铁粉和尾矿。发明人发现，通过对还原冶炼过程所得金属化球团进行水淬处理，可以有助于含硫物均匀分散在金属化球团中，从而可以得到具有疏松结构的高活性镍铁粉，使得在镍铁粉内部形成连通的网状结构，进而利于后续羰基化合物的合成，并且经过磨矿、磁选处理所得镍铁粉具有较细的粒径，从而可以显著提高与一氧化碳的接触面积，进而进一步提高羰基化合物合成率，较现有技术采用雾化制粒相比，本发明采用磨矿磁选后的镍铁粉不需要进行二次加工即可满足下一步羰基镍合成反应的粒度要求。具体的，水淬-磨矿-磁选装置可以为水淬装置、磨矿装置和磁选装置的联用装置。Water quenching-grinding-magnetic separation device 300: According to an embodiment of the invention, the water quenching-grinding-magnetic separation device 300 has metallization a pellet inlet 301, a nickel iron powder outlet 302 and a tailings outlet 303, the metallized pellet inlet 301 is connected to the metallized pellet outlet 202, and is suitable for water quenching-grinding-magnetic separation of the obtained metallized pellets described above. Treatment, so that nickel iron powder and tailings can be obtained. The inventors have found that by subjecting the metallized pellets obtained in the reduction smelting process to water quenching treatment, the sulfur-containing substances can be uniformly dispersed in the metallized pellets, thereby obtaining a highly active nickel-iron powder having a loose structure, so that The nickel-iron powder forms a connected network structure inside, which facilitates the synthesis of the subsequent carbonyl compound, and the nickel-iron powder obtained by the grinding and magnetic separation treatment has a fine particle diameter, thereby significantly increasing the contact area with carbon monoxide, and further Compared with the prior art, the synthesis rate of the carbonyl compound is higher than that of the prior art, and the nickel-iron powder after the magnetic separation of the invention can meet the particle size requirement of the next nickel carbonyl synthesis reaction without secondary processing. Specifically, the water quenching-grinding-magnetic separation device may be a combination device of a water quenching device, a grinding device, and a magnetic separation device.
根据本发明的一个实施例，镍铁粉中镍含量并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，镍铁粉中镍含量可以为5～15wt％。发明人发现，现有羰基镍合成工艺中为了得到高纯度的羰基镍粉，通常需要采用含镍量超过50wt％的铜镍合金或高纯氧化镍，导致原料生产成本较高，不易采购，而本发明对镍铁粉中镍品位要求门槛较低，采用镍含量仅为5～15wt％的镍铁粉作为羰基镍粉的合成原料，可以制备得到高纯度的羰基镍粉，从而在拓宽羰基镍粉生产原料来源的同时显著降低原料成本。According to an embodiment of the present invention, the nickel content in the nickel iron powder is not particularly limited, and those skilled in the art may select according to actual needs. According to a specific embodiment of the present invention, the nickel content in the nickel iron powder may be 5-15 wt. %. The inventors have found that in order to obtain high-purity nickel carbonyl powder in the existing nickel carbonyl synthesis process, it is generally required to use a copper-nickel alloy or a high-purity nickel oxide containing more than 50% by weight of nickel, resulting in high raw material production cost and difficulty in procurement. The invention has low threshold for nickel grade in nickel iron powder, and nickel iron powder with nickel content of only 5-15 wt% is used as a synthetic raw material of carbonyl nickel powder, and high purity nickel carbonyl powder can be prepared, thereby broadening nickel carbonyl. The source of raw materials for powder production also significantly reduces the cost of raw materials.
根据本发明的再一个实施例，镍铁粉中硫含量并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，镍铁粉中硫含量可以高于1wt％，优选为1～5wt％。发明人发现，在一定范围内，镍铁粉中硫含量越高，使得镍铁粉活性越高，从而越有利于羰基镍合成反应的快速进行，并且羰基镍合成率也较高，较现有技术在羰基镍合成步骤中加入含硫物作为催化剂相比，本发明并不需要额外加入催化剂，从而缩短了制备工艺流程，然而镍铁粉含硫量过高，一方面会导致镍铁粉中镍铁含量同时降低，另一方面会造成高硫煤资源的浪费。According to still another embodiment of the present invention, the sulfur content in the nickel iron powder is not particularly limited, and those skilled in the art may select according to actual needs. According to a specific embodiment of the present invention, the sulfur content in the nickel iron powder may be higher than 1 wt. % is preferably from 1 to 5% by weight. The inventors found that, within a certain range, the higher the sulfur content in the nickel-iron powder, the higher the activity of the nickel-iron powder, which is more favorable for the rapid progress of the nickel carbonyl synthesis reaction, and the nickel carbonyl synthesis rate is also higher, compared with the existing one. Compared with the method of adding sulfur-containing substance as a catalyst in the nickel carbonyl synthesis step, the invention does not need to add an additional catalyst, thereby shortening the preparation process. However, the sulphur content of the nickel-iron powder is too high, and on the one hand, the nickel-iron powder is caused. The nickel-iron content is reduced at the same time, and on the other hand, the waste of high-sulfur coal resources is caused.
