CN103193213A - Method for comprehensively utilizing low-grade phosphate ores - Google Patents
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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
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
At present both at home and abroad the method for wet processing low-grade phosphate ore stone is mainly: earlier low-grade phosphate ore stone is carried out floating and enriching and handle, make P in the mineral aggregate
2O
5Content is by being promoted to below 25% more than 30% in the raw ore, be that raw material leaches reaction with sulfuric acid and Rock Phosphate (72Min BPL) 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 purifying purification, phosphogypsum is stored up processing, because a large amount of phosphogypsums exists environment is threatened, on comprehensive utilization of phosphogypsum, done number of research projects at present both at home and abroad, for example: with phosphogypsum as the application of cement additire in cement industry, the technical study of preparing calcium sulphate whiskers from ardealite, phosphogypsum calcining preparation active calcium oxide reclaims 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 big technical difficult problem in phosphorous chemical industry field.
At present both at home and abroad in the Rock Phosphate (72Min BPL) except phosphoric other element utilize present situation: except containing phosphoric, the composition of another one maximum is CaO in the Rock Phosphate (72Min BPL), and its content is about 50%; Also have MgO, K
2The content of compositions such as O is also higher, and these compositions are used as impurity mostly and discard in the treating processes of Rock Phosphate (72Min BPL) at present; The rare earth elements such as yttrium oxide that also contain content about 0.08% in the Rock Phosphate (72Min BPL) on ground such as Guizhou are owing to its high added value has been subjected to some research organizations pay much.
The method of the low-grade red soil nickel ore of wet processing is both at home and abroad at present:
(1) normal pressure sulfuric acid leaching: this method is to be leaching agent with sulfuric acid, controls reaction conditionss such as certain liquid-solid ratio, acidity, temperature, under normal pressure metals such as nickel, cobalt, iron, magnesium is leached from mineral aggregate; Add neutralizing agent (Wingdale, calcium hydroxide then, perhaps other alkaline matter) impurity such as iron, aluminium, silicon is removed, obtain nickel sulfate solution after the press filtration of removal of impurities ore pulp and scrap slag, scrap slag and efflux behind washery slag, nickel sulfate solution then uses sodium hydroxide (perhaps 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 behind the abstraction impurity removal; Liquid evaporative crystallization reclaim(ed) sulfuric acid magnesium behind the heavy nickel perhaps directly adds alkaline matter (Wingdale, calcium hydroxide, yellow soda ash etc.) and carries out precipitation process, and liquid effluxes after the processing that obtains; This treatment process is owing to be metal target with nickel, cobalt and a spot of magnesium only, and the rate of recovery of magnesium is low, the acid and alkali consumption height, and the quantity of slag is big and can't fully utilize, thereby causes production cost high.
(2) high pressure sulfuric acid leaching: this method is to be leaching agent with sulfuric acid, and control certain reaction temperature is handled laterite under the pressurization situation; Pressurized acid leaching technology starts from the hair Ah (MOA) of Cuba's the 1950's the earliest, Australian Mu Lin-Mu Lin after the nineties in 20th century, Bu Long, examining pressurized acid leaching factories such as gas goes into operation in succession, but many problems are appearring aspect technology and the equipment, the basic procedure of this technology is that ore enters autoclave through high pressure (4-5MPa) through after the broken slurrying, high temperature (230-260 ℃) is acid to be leached, carry out liquid-solid separation after the leaching, then leach liquor is neutralized, deironing, liquid carries out the separation of nickel cobalt by extraction after the deironing, also can further smelt according to different needs obtain different nickel cobalt products; The rate of recovery of this technology nickel cobalt can reach more than 90%, but this technology investment cost is big, and is relatively stricter to the requirement of equipment and material, because impurity such as magnesium are bigger for the influence of sulfuric acid consumption, so this technology be fit to be handled and to be contained magnesium less than 10%, particularly less than 5% red soil nickel ore; In addition, in this technology operational process, equipment is prone to scale formation, production is affected greatly, and the cost of equipment maintenance height, slag can't rationally utilize, and the existence of these a series of problems makes the large-area applications popularization of this method be subjected to certain influence.
(3) reduction roasting-ammonia leaching method: therefore reduction roasting-ammonia leaching technology claim the Caron flow process again by professor's Caron invention, and wherein, ammonia soaks and adopts NH in the process
3And CO
2Nickel in the roasted ore and cobalt are converted into ammonia complex enter solution, the advantage of this technology is that reagent can recycle, consumption is little, shortcoming is that the nickel cobalt rate of recovery is low, the nickel cobalt rate of recovery is respectively about 75% and 60%, and because mineral aggregate need be dried roasting, energy consumption is bigger, can not realize the comprehensive reutilization of resource.
