CN103193213B - Method for comprehensively utilizing low-grade phosphate ores - Google Patents

Method for comprehensively utilizing low-grade phosphate ores Download PDF

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CN103193213B
CN103193213B CN201310145437.XA CN201310145437A CN103193213B CN 103193213 B CN103193213 B CN 103193213B CN 201310145437 A CN201310145437 A CN 201310145437A CN 103193213 B CN103193213 B CN 103193213B
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胡雷
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Abstract

The invention discloses a method for comprehensively utilizing low-grade phosphate ores. In the traditional method, acid phosphate is used as a catalyst to participate in a reaction and used for removing iron and recovering iron hydroxide and phosphate radicals, the investment is increased because novel working sections and equipment are additionally provided in the process, and in addition, the liquid-solid separation process is more difficult because the iron hydroxide is a colloid. The method comprises the following steps of: carrying out ball-milling treatment on nickel laterite ores and low-grade phosphate ores in respective ore grinding systems; mixing the obtained nickel laterite ores and low-grade phosphate ores and concentrated hydrochloric acid with the mass percentage of 20-35%, and carrying out leaching reaction; carrying out solid-liquid separation on the obtained leaching residues and leaching liquid in a filter press, wherein the residue cleaning process is also carried out in the filter press; and mixing a cleaning solution and the leaching liquid, settling by using lime milk to obtain chromium, and then, carrying out a nickel settlement reaction and a magnesium settlement reaction by using the lime milk. According to the invention, the characteristics of components of the phosphate ores and the nickel laterite ores are reasonably utilized, and the comprehensive utilization of the leaching residues of the nickel laterite ores is realized.

Description

A kind of method that fully utilizes low-grade phosphate ore stone
Technical field
The present invention relates to non-ferrous metal hydrometallurgy field, specifically a kind of method that fully utilizes low-grade phosphate ore stone.
Background technology
The method of wet processing low-grade phosphate ore stone is mainly both at home and abroad at present: first low-grade phosphate ore stone is carried out to floating and enriching processing, make the P in mineral aggregate 2o 5content being promoted to more than 30% below 25% in raw ore, take sulfuric acid and Rock Phosphate (72Min BPL) carries out Leaching reaction as raw material again, generate the leach liquor of phosphoric acid and the leached mud (being commonly called as phosphogypsum) of sulfur acid calcium, the leach liquor of phosphoric acid can make purification of phosphoric acid or phosphoric acid salt goods after purification, phosphogypsum is stored up processing, because a large amount of phosphogypsums exists, environment is threatened, in the comprehensive utilization of phosphogypsum, done at present a large amount of research work both at home and abroad, for example: using phosphogypsum application in cement industry as cement additire, the technical study of preparing calcium sulphate whiskers from ardealite, phosphogypsum calcining is prepared active calcium oxide and is reclaimed sulfurous gas relieving haperacidity technology etc. simultaneously, these research work have obtained progress to a certain extent, yet, the problem of utilizing of phosphogypsum remains a large technical difficult problem in phosphorous chemical industry field.
At present both at home and abroad in Rock Phosphate (72Min BPL) except phosphoric other element utilize present situation: in Rock Phosphate (72Min BPL), except containing phosphoric, the composition of another one maximum is CaO, and its content is in 50% left and right; Also have MgO, K 2the content of the compositions such as O is also higher, and these compositions, in the treating processes of Rock Phosphate (72Min BPL), are used as impurity discarded mostly at present; In the Rock Phosphate (72Min BPL) on the ground such as Guizhou, also contain the rare earth elements such as yttrium oxide of content 0.08% left and right, because its high added value has been subject to the attention of some research institutions.