根据本发明的又一个实施例，镍铁粉粒度并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，镍铁粉粒度小于45微米的占镍铁粉总质量的90％以上。发明人发现，该粒径范围的镍铁粉活性较高，且在羰基镍合成过程中与一氧化碳接触面积较大，从而可以显著提高羰基镍的合成率。According to still another embodiment of the present invention, the particle size of the nickel iron powder is not particularly limited, and those skilled in the art can select according to actual needs. According to a specific embodiment of the present invention, the nickel iron powder has a particle size of less than 45 micrometers. More than 90% of the total mass. The inventors have found that the nickel-iron powder having a high particle size range has a high activity and a large contact area with carbon monoxide during the synthesis of nickel carbonyl, so that the synthesis rate of nickel carbonyl can be remarkably improved.
羰基合成装置400：根据本发明的实施例，羰基合成装置400具有一氧化碳入口401、镍铁粉入口402、气态混合物出口403和铁粉出口404，镍铁粉入口402和镍铁粉出口302相连，且适于将镍铁粉与一氧化碳逆流接触，从而可以得到含有羰基镍、羰基铁和一氧化碳的气态混合物以及铁粉。发明人发现，采用高活性的镍铁粉与一氧化碳直接接触即可反应生成羰基化合物，并且羰基化合物合成率较高，与现有技术相比，本发明在羰基化合物合成过程中并不需要加入催化剂，从而缩短了工艺流程。 Carbonylation Unit 400: According to an embodiment of the invention, the oxo synthesis unit 400 has a carbon monoxide inlet 401, a nickel iron powder inlet 402, a gaseous mixture outlet 403 and an iron powder outlet 404, the nickel iron powder inlet 402 and the nickel iron powder outlet 302 being connected, It is also suitable for countercurrent contact of nickel iron powder with carbon monoxide, so that a gaseous mixture containing nickel carbonyl, iron carbonyl and carbon monoxide and iron powder can be obtained. The inventors have found that the use of highly active nickel iron powder in direct contact with carbon monoxide can react to form a carbonyl compound, and the synthesis rate of the carbonyl compound is relatively high. Compared with the prior art, the present invention does not require the addition of a catalyst during the synthesis of the carbonyl compound. , thus shortening the process flow.
根据本发明的一个实施例，镍铁粉与一氧化碳反应条件并不受特别限制，本领域技术人员可以根据实际需要进行选择，根据本发明的具体实施例，镍铁粉与一氧化碳接触可以在110～230摄氏度和2～10MPa的条件下进行30～42小时。由此，可以显著提高羰基化合物的合成率。According to an embodiment of the present invention, the reaction conditions of the nickel iron powder and the carbon monoxide are not particularly limited, and those skilled in the art can select according to actual needs. According to a specific embodiment of the present invention, the nickel iron powder can be contacted with carbon monoxide at 110~. It is carried out at 230 ° C and 2 to 10 MPa for 30 to 42 hours. Thereby, the synthesis rate of the carbonyl compound can be remarkably improved.