The iron removal technology of present domestic and international low-grade red soil nickel ore leach liquor: wet processing red soil nickel ore, the iron in the leach liquor all are as impurity removal, and deironing has three kinds of methods, neutralization precipitation method, goethite process and yellow modumite method usually.In addition, the way that also has the scholar's research employing to extract deironing is removed the iron in the leach liquor at low temperatures, reclaims iron product simultaneously.Adopt this several method deironing, all can obtain de-ferrous effect preferably; It is exactly to need to increase independent workshop section to carry out the processing of ferro element that but these methods have a common characteristic, has caused the input of artificial and equipment to increase, and technical process prolongs, and investment enlarges.
Chinese patent application 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, this method in the red soil nickel ore leaching process, used acid phosphate as catalyzer in order to improve the leaching yield of metal; After solid-liquid separation, also use acid phosphate to come deironing in the leach liquor iron removal, and phosphate radical reclaimed produce the ironic hydroxide product simultaneously; In leach liquor in Ni, Co, the isoionic precipitation process of Mg, used yellow soda ash 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 preparation magnesium oxide, magnesia digestion is sized mixing afterwards to turn back to removal of impurities and precipitate in the rough cobalt nickel product process as alkali and is used; Simultaneously, in technological process, the sodium product has been carried out the evaporation concentration recovery.The omnidistance alkali source that uses of this technical process is yellow soda ash, use as alkali even if returned the magnesium oxide of part during the course, but its alkalescence of tracing to its source comes from yellow soda ash, and the alkali supplementary product onsumption is with high costs; This flow process adopts acid phosphate to make catalyzer and participates in reaction, 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 investment to increase, and ironic hydroxide is colloid, and liquid-solid sepn process is difficulty comparatively, can bring inconvenience in the production implementation process; This flow process has been carried out the evaporation concentration recovery to the sodium product, because series product added values such as sodium sulfate are extremely low, the concentration in this system is also lower, adopts the mode of evaporation concentration to reclaim and need do corresponding assessment in economy; In sum, also there is certain problem in this method on industrial applications.
The selection of acid source and alkali source in the red soil nickel ore wet smelting process: in the selection of acid source, selection use sulfuric acid is in the majority as acid source, in the selection of alkali source with the basic salt (yellow soda ash of sodium, sodium hydroxide etc.) be main, Chinese patent application numbers 201210202583.7 disclose a kind of from red soil nickel ore the method for comprehensively recovering valuable metal, this method has used sulfuric acid as acid source, with milk of lime as alkali source, the defective that this soda acid source is selected is to receive chromium with milk of lime, sinking nickel with milk of lime, 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, the calcium sulfate dissolving enters into leach liquor in the molten process of acid, calcium ion wherein can affect greatly technology in workshop section's foulings such as extractions subsequently.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective that above-mentioned prior art exists, a kind of method that fully utilizes low-grade phosphate ore stone is provided, this method takes into full account low-grade phosphate ore stone and red soil nickel ore composition characteristics, comprehensively reclaims 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 ball-milling processing in ore grinding system separately, and the mineral aggregate behind the ball milling is dewatered, obtain red soil nickel ore and the low-grade phosphate ore stone of water ratio≤35%;
2) red soil nickel ore that step 1) is obtained and low-grade phosphate ore stone and mass percent are that the concentrated hydrochloric acid of 20-35% mixes, leach reaction, leach reaction pH value, temperature and time by control, make the phosphate radical reaction of most Fe that leach and leaching, generating the tertiary iron phosphate precipitation enters in the leached mud, most Ni, Co, Mg and Ca element are leached enter in the leach liquor, owing to the existence of tertiary iron phosphate in slag, can significantly improve the separating and filtering speed of leached mud and leach liquor;
3) with 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 the slag, make the leached mud nutrient laden, leached mud need use an amount of reuse water to wash, the washery slag process is also carried out in pressure filter, the washing lotion that obtains and leach liquor are mixed into receives the chromium reaction, and the batching as phosphate fertilizer or composite fertilizer after the revolution kiln dry of the leached mud after the washing is used, and makes leached mud turn waste into wealth;
4) washing lotion and leach liquor earlier precipitate receipts chromium with milk of lime, sink nickel reactant and heavy reactive magnesium with milk of lime more afterwards.