The method of wet processing low-grade laterite nickel ore is both at home and abroad at present:
(1) normal pressure sulfuric acid leaching: the method is to take sulfuric acid as leaching agent, controls the reaction conditionss such as certain liquid-solid ratio, acidity, temperature, under normal pressure, the metals such as nickel, cobalt, iron, magnesium is leached from mineral aggregate; Then add neutralizing agent (Wingdale, calcium hydroxide, or other alkaline matter) impurity such as iron, aluminium, silicon are removed, after the press filtration of removal of impurities ore pulp, obtain nickel sulfate solution and scrap slag, scrap slag after washery slag outside row, nickel sulfate solution uses sodium hydroxide (or calcium hydroxide, magnesium hydroxide) to sink nickel reactant; The nickel slag that obtains is molten through acid, obtain the deep processed product of nickel cobalt after abstraction impurity removal; Liquid evaporative crystallization reclaim(ed) sulfuric acid magnesium after heavy nickel, or directly add alkaline matter (Wingdale, calcium hydroxide, sodium carbonate etc.) to carry out precipitation process, after the processing obtaining, liquid is arranged outward; This treatment process is metal target owing to only take nickel, cobalt and a small amount of magnesium, and the rate of recovery of magnesium is low, and acid and alkali consumption is high, and the quantity of slag is large and cannot fully utilize, thereby causes production cost high.
(2) high pressure sulfuric acid leaching: the method is to take sulfuric acid as leaching agent, controls certain temperature of reaction, in pressurization situation, laterite is processed, pressurized acid leaching technique starts from the hair Ah (MOA) of Cuba's the 1950's the earliest, Mu Lin-the Mu Lin of Australia after the nineties in 20th century, Bu Long, examining the pressurized acid leaching factories such as gas goes into operation in succession, but aspect technology and equipment, there are many problems, the basic procedure of this technique is that ore enters autoclave through high pressure (4-5MPa) after broken slurrying, high temperature (230-260 ℃) acidic leaching, after leaching, carry out liquid-solid separation, then leach liquor is neutralized, deironing, after deironing, liquid carries out Separation of nickel and cobalt by extraction, also can need further to smelt and obtain different nickel cobalt products according to difference, the rate of recovery of this technique nickel cobalt can reach more than 90%, but this technology investment cost is large, stricter to the requirement of equipment and material, because the impurity such as magnesium are larger for the impact of sulfuric acid consumption, so this technique is applicable to processing containing magnesium, be less than 10%, be particularly less than 5% red soil nickel ore, in addition, in this process operation process, equipment is prone to scale formation, affect greatly, and cost of equipment maintenance is high to producing, and slag cannot rationally utilize, and the existence of this series of problems makes the large-area applications popularization of the method be subject to certain impact.
Therefore (3) reduction roasting-ammonia leaching method: reduction roasting-ammonia leaching technique is invented by professor Caron, claims again Caron flow process, and wherein, ammonia soaks and in process, adopts NH 3and CO 2nickel in roasted ore and cobalt are converted into ammonia complex and enter solution, the advantage of this technique is that reagent can recycle, consumption is little, shortcoming is that nickel and cobalt recovery rate is low, nickel and cobalt recovery rate is respectively 75% and 60% left and right, and because mineral aggregate need to be dried roasting, energy consumption is larger, can not realize the comprehensive reutilization of resource.
The iron removal technology of at present domestic and international low-grade laterite nickel ore leach liquor: wet processing red soil nickel ore, the iron in leach liquor is all as impurity removal, deironing has three kinds of methods, neutralization precipitation method, goethite process and yellow modumite method conventionally.In addition, also have scholar's research to adopt the way of extraction deironing to remove at low temperatures the iron in leach liquor, reclaim iron product simultaneously.Adopt this several method deironing, all can obtain good de-ferrous effect; But it is exactly need to increase independent workshop section to carry out the processing of ferro element that these methods have a common feature, caused the input of artificial and equipment to increase, technical process extends, and investment expands.