提纯装置500：根据本发明的实施例，提纯装置500具有气态混合物入口501、气态羰基镍出口502和第一一氧化碳出口503，气态混合物入口501与气态混合物出口403相连，且适于将含有羰基镍、羰基铁和一氧化碳的气态混合物进行提纯处理，从而可以分别得到气态羰基镍和第一一氧化碳。由此，可以显著提高后续所得羰基镍粉的纯度。该步骤中，具体的，首先将羰基镍、羰基铁和一氧化碳的气态混合物进行冷凝处理，气态混合物中的羰基镍和羰基铁冷凝变为液体，而其中的一氧化碳则以气体形式存在，然后对所得含有羰基镍和羰基铁的液态混合物进行精馏处理，从而可以分离得到高纯度的气态羰基镍。需要说明的是，本领域技术人员可以根据实际需要对所采用冷凝和精馏的具体操作条件进行选择。Purification apparatus 500: According to an embodiment of the invention, purification apparatus 500 has a gaseous mixture inlet 501, a gaseous nickel carbonyl outlet 502, and a first carbon monoxide outlet 503, and a gaseous mixture inlet 501 is coupled to the gaseous mixture outlet 403 and is adapted to contain nickel carbonyl A gaseous mixture of carbonyl iron and carbon monoxide is purified to obtain gaseous nickel carbonyl and first carbon monoxide, respectively. Thereby, the purity of the subsequently obtained nickel carbonyl powder can be remarkably improved. In this step, specifically, a gaseous mixture of nickel carbonyl, carbonyl iron and carbon monoxide is first condensed, and the nickel carbonyl and the carbonyl iron in the gaseous mixture are condensed into a liquid, and the carbon monoxide therein is present in the form of a gas, and then the resulting The liquid mixture containing nickel carbonyl and iron carbonyl is subjected to rectification treatment, whereby high purity gaseous nickel carbonyl can be isolated. It should be noted that the specific operating conditions of the condensation and rectification employed may be selected by those skilled in the art according to actual needs.
分解装置600：根据本发明的实施例，分解装置600具有气态羰基镍入口601、羰基镍粉出口602和第二一氧化碳出口603，气态羰基镍入口601和气态羰基镍出口502相连，且适于将气态羰基镍进行分解处理，从而可以分别得到羰基镍粉和第二一氧化碳。具体的，羰基镍不稳定，在加热时可以迅速分解为镍和一氧化碳，从而可以得到高纯度的羰基镍粉。需要说明的是，本领域技术人员可以根据实际需要对分解处理的条件进行选择。Decomposition device 600: According to an embodiment of the invention, the decomposition device 600 has a gaseous nickel carbonyl inlet 601, a nickel carbonyl powder outlet 602 and a second carbon monoxide outlet 603, the gaseous nickel carbonyl inlet 601 and the gaseous nickel carbonyl outlet 502 are connected, and is suitable for The gaseous nickel carbonyl is decomposed to obtain nickel carbonyl powder and second carbon monoxide, respectively. Specifically, the nickel carbonyl is unstable and can be rapidly decomposed into nickel and carbon monoxide upon heating, so that high-purity nickel carbonyl powder can be obtained. It should be noted that those skilled in the art can select the conditions of the decomposition process according to actual needs.
根据本发明实施例的利用红土镍矿制备羰基镍粉的***采用红土镍矿作为制备羰基镍粉的原料，虽然红土镍矿中镍的品位较低，但是采用本发明的***仍可以制备得到高纯度的羰基镍粉，从而在拓宽原料来源的同时降低羰基镍粉的生产成本，同时通过采用高硫煤作为还原剂，不仅可以有效还原红土镍矿中的镍铁氧化物，而且可以得到高活性的高硫镍铁粉，由于镍铁粉中的硫在羰化合成反应过程中起催化活化作用，从而使其与一氧化碳直接接触即可反应生成羰基化合物，并且羰基化合物合成率较高，与现有技术相比，本发明在羰基化合物合成过程中并不需要加入催化剂，从而缩短了工艺流程，其次通过对冶炼过程所得金属化球团进行水淬处理，可以有助于含硫物均匀分散在金属化球团中，从而可以得到具有疏松结构的高活性镍铁粉，并且经过磨矿磁选处理所得镍铁粉具有较细的粒径，从而可以显著提高与一氧化碳的接触面积，进而进一步提高羰基化合物合成率，另外采用廉价的高硫煤作为还原剂，不仅可以有效降低生产成本，而且可以使得其中的硫作为有益成分被应用到羰基化合物合成过程中，且在羰基化合物合成过程中不产生气态含硫物，不会造成大气污染。The system for preparing nickel carbonyl powder by using laterite nickel ore according to an embodiment of the present invention uses laterite nickel ore as a raw material for preparing nickel carbonyl powder. Although the grade of nickel in the laterite nickel ore is low, the system of the present invention can still be prepared high. Purity of nickel carbonyl powder, which can reduce the production cost of nickel carbonyl powder while broadening the source of raw materials, and at the same time, by using high sulfur coal as a reducing agent, not only can nickel iron oxide in the laterite nickel ore be effectively reduced, but also high activity can be obtained. The high-sulfur nickel-iron powder, because the sulfur in the nickel-iron powder plays a catalytic activation during the carbonylation synthesis reaction, so that it can react with carbon monoxide to react to form a carbonyl compound, and the carbonyl compound has a high synthesis rate. Compared with the prior art, the invention does not need to add a catalyst in the synthesis process of the carbonyl compound, thereby shortening the process flow, and secondly, by subjecting the metallized pellet obtained in the smelting process to water quenching treatment, the sulfur-containing substance can be uniformly dispersed in the process. Metallized pellets, thereby obtaining a highly active nickel-iron powder having a loose structure and being subjected to grinding The obtained ferronickel powder has a fine particle diameter, thereby significantly increasing the contact area with carbon monoxide, thereby further increasing the synthesis rate of the carbonyl compound, and using inexpensive high-sulfur coal as a reducing agent, not only can effectively reduce the production cost, but also The sulfur is applied as a beneficial component to the synthesis process of the carbonyl compound, and no gaseous sulfur-containing substance is generated during the synthesis of the carbonyl compound, and no air pollution is caused.