Problem solved by the invention: (1) low-grade phosphate ore stone low cost is utilized problem; (2) comprehensive utilization of elements problems such as calcium, magnesium in the low-grade phosphate ore stone; (3) the red soil nickel ore peracid leaches the difficult problem of filtration of reaction; (4) the low cost production problem of calcium chloride product in the system; (5) the reasonable handling problem of red soil nickel ore leached mud; (6) low-cost high-efficiency reclaims in the laterite metals such as nickel cobalt magnesium.
The present invention will grind good low-grade phosphate ore stone and red soil nickel ore earlier and soak reaction altogether under hydrochloric acid system, make ferro element in the laterite and the phosphoric in the Rock Phosphate (72Min BPL) when nickel, calcium plasma leach, the precipitation that forms tertiary iron phosphate enters into slag, make the leached mud nutrient laden, turn waste into wealth, simultaneously significantly improve the solid-liquid separation filtration velocity, significantly enhance productivity; Calcium ion in the Rock Phosphate (72Min BPL) exists in the leach liquor with the calcium chloride form, for subsequent production calcium chloride is laid a good foundation, has also rationally utilized the calcium resource in the Rock Phosphate (72Min BPL); Use hydrochloric acid as acid source in the leaching process, leach liquor uses milk of lime as alkali source, and the one, significantly reduced cost of supplementary product, the 2nd, improved the calcium chloride concentration in the leach liquor, the 3rd, improved the isoionic product purity of milk of lime coprecipitated nickel hydroxide cobalt magnesium.Technical process is short, and it is cheap to produce comprehensive cost.
As further technical scheme of the present invention:
The detailed process of described receipts chromium reaction is as follows: pH is at 3.5-4.5 in the control reaction, control temperature and reaction times, when receiving chromium, remove Al, Si and a spot of Fe impurity in the leach liquor, after separating, the reaction slurry filtration obtains liquid and chromium slag behind the dechromisation, because no calcium sulfate exists, can make that the chromium content in the chromium slag improves.The chromium slag washs with reuse water in pressure filter, and the slag washing water that obtains enters one section heavy nickel reactant.
The detailed process of described heavy nickel reactant is as follows: add milk of lime behind the dechromisation in the liquid and carry out one section heavy nickel reactant, pH is at 7.5-8.5 in control, filtration obtains liquid behind one section nickel hydroxide slag and the one section heavy nickel, one section nickel hydroxide slag washs with tap water or steam condensate, washing lotion enters two sections heavy nickel workshop sections, and the one section nickel hydroxide slag acid after the washing is molten, acid solution is prepared cobalt nickel product through the extracting refining process; Add milk of lime behind one section heavy nickel in the liquid and carry out two sections heavy nickel reactants, pH is at 8.5-9.5 in control, filters to obtain liquid behind two sections nickel hydroxide slags and the two sections heavy nickel, returns after this part two sections nickel hydroxide slag is sized mixing with reuse water and leaches reaction.
The detailed process of described heavy reactive magnesium is as follows: add milk of lime behind two sections heavy nickel in the liquid and sink reactive magnesium, pH is at 10.0-11.0 in control, filtration obtains liquid behind magnesium hydroxide and the heavy magnesium, magnesium hydroxide is with tap water or vapor condensation water washing after-filtration, filtrate effluxes, and filter residue oven dry back is as magnesium products; Be mainly the calcium chloride composition in the liquid behind the heavy magnesium, liquid returns former process as reuse water behind most of heavy magnesium, as leaching process size mixing water, leach slag washing water, milk of lime preparation water, high chromium wash heat and wash water and the two sections heavy nickel slags water of sizing mixing and use, realize the circulation enrichment of calcium chloride; Unnecessary reuse water is opened a way to evaporation concentration, rotary kiln oven dry workshop section production anhydrous chlorides of rase calcium product, and the water of condensation that evaporation concentration produces uses as the interpolation water of one section nickel hydroxide slag of washing and magnesium hydroxide slag.Two sections heavy nickel are in order to improve the purity of nickel yield and raising magnesium products.
The mineral aggregate particle diameter of the red soil nickel ore behind the 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 so that the Fe concentration of leach liquor is down to below the 1g/L.
The reuse water that contains calcium chloride partly is used for regulating the liquid-solid ratio that leaches reaction process.