Chinese Patent Application No. 200910095079.X discloses nickel ferro-cobalt magnesium in a kind of normal temperature and pressure high efficiency extraction red soil nickel ore and has utilized the method for waste residue, the method in red soil nickel ore leaching process, used acid phosphate as catalyzer in order to improve the leaching yield of metal; After solid-liquid separation, in leach liquor iron removal, also with acid phosphate, carry out deironing, and phosphate radical is reclaimed and produces ironic hydroxide product simultaneously; In leach liquor in Ni, Co, the isoionic precipitation process of Mg, used sodium carbonate as alkali source, be settled out nickelous carbonate, cobaltous carbonate and magnesiumcarbonate product, and in follow-up treating processes, calcine self-produced part magnesiumcarbonate product and prepare magnesium oxide, magnesia digestion turns back to removal of impurities and precipitates in rough cobalt nickel product process as alkali after sizing mixing and uses; Meanwhile, in technological process, sodium product has been carried out to evaporation concentration recovery.The omnidistance alkali source using of this technical process is sodium carbonate, use, but its alkalescence of tracing to its source comes from sodium carbonate even if returned to during the course the magnesium oxide of part as alkali, and alkali supplementary product onsumption is with high costs; This flow process adopts acid phosphate to make catalyzer and participates in reaction, and because acid phosphate belongs to Chemicals, procurement price is higher, causes production auxiliary materials with high costs; This flow process is used acid phosphate deironing, and reclaims ironic hydroxide and phosphate radical, and this process has increased new workshop section and equipment, causes increase of investment, and ironic hydroxide is colloid, and liquid-solid sepn process is difficulty comparatively, can in production implementation process, bring inconvenience; This flow process has been carried out evaporation concentration recovery to sodium product, and because the series product added values such as sodium sulfate are extremely low, the concentration in this system is also lower, and the mode of employing evaporation concentration reclaims need do corresponding assessment in economy; In sum, also there is certain problem in the method in industrial applications.
The selection of acid source and alkali source in red soil nickel ore wet smelting process: in the selection of acid source, choice for use sulfuric acid is in the majority as acid source, in the selection of alkali source with the basic salt (sodium carbonate of sodium, sodium hydroxide etc.) be main, Chinese Patent Application No. 201210202583.7 disclose a kind of from red soil nickel ore the method for comprehensively recovering valuable metal, the method has been used sulfuric acid as acid source, using milk of lime as alkali source, the defect that this soda acid source is selected is to receive chromium with milk of lime, with milk of lime, sinking nickel, and in the product of the heavy magnesium with milk of lime more or less be entrained with calcium sulfate, the disadvantageous effect that the existence of this part calcium sulfate brings has following two aspects: the one, caused the purity drop of product, the 2nd, in the molten process of acid, calcium sulfate dissolves and enters into leach liquor, calcium ion wherein subsequently can be in workshop section's foulings such as extractions, technique is affected greatly.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defect that above-mentioned prior art exists, a kind of method that fully utilizes low-grade phosphate ore stone is provided, the method takes into full account low-grade phosphate ore stone and red soil nickel ore composition feature, comprehensively reclaims the elements such as phosphorus, calcium, nickel, cobalt, chromium, magnesium.
For this reason, the present invention adopts following technical scheme: a kind of method that fully utilizes low-grade phosphate ore stone, and its step is as follows:
1) red soil nickel ore and low-grade phosphate ore stone are carried out to ball-milling processing in ore grinding system separately, and the mineral aggregate after ball milling is dewatered, obtain red soil nickel ore and the low-grade phosphate ore stone of water ratio≤35%;
2) by step 1) red soil nickel ore that obtains and low-grade phosphate ore stone is 20-35% with mass percent concentrated hydrochloric acid mixes, carry out Leaching reaction, by controlling pH value, the temperature and time of Leaching reaction, most Fe that leach are reacted with the phosphate radical of leaching, generating tertiary iron phosphate precipitation enters in leached mud, make most Ni, Co, Mg and Ca Elements Leaching enter in leach liquor simultaneously, due to the existence of tertiary iron phosphate in slag, can significantly improve the separating and filtering speed of leached mud and leach liquor;
3) by step 2) leached mud and the leach liquor that obtain carry out solid-liquid separation in pressure filter, because tertiary iron phosphate is present in slag, make leached mud nutrient laden, leached mud need be used appropriate reuse water to wash, washery slag process is also carried out in pressure filter, the washing lotion obtaining is mixed into receipts chromium with leach liquor and reacts, and the batching as phosphate fertilizer or composite fertilizer after revolution kiln dry of the leached mud after washing is used, and leached mud is turned waste into wealth;
4) washing lotion and leach liquor first precipitate and receive chromium with milk of lime, sink nickel reactant and heavy reactive magnesium more afterwards with milk of lime.