参考图5，根据本发明的实施例，第一一氧化碳出口503与一氧化碳入口401相连，且 适于将提纯装置500分离所得第一一氧化碳返回至羰基合成装置400与镍铁粉接触，从而可以显著提高一氧化碳循环利用率。Referring to FIG. 5, according to an embodiment of the present invention, a first carbon monoxide outlet 503 is connected to a carbon monoxide inlet 401, and The first carbon monoxide suitable for separating the purification device 500 is returned to the oxo synthesis unit 400 in contact with the nickel iron powder, so that the carbon monoxide cycle utilization ratio can be remarkably improved.
参考图6，根据本发明的实施例，第二一氧化碳出口603与一氧化碳入口401相连，且适于将分解装置600分解所得第二一氧化碳返回至羰基合成装置400与镍铁粉接触，从而可以进一步提高一氧化碳循环利用率。Referring to FIG. 6, according to an embodiment of the present invention, the second carbon monoxide outlet 603 is connected to the carbon monoxide inlet 401, and is adapted to return the second carbon monoxide decomposed by the decomposition device 600 to the oxo synthesis device 400 for contact with the nickel iron powder, thereby further improving Carbon monoxide cycle utilization.
下面参考具体实施例，对本发明进行描述，需要说明的是，这些实施例仅仅是描述性的，而不以任何方式限制本发明。The invention is described below with reference to the specific embodiments, which are intended to be illustrative, and not to limit the invention in any way.
实施例1Example 1
取镍含量为1.56wt％的红土镍矿，配入硫含量为4％的高硫煤、工业碱混匀后制球并烘干，其中，红土镍矿、高硫煤和工业碱按照质量比为100：17：5％进行混合，干燥后的混合球团布入转底炉进行冶炼，冶炼条件1300℃，时间35min，还原后的金属化球团经水淬-磨矿-磁选装置处理后得到镍含量6.5wt％，铁含量68.6wt％，S含量2.0wt％的镍铁粉，产品平均粒径25μm，将镍铁粉送入羰基合成装置内与CO逆流接触发生羰化反应生成含有羰基镍和羰基铁气态混合物，羰化条件为：压力7MPa，温度180℃，时间35h，CO气体浓度85％，合成率96％，将含有羰基镍和羰基铁气态混合物输送至冷凝器内冷凝成液态羰基化合物，再送入精馏塔进行精馏得到高纯气态羰基镍，最后将气态羰基镍送入分解装置进行分解得到镍含量99.5wt％的羰基镍粉，经铁粉再选装置选出的铁粉中铁含量为73wt％。The laterite nickel ore with a nickel content of 1.56wt% is blended with high-sulfur coal with a sulfur content of 4% and mixed with an industrial alkali to form a ball and dried. The laterite nickel ore, high-sulfur coal and industrial alkali are mass-produced according to the mass ratio. 100:17:5% mixing, the dried mixed pellets were placed in a rotary hearth furnace for smelting, the smelting conditions were 1300 ° C, time 35 min, and the reduced metallized pellets were treated by a water quenching-grinding-magnetic separation device. A nickel iron powder having a nickel content of 6.5 wt%, an iron content of 68.6 wt%, and an S content of 2.0 wt% is obtained. The average particle size of the product is 25 μm. The nickel iron powder is fed into the oxo unit and reacted with CO in a countercurrent contact to form a carbonyl group. A gaseous mixture of nickel and carbonyl iron, carbonylation conditions: pressure 7 MPa, temperature 180 ° C, time 35 h, CO gas concentration 85%, synthesis rate 96%, the gaseous mixture containing nickel carbonyl and carbonyl iron is sent to the condenser to condense into a liquid The carbonyl compound is sent to a rectification column for rectification to obtain a high-purity gaseous nickel carbonyl. Finally, the gaseous nickel carbonyl is sent to a decomposition device for decomposition to obtain a nickel carbonyl powder having a nickel content of 99.5 wt%, and iron selected by an iron powder re-election device. The iron content in the powder is 73wt .