The present invention and the difference of patent 200910095079.X formerly: the phosphorus raw material that formerly use in the patent (1) is as the industrial chemicals acid phosphate, and with high costs, the phosphorus source of using among the present invention is Rock Phosphate (72Min BPL); (2) formerly in the patent leaching process, acid phosphate plays act as catalyst action, what the Rock Phosphate (72Min BPL) that uses among the present invention took place in leaching reaction process is to leach earlier to generate phosphate radical, phosphate radical generates tertiary iron phosphate with the iron ion reaction of leaching again and enters into slag, the reaction mechanism difference; (3) formerly in the patent removing of ferro element be in individual section, to carry out, and phosphate radical is recycled, and the iron product of generation is ironic hydroxide, and deironing is carried out synchronously with leaching among the present invention, do not have independently deironing workshop section, phosphate radical does not recycle yet; (4) alkali source that formerly uses in the patent is yellow soda ash, and the alkali source that uses among the present invention is milk of lime; What (5) formerly evaporation concentration reclaimed in the patent is low value-added sodium salt, is the higher calcium chloride product of added value and evaporation concentration reclaims among the present invention; (6) formerly in the patent magnesium products be magnesiumcarbonate and magnesium oxide, and the magnesium products among the present invention is magnesium hydroxide.
The beneficial effect that the present invention has: (1) has rationally utilized the characteristics on Rock Phosphate (72Min BPL) and the red soil nickel ore composition, the proposition of novelty the two soak reaction altogether, realized the comprehensive utilization of red soil nickel ore leached mud, simultaneously, owing to soak the existence of tertiary iron phosphate in the process altogether, significantly improve the filtration velocity of red soil nickel ore leached mud, improved production efficiency; (2) realized that low-grade phosphate ore stone need not to handle 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 the Rock Phosphate (72Min BPL), calcium resource, the environmental issue of having evaded a large amount of phosphogypsums in the Rock Phosphate (72Min BPL) sulfation leaching process, turn waste into wealth, make calcium wherein become product with the calcium chloride form, make magnesium wherein become product with the magnesium hydroxide form; (4) contain the heavy magnesium of calcium chloride after the liquid major part use as the reuse water retrieval system, make that the calcium chloride concentration in system's solution is promoted cheaply, reduced the cost of Calcium Chloride Production; (5) acid source and the alkali source in the reasonably combined system, make the calcium ion content in the precipitation products such as chromium, nickel, magnesium significantly reduce, reduced the additional processing cost of metals such as chromium, nickel, cobalt, magnesium, simultaneously, the added value that the raising of each product quality brings has also significantly been shared production cost; (6) realize that metal such as red soil nickel ore nickel cobalt magnesium leaches to remove with ferro element and carry out synchronously, removed the workshop section of independent deironing, shortened technical process, reduced cost of investment and operation cost.
Description of drawings
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 ball milling (wet-milling) processing in ore grinding system separately, the mineral aggregate particle diameter of the red soil nickel ore behind the ball milling and low-grade phosphate ore stone at 100 orders with interior ratio 〉=95%, and the mineral aggregate behind the ball milling dewatered, obtain red soil nickel ore and the low-grade phosphate ore stone of water ratio≤35%.
2) red soil nickel ore that step 1) is obtained and low-grade phosphate ore stone and mass percent are that the concentrated hydrochloric acid of 20-35% mixes, and the add-on of Rock Phosphate (72Min BPL) is as the criterion so that the Fe concentration of leach liquor is down to below the 1g/L.In closed chuck still, leach reaction, steam as thermal source in chuck to the reaction process heat supply, chuck still outer wall is done insulation and is handled, leach reaction pH value (pH value≤1.5), temperature (800-100 ℃) and time (2-3h) by control, make the phosphate radical reaction of most Fe that leach and leaching, generate the tertiary iron phosphate precipitation and enter in the leached mud, most Ni, Co, Mg and Ca element are leached enter in the leach liquor.
3) with 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 the slag, make the leached mud nutrient laden, leached mud need use an amount of reuse water to wash, the washery slag process is also carried out in pressure filter, the washing lotion that obtains and leach liquor are mixed into receives the chromium reaction, and the batching as phosphate fertilizer or composite fertilizer after the revolution kiln dry of the leached mud after the washing is used.