Problem solved by the invention: (1) low-grade phosphate ore stone low cost is utilized problem; (2) problem of complex utilization of the element such as calcium, magnesium in low-grade phosphate ore stone; (3) the difficult problem of the filtration of red soil nickel ore peracid Leaching reaction; (4) the low cost production problem of calcium chloride product in system; (5) the reasonable processing problem of red soil nickel ore leached mud; (6) low-cost high-efficiency reclaims in laterite the metals such as nickel cobalt magnesium.
The present invention first carries out total immersion reaction by the low-grade phosphate ore stone of milled and red soil nickel ore under hydrochloric acid system, make ferro element in laterite and the phosphoric in Rock Phosphate (72Min BPL) when nickel, calcium plasma leach, the precipitation that forms tertiary iron phosphate enters into slag, make leached mud nutrient laden, turn waste into wealth, significantly improve solid-liquid separation filtration velocity, significantly enhance productivity simultaneously; Calcium ion in Rock Phosphate (72Min BPL) exists in leach liquor with calcium chloride form, for subsequent production calcium chloride is laid a good foundation, has also rationally utilized the calcium resource in Rock Phosphate (72Min BPL); In leaching process, use hydrochloric acid as acid source, leach liquor is used milk of lime as alkali source, and the one, significantly reduced cost of supplementary product, the 2nd, improved the calcium chloride concentration in leach liquor, the 3rd, improved the isoionic product purity of milk of lime coprecipitated nickel hydroxide cobalt magnesium.Technical process is short, produces comprehensive cost cheap.
As further technical scheme of the present invention:
The detailed process of described receipts chromium reaction is as follows: control reaction pH at 3.5-4.5, control temperature and reaction times, when receiving chromium, remove Al, Si in leach liquor and a small amount of Fe impurity, after reaction slurry filtration separation, obtain liquid and chromium slag after dechromisation, owing to existing without calcium sulfate, can make the chromium content in chromium slag improve.Chromium slag washs with reuse water in pressure filter, and the slag washing water obtaining enters one section of heavy nickel reactant.
The detailed process of described heavy nickel reactant is as follows: in liquid after dechromisation, add milk of lime to carry out one section of heavy nickel reactant, control pH at 7.5-8.5, filtration obtains liquid after one section of nickel hydroxide slag and one section of heavy nickel, one section of nickel hydroxide slag washs with tap water or steam condensate, washing lotion enters Er Duanchen nickel workshop section, and the one section of nickel hydroxide slag acid after washing is molten, acid solution is prepared cobalt nickel product through extracting refining process; In liquid after one section of heavy nickel, add milk of lime to carry out two sections of heavy nickel reactants, control pH at 8.5-9.5, filter and obtain liquid after two sections of nickel hydroxide slags and two sections of heavy nickel, this part two sections of nickel hydroxide slag returns to Leaching reaction after sizing mixing with reuse water.
The detailed process of described heavy reactive magnesium is as follows: toward adding in liquid after two sections of heavy nickel milk of lime to sink reactive magnesium, control pH at 10.0-11.0, filtration obtains liquid after magnesium hydroxide and heavy magnesium, magnesium hydroxide is with filtering after tap water or vapor condensation water washing, filtrate is arranged outward, filter residue dry after as magnesium products; After heavy magnesium, in liquid, be mainly calcium chloride composition, after most of heavy magnesium, liquid returns to former process as reuse water, as leaching process size mixing water, leach slag washing water, milk of lime preparation water, high chromium slag bath water and the two sections of heavy nickel slags water of sizing mixing and use, realize the circulation enrichment of calcium chloride; Unnecessary reuse water is opened a way and is dried workshop section's production anhydrous chlorides of rase calcium product to evaporation concentration, rotary kiln, and the water of condensation that evaporation concentration produces is used as the interpolation water of one section of nickel hydroxide slag of washing and magnesium hydroxide slag.Two sections of heavy nickel are in order to improve the purity of nickel yield and raising magnesium products.
The aggregate diameter of the red soil nickel ore after ball milling and low-grade phosphate ore stone at 100 orders with interior ratio >=95%.
The add-on of Rock Phosphate (72Min BPL) is as the criterion below so that the Fe concentration of leach liquor is down to 1g/L.
The reuse water of chloride containing calcium is partly for regulating the liquid-solid ratio of Leaching reaction process.