实施例2Example 2
取镍含量为1.75wt％的红土镍矿，配入硫含量为7％的高硫煤、石灰石混匀后制球并烘干，其中，红土镍矿、高硫煤和石灰石按照质量比为100：12：10进行混合，干燥后的混合球团布入转底炉进行冶炼，冶炼条件1280℃，时间45min，还原后的金属化球团经水淬-磨矿-磁选装置处理后得到镍含量7.2wt％，铁含量71.43wt％，S含量3.0wt％的镍铁粉，产品平均粒径30μm，将镍铁粉送入羰基合成装置内与CO逆流接触发生羰化反应生成含有羰基镍和羰基铁气态混合物，羰化条件为：压力3MPa，温度130℃，时间42h，CO气体浓度90％，合成率95％，将含有羰基镍和羰基铁气态混合物输送至冷凝器内冷凝成液态羰基化合物，再送入精馏塔进行精馏得到高纯气态羰基镍，最后将气态羰基镍送入分解装置进行分解得到镍含量99.5wt％的羰基镍粉，经铁粉再选装置选出的铁粉中铁含量为77wt％。The laterite nickel ore with a nickel content of 1.75wt% is blended with high-sulfur coal and limestone with a sulfur content of 7%, and then ball is prepared and dried. The laterite nickel ore, high-sulfur coal and limestone are in a mass ratio of 100: The mixture was mixed at 12:10, and the dried pellets were placed in a rotary hearth furnace for smelting. The smelting conditions were 1280 ° C for 45 min. The reduced metallized pellets were treated with a water quenching-grinding-magnetic separation device to obtain nickel content. 7.2wt%, iron content 71.43wt%, S content 3.0wt% nickel iron powder, the average particle size of the product is 30μm, the nickel iron powder is sent into the oxo unit and reacted with CO in a countercurrent contact to form a carbonyl containing reaction to form nickel carbonyl and carbonyl. The gaseous mixture of iron, the carbonylation conditions are: pressure 3MPa, temperature 130 ° C, time 42h, CO gas concentration 90%, synthesis rate 95%, the gaseous mixture containing nickel carbonyl and carbonyl iron is sent to the condenser to condense into a liquid carbonyl compound, Then, it is sent to the rectification column for rectification to obtain high-purity gaseous nickel carbonyl. Finally, the gaseous nickel carbonyl is sent to a decomposition device for decomposition to obtain nickel carbonyl powder having a nickel content of 99.5 wt%, and iron content in the iron powder selected by the iron powder re-election device. 77% by weight .
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针 对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。In the description of the present specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" and the like means a specific feature described in connection with the embodiment or example. A structure, material or feature is included in at least one embodiment or example of the invention. In this specification, the schematic representation of the above terms does not necessarily require a needle The same is true for the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in a suitable manner in any one or more embodiments or examples. In addition, various embodiments or examples described in the specification, as well as features of various embodiments or examples, may be combined and combined.
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。 Although the embodiments of the present invention have been shown and described, it is understood that the above-described embodiments are illustrative and are not to be construed as limiting the scope of the invention. The embodiments are subject to variations, modifications, substitutions and variations.