The present invention and the formerly difference of patent 200910095079.X: the phosphorus raw material that (1) is formerly used in patent is for industrial chemicals acid phosphate, and with high costs, the phosphorus source of using in the present invention is Rock Phosphate (72Min BPL); (2) formerly in patent leaching process, acid phosphate plays act as catalyst action, what the Rock Phosphate (72Min BPL) using in the present invention occurred in Leaching reaction process is first to leach generation phosphate radical, phosphate radical reacts generation tertiary iron phosphate again and enters into slag with the iron ion leaching, reaction mechanism is different; (3) formerly removing of ferro element is to carry out in individual section in patent, and phosphate radical is recycled, and the iron product of generation is ironic hydroxide, and in the present invention, deironing is synchronously carried out with leaching, there is no independently deironing workshop section, phosphate radical does not recycle yet; (4) alkali source formerly using in patent is sodium carbonate, and the alkali source using in the present invention is milk of lime; (5) what formerly evaporation concentration reclaimed in patent is low value-added sodium salt, and in the present invention, evaporation concentration reclaims, is the calcium chloride product that added value is higher; (6) formerly magnesium products is magnesiumcarbonate and magnesium oxide in patent, and magnesium products in the present invention is magnesium hydroxide.
The beneficial effect that the present invention has: (1) has rationally utilized the feature on Rock Phosphate (72Min BPL) and red soil nickel ore composition, the proposition of novelty the total immersion reaction of the two, realized the comprehensive utilization of red soil nickel ore leached mud, simultaneously, existence due to tertiary iron phosphate in total immersion process, the filtration velocity that has significantly improved red soil nickel ore leached mud, has improved production efficiency; (2) realize low-grade phosphate ore stone without processing and can rationally utilize through ore dressing, reduced the use cost of low-grade phosphate ore stone; (3) realized the comprehensive utilization of the magnesium in Rock Phosphate (72Min BPL), calcium resource, the environmental issue of having evaded a large amount of phosphogypsums in Rock Phosphate (72Min BPL) sulfation leaching process, turn waste into wealth, make calcium wherein become product with calcium chloride form, make magnesium wherein become product with magnesium hydroxide form; (4) after the heavy magnesium of chloride containing calcium, liquid major part is used as reuse water retrieval system, and the calcium chloride concentration in system solution is promoted cheaply, has reduced the cost of Calcium Chloride Production; (5) acid source and the alkali source in reasonably combined system, calcium ion content in the precipitation products such as chromium, nickel, magnesium is significantly reduced, the additional processing cost that has reduced the metals such as chromium, nickel, cobalt, magnesium, meanwhile, the added value that the raising of each product quality brings has also significantly been shared production cost; (6) realize the metal such as red soil nickel ore nickel cobalt magnesium and leach to remove to synchronize with ferro element and carry out, removed the workshop section of independent deironing, shortened technical process, reduced cost of investment and operation cost.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
The method of comprehensive utilization low-grade phosphate ore stone as shown in Figure 1, its step is as follows:
1) red soil nickel ore and low-grade phosphate ore stone are carried out to ball milling (wet-milling) processing in ore grinding system separately, the aggregate diameter of the red soil nickel ore after ball milling and low-grade phosphate ore stone at 100 orders with interior ratio >=95%, and the mineral aggregate after ball milling is dewatered, obtain red soil nickel ore and the low-grade phosphate ore stone of water ratio≤35%.
2) by step 1) red soil nickel ore that obtains and low-grade phosphate ore stone is 20-35% with mass percent concentrated hydrochloric acid mixes, the add-on of Rock Phosphate (72Min BPL) is as the criterion below so that the Fe concentration of leach liquor is down to 1g/L.In closed chuck still, carry out Leaching reaction, steam as thermal source in chuck to reaction process heat supply, chuck still outer wall is done insulation and is processed, by controlling pH value (pH value≤1.5), temperature (800-100 ℃) and the time (2-3h) of Leaching reaction, most Fe that leach are reacted with the phosphate radical of leaching, generate tertiary iron phosphate precipitation and enter in leached mud, make most Ni, Co, Mg and Ca Elements Leaching enter in leach liquor simultaneously.
3) by step 2) leached mud and the leach liquor that obtain carry out solid-liquid separation in pressure filter, because tertiary iron phosphate is present in slag, make leached mud nutrient laden, leached mud need be used appropriate reuse water to wash, washery slag process is also carried out in pressure filter, the washing lotion obtaining is mixed into receipts chromium with leach liquor and reacts, and the batching as phosphate fertilizer or composite fertilizer after revolution kiln dry of the leached mud after washing is used.
4) washing lotion and leach liquor first precipitate and receive chromium with milk of lime after mixing, control reaction pH at 3.5-4.5, control temperature at 40-60 ℃, control reaction times 2-3h, when receiving chromium, remove Al, Si in leach liquor and a small amount of Fe impurity, after the separation of reaction slurry filtration, obtain liquid and chromium slag after dechromisation, chromium slag washs with reuse water in pressure filter, and the slag washing water obtaining enters one section of heavy nickel reactant.
In liquid after dechromisation, add milk of lime, control temperature at 40-60 ℃, control reaction times 2-3h, control pH and carry out one section of heavy nickel reactant at 7.5-8.5, filtration obtains liquid after one section of nickel hydroxide slag and one section of heavy nickel, one section of nickel hydroxide slag washs with tap water or steam condensate, and washing lotion enters Er Duanchen nickel workshop section, and the one section of nickel hydroxide slag acid after washing is molten, acid solution is prepared cobalt nickel product through extracting refining process; In liquid after one section of heavy nickel, add milk of lime, control temperature at 40-60 ℃, control reaction times 2-3h, control pH and carry out two sections of heavy nickel reactants at 8.5-9.5, filtration obtains liquid after two sections of nickel hydroxide slags and two sections of heavy nickel, because the pH of precipitation is high, make to contain a certain amount of magnesium hydroxide in two sections of heavy nickel slags, this part slag returns to Leaching reaction after sizing mixing with reuse water.
In liquid after two sections of heavy nickel, add milk of lime, control temperature at 40-60 ℃, control reaction times 2-3h, control pH and sink reactive magnesium at 10.0-11.0, filtration obtains liquid after magnesium hydroxide and heavy magnesium, magnesium hydroxide is with filtering after tap water or vapor condensation water washing, and filtrate is arranged outward, filter residue dry after as magnesium products; After heavy magnesium, in liquid, be mainly calcium chloride composition, after most of heavy magnesium liquid as leaching process size mixing water, leach slag washing water, milk of lime preparation water, high chromium slag bath water and the two sections of heavy nickel slags water of sizing mixing and use, realize the circulation enrichment of calcium chloride; Unnecessary reuse water is opened a way and is dried workshop section's production anhydrous chlorides of rase calcium product to evaporation concentration, rotary kiln, and the water of condensation that evaporation concentration produces is used as the interpolation water of one section of nickel hydroxide slag of washing and magnesium hydroxide slag.
The present invention's supplementary notes: (1) is mixed total immersion with low-grade phosphate ore stone with metallic ore and gone out, synchronous deironing in the process leaching, utilize unique physical property of tertiary iron phosphate to improve the slurry filtration speed that leaches, and the theory that makes leached mud Fertilizer Transformed, resource utilization is not only applicable to the common leaching process of red soil nickel ore, also be applicable to the common leaching process with other metallic ore, such as the leaching of copper cobalt ore, zinc ore concentrate etc. leached etc.(2) with low-grade phosphate ore stone, mix total immersion with metallic ore and go out, usining sulfuric acid or other acid carries out as acid source the process that total immersion goes out and also should belong to protection category of the present invention.Therefore (3) one sections of heavy nickel slags, before entering next procedure, need be washed chlorine, calcium, magnesium ion operation with tap water or steam condensate, and one section of heavy nickel slag pressure filter is can washing press, washes rear liquid and enters two sections of heavy nickel processes.(4) magnesium hydroxide slag, before export trade, need be washed chlorine, calcium ion operation with tap water or steam condensate, so magnesium hydroxide slag pressure filter is can washing press, washes rear liquid and arranges other flow process outward and use, and does not enter this flow process and uses.