Claims (9)

  1. 一种利用红土镍矿制备羰基镍粉的方法，其特征在于，包括：A method for preparing nickel carbonyl powder by using laterite nickel ore, characterized in that it comprises:
    (1)将红土镍矿、高硫煤和添加剂进行混合造球，以便得到混合球团；(1) mixing red earth nickel ore, high sulfur coal and additives to obtain a mixed pellet;
    (2)将所述混合球团进行还原冶炼处理，以便得到金属化球团；(2) subjecting the mixed pellets to reduction smelting treatment to obtain metallized pellets;
    (3)将所述金属化球团进行水淬-磨矿-磁选处理，以便分别得到镍铁粉和尾矿；(3) subjecting the metallized pellets to water quenching-grinding-magnetic separation treatment to obtain nickel iron powder and tailings, respectively;
    (4)将所述镍铁粉与一氧化碳接触，以便得到含有羰基镍、羰基铁和一氧化碳的气态混合物以及铁粉；(4) contacting the nickel iron powder with carbon monoxide to obtain a gaseous mixture containing nickel carbonyl, iron carbonyl and carbon monoxide, and iron powder;
    (5)将所述含有羰基镍、羰基铁和一氧化碳的气态混合物进行提纯处理，以便分别得到气态羰基镍和第一一氧化碳；以及(5) purifying the gaseous mixture containing nickel carbonyl, carbonyl iron and carbon monoxide to obtain gaseous nickel carbonyl and first carbon monoxide, respectively;
    (6)将所述气态羰基镍进行分解处理，以便分别得到羰基镍粉和第二一氧化碳。(6) The gaseous nickel carbonyl is subjected to decomposition treatment to obtain nickel carbonyl powder and second carbon monoxide, respectively.
  2. 根据权利要求1所述的方法，其特征在于，进一步包括：The method of claim 1 further comprising:
    (7)将所述第一一氧化碳返回至步骤(4)与所述镍铁粉接触。(7) returning the first carbon monoxide to the step (4) in contact with the nickel iron powder.
  3. 根据权利要求1所述的方法，其特征在于，进一步包括：The method of claim 1 further comprising:
    (8)将所述第二一氧化碳返回至步骤(4)与所述镍铁粉接触。(8) returning the second carbon monoxide to the step (4) in contact with the nickel iron powder.
  4. 根据权利要求1所述的方法，其特征在于，在步骤(1)中，所述高硫煤中硫含量高于3wt％。The method according to claim 1, wherein in the step (1), the sulfur content in the high sulfur coal is higher than 3% by weight.
  5. 根据权利要求4所述的方法，其特征在于，在步骤(1)中，所述添加剂为选自钾盐、钠盐、钙盐、碱金属氧化物和碱土金属氧化物中的至少一种。The method according to claim 4, wherein in the step (1), the additive is at least one selected from the group consisting of a potassium salt, a sodium salt, a calcium salt, an alkali metal oxide, and an alkaline earth metal oxide.
  6. 一种利用红土镍矿制备羰基镍粉的***，其特征在于，包括：A system for preparing nickel carbonyl powder by using laterite nickel ore, characterized by comprising:
    混合造球装置，所述混合造球装置具有红土镍矿入口、高硫煤入口、添加剂入口和混合球团出口，且适于将红土镍矿、高硫煤和添加剂进行混合造球，以便得到混合球团；a mixing pelletizing device having a laterite nickel ore inlet, a high sulfur coal inlet, an additive inlet, and a mixing pellet outlet, and is suitable for mixing a laterite nickel ore, a high sulfur coal, and an additive to obtain Mixed pellets;
    还原冶炼装置，所述还原冶炼装置具有混合球团入口和金属化球团出口，所述混合球团入口和所述混合球团出口相连，且适于将所述混合球团进行还原冶炼处理，以便得到金属化球团；a reduction smelting apparatus having a mixing pellet inlet and a metallized pellet outlet, the mixing pellet inlet being connected to the mixing pellet outlet, and adapted to perform the reduction smelting treatment of the mixing pellet In order to obtain metallized pellets;
    水淬-磨矿-磁选装置，所述水淬-磨矿-磁选装置具有金属化球团入口、镍铁粉出口和尾矿出口，所述金属化球团入口与所述金属化球团出口相连，且适于将所述金属化球团进行水淬-磨矿-磁选处理，以便分别得到镍铁粉和尾矿；a water quenching-grinding-magnetic separation device having a metallized pellet inlet, a nickel iron powder outlet, and a tailings outlet, the metallized pellet inlet and the metallized sphere The group outlet is connected, and is suitable for performing water quenching-grinding-magnetic separation treatment on the metallized pellets to obtain nickel iron powder and tailings respectively;