Claims (5)

1. fully utilize a method for low-grade phosphate ore stone, its step is as follows:
1) red soil nickel ore and low-grade phosphate ore stone are carried out to ball-milling processing in ore grinding system separately, and the mineral aggregate after ball milling is dewatered, obtain red soil nickel ore and the low-grade phosphate ore stone of water ratio≤35%;
2) by step 1) red soil nickel ore that obtains and low-grade phosphate ore stone is 20-35% with mass percent concentrated hydrochloric acid mixes, carry out Leaching reaction, by controlling pH value, the temperature and time of Leaching reaction, most Fe that leach are reacted with the phosphate radical of leaching, generate tertiary iron phosphate precipitation and enter in leached mud, make most Ni, Co, Mg and Ca Elements Leaching enter in leach liquor simultaneously;
3) by step 2) leached mud and the leach liquor that obtain carry out solid-liquid separation in pressure filter, because tertiary iron phosphate is present in slag, make leached mud nutrient laden, leached mud need be used appropriate reuse water to wash, washery slag process is also carried out in pressure filter, the washing lotion obtaining is mixed into receipts chromium with leach liquor and reacts, and the batching as phosphate fertilizer or composite fertilizer after revolution kiln dry of the leached mud after washing is used;
4) washing lotion and leach liquor first precipitate and receive chromium with milk of lime, sink nickel reactant and heavy reactive magnesium more afterwards with milk of lime;
The detailed process of described receipts chromium reaction is as follows: control reaction pH at 3.5-4.5, control temperature and reaction times, when receiving chromium, remove Al, Si in leach liquor and a small amount of Fe impurity, after reaction slurry filtration separation, obtain liquid and chromium slag after dechromisation, chromium slag washs with reuse water in pressure filter, and the slag washing water obtaining enters one section of heavy nickel reactant.
2. the method for comprehensive utilization low-grade phosphate ore stone according to claim 1, it is characterized in that, the detailed process of described heavy nickel reactant is as follows: in liquid after dechromisation, add milk of lime to carry out one section of heavy nickel reactant, control pH at 7.5-8.5, filtration obtains liquid after one section of nickel hydroxide slag and one section of heavy nickel, one section of nickel hydroxide slag washs with tap water or steam condensate, washing lotion enters Er Duanchen nickel workshop section, and the one section of nickel hydroxide slag acid after washing is molten, acid solution is prepared cobalt nickel product through extracting refining process; In liquid after one section of heavy nickel, add milk of lime to carry out two sections of heavy nickel reactants, control pH at 8.5-9.5, filter and obtain liquid after two sections of nickel hydroxide slags and two sections of heavy nickel, this part two sections of nickel hydroxide slag returns to Leaching reaction after sizing mixing with reuse water.
3. the method for comprehensive utilization low-grade phosphate ore stone according to claim 2, it is characterized in that, the detailed process of described heavy reactive magnesium is as follows: toward adding in liquid after two sections of heavy nickel milk of lime to sink reactive magnesium, control pH at 10.0-11.0, filtration obtains liquid after magnesium hydroxide and heavy magnesium, magnesium hydroxide is with filtering after tap water or vapor condensation water washing, and filtrate is arranged outward, filter residue dry after as magnesium products; After heavy magnesium, in liquid, be mainly calcium chloride composition, after most of heavy magnesium, liquid returns to former process as reuse water, as leaching process size mixing water, leach slag washing water, milk of lime preparation water, high chromium slag bath water and the two sections of heavy nickel slags water of sizing mixing and use, realize the circulation enrichment of calcium chloride; Unnecessary reuse water is opened a way and is dried workshop section's production anhydrous chlorides of rase calcium product to evaporation concentration, rotary kiln, and the water of condensation that evaporation concentration produces is used as the interpolation water of one section of nickel hydroxide slag of washing and magnesium hydroxide slag.
4. the method for comprehensive utilization low-grade phosphate ore stone according to claim 1, is characterized in that, the aggregate diameter of the red soil nickel ore after ball milling and low-grade phosphate ore stone at 100 orders with interior ratio >=95%.
5. the method for comprehensive utilization low-grade phosphate ore stone according to claim 1, is characterized in that, the add-on of Rock Phosphate (72Min BPL) is as the criterion below so that the Fe concentration of leach liquor is down to 1g/L.
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CN106987728B (en) * 2017-03-28 2019-08-13 中南大学 A method of normal pressure phosphoric acid, which leaches nickel cobalt and synchronizes, from lateritic nickel ore prepares ferric phosphate
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