    羰基合成装置，所述羰基合成装置具有一氧化碳入口、镍铁粉入口、气态混合物出口和铁粉出口，所述镍铁粉入口和所述镍铁粉出口相连，且适于将所述镍铁粉与一氧化碳接触，以便得到含有羰基镍、羰基铁和一氧化碳的气态混合物以及铁粉；An oxo synthesis apparatus having a carbon monoxide inlet, a nickel iron powder inlet, a gaseous mixture outlet, and an iron powder outlet, the nickel iron powder inlet being connected to the nickel iron powder outlet, and adapted to be the nickel iron powder Contacting with carbon monoxide to obtain a gaseous mixture containing nickel carbonyl, iron carbonyl and carbon monoxide, and iron powder;
    提纯装置，所述提纯装置具有气态混合物入口、气态羰基镍出口和第一一氧化碳出口， 所述气态混合物入口与所述气态混合物出口相连，且适于将所述含有羰基镍、羰基铁和一氧化碳的气态混合物进行提纯处理，以便分别得到气态羰基镍和第一一氧化碳；以及a purification apparatus having a gaseous mixture inlet, a gaseous nickel carbonyl outlet, and a first carbon monoxide outlet, The gaseous mixture inlet is connected to the gaseous mixture outlet and is adapted to purify the gaseous mixture containing nickel carbonyl, carbonyl iron and carbon monoxide to obtain gaseous nickel carbonyl and first carbon monoxide, respectively;
    分解装置，所述分解装置具有气态羰基镍入口、羰基镍粉出口和第二一氧化碳出口，所述气态羰基镍入口和所述气态羰基镍出口相连，且适于将所述气态羰基镍进行分解处理，以便分别得到羰基镍粉和第二一氧化碳。a decomposition apparatus having a gaseous nickel carbonyl inlet, a nickel carbonyl powder outlet, and a second carbon monoxide outlet, the gaseous nickel carbonyl inlet being connected to the gaseous nickel carbonyl outlet, and adapted to decompose the gaseous nickel carbonyl In order to obtain nickel carbonyl powder and second carbon monoxide, respectively.
  7. 根据权利要求6所述的***，其特征在于，所述还原冶炼装置为选自转底炉、回转窑和隧道窑中的至少一种。The system according to claim 6, wherein said reduction smelting means is at least one selected from the group consisting of a rotary hearth furnace, a rotary kiln and a tunnel kiln.
  8. 根据权利要求6所述的***，其特征在于，所述第一一氧化碳出口与所述一氧化碳入口相连，且适于将所述第一一氧化碳返回所述羰基合成装置与所述镍铁粉接触。The system of claim 6 wherein said first carbon monoxide outlet is connected to said carbon monoxide inlet and is adapted to return said first carbon monoxide to said oxo unit in contact with said nickel iron powder.
  9. 根据权利要求6所述的***，其特征在于，所述第二一氧化碳出口与所述一氧化碳入口相连，且适于将所述第二一氧化碳返回所述羰基合成装置与所述镍铁粉接触。 The system of claim 6 wherein said second carbon monoxide outlet is coupled to said carbon monoxide inlet and adapted to return said second carbon monoxide to said oxo unit for contact with said nickel iron powder.
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CN107138163A (en) * 2017-06-09 2017-09-08 太原理工大学 A kind of utilization lateritic nickel ore prepares method and the application of synthetic methane catalyst
CN110732679A (en) * 2019-11-06 2020-01-31 合肥学院 nanometer zero-valent iron-nickel composite material prepared based on laterite-nickel ore and method thereof
CN114014373A (en) * 2021-10-22 2022-02-08 金川镍钴研究设计院有限责任公司 Process method for producing carbonyl nickel powder and carbonyl iron powder from nickel iron particles

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CN107138163A (en) * 2017-06-09 2017-09-08 太原理工大学 A kind of utilization lateritic nickel ore prepares method and the application of synthetic methane catalyst
CN110732679A (en) * 2019-11-06 2020-01-31 合肥学院 nanometer zero-valent iron-nickel composite material prepared based on laterite-nickel ore and method thereof
CN110732679B (en) * 2019-11-06 2022-07-01 合肥学院 Nano zero-valent iron-nickel composite material prepared based on laterite-nickel ore and preparation method thereof
CN114014373A (en) * 2021-10-22 2022-02-08 金川镍钴研究设计院有限责任公司 Process method for producing carbonyl nickel powder and carbonyl iron powder from nickel iron particles

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