4) precipitate receipts chromium with milk of lime earlier after washing lotion and leach liquor mix, pH is at 3.5-4.5 in the control reaction, the control temperature is at 40-60 ℃, control reaction times 2-3h, when receiving chromium, remove Al, Si and a spot of Fe impurity in the leach liquor, after separating, the reaction slurry filtration obtains liquid and chromium slag behind the dechromisation, the chromium slag washs with reuse water in pressure filter, and the slag washing water that obtains enters one section heavy nickel reactant.
Add milk of lime in the liquid behind the dechromisation, the control temperature is at 40-60 ℃, control reaction times 2-3h, control pH carries out one section heavy nickel reactant at 7.5-8.5, filtration obtains liquid behind one section nickel hydroxide slag and the one section heavy nickel, one section nickel hydroxide slag washs with tap water or steam condensate, and washing lotion enters two sections heavy nickel workshop sections, and the one section nickel hydroxide slag acid after the washing is molten, acid solution is prepared cobalt nickel product through the extracting refining process; Add milk of lime in the liquid behind one section heavy nickel, the control temperature is at 40-60 ℃, control reaction times 2-3h, control pH carries out two sections heavy nickel reactants at 8.5-9.5, filtration obtains liquid behind two sections nickel hydroxide slags and the two sections heavy nickel, because the pH height of precipitation makes and contains a certain amount of magnesium hydroxide in two sections heavy nickel slags, returns after this part slag is sized mixing with reuse water and leaches reaction.
Add milk of lime in the liquid behind two sections heavy nickel, the control temperature is at 40-60 ℃, control reaction times 2-3h, control pH sinks reactive magnesium at 10.0-11.0, filtration obtains liquid behind magnesium hydroxide and the heavy magnesium, magnesium hydroxide is with tap water or vapor condensation water washing after-filtration, and filtrate effluxes, and filter residue oven dry back is as magnesium products; Be mainly the calcium chloride composition in the liquid behind the heavy magnesium, behind most of heavy magnesium liquid as leaching process size mixing water, leach slag washing water, milk of lime preparation water, high chromium wash heat and wash water and the two sections heavy nickel slags water of sizing mixing and use, realize the circulation enrichment of calcium chloride; Unnecessary reuse water is opened a way to evaporation concentration, rotary kiln oven dry workshop section production anhydrous chlorides of rase calcium product, and the water of condensation that evaporation concentration produces uses as the interpolation water of one section nickel hydroxide slag of washing and magnesium hydroxide slag.
The present invention's supplementary notes: (1) mixes leaching altogether with low-grade phosphate ore stone with metallic ore, deironing synchronously in the process that leaches, utilize unique rerum natura of tertiary iron phosphate to improve the slurry filtration speed that leaches, and make the theory of leached mud fertilizerization, resource utilization not be only applicable to the common leaching process of red soil nickel ore, be applicable to also and the common leaching process of other metallic ore that for example the leaching of copper cobalt ore, zinc ore concentrate etc. leach etc.(2) mix leaching altogether with metallic ore with low-grade phosphate ore stone, also should belong to protection category of the present invention with sulfuric acid or other acid as the process that acid source carries out common leaching.(3) one sections heavy nickel slags need to wash chlorine, calcium, magnesium ion operation with tap water or steam condensate, but therefore one section heavy nickel slag pressure filter are washing press before entering next procedure, wash back liquid and enter two sections heavy nickel processes.(4) the magnesium hydroxide slag is before export trade, need wash chlorine, calcium ion operation with tap water or steam condensate, but so magnesium hydroxide slag pressure filter be washing press, wash back liquid and efflux other flow process and use, do not enter the use of this flow process.
Claims (6)
1. method that fully utilizes low-grade phosphate ore stone, its step is as follows:
1) red soil nickel ore and low-grade phosphate ore stone are carried out ball-milling processing in ore grinding system separately, and the mineral aggregate behind the ball milling is dewatered, obtain red soil nickel ore and the low-grade phosphate ore stone of water ratio≤35%;
2) red soil nickel ore that step 1) is obtained and low-grade phosphate ore stone and mass percent are that the concentrated hydrochloric acid of 20-35% mixes, leach reaction, leach reaction pH value, temperature and time by control, make the phosphate radical reaction of most Fe that leach and leaching, generate the tertiary iron phosphate precipitation and enter in the leached mud, most Ni, Co, Mg and Ca element are leached enter in the leach liquor;
3) with 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 the slag, make the leached mud nutrient laden, leached mud need use an amount of reuse water to wash, the washery slag process is also carried out in pressure filter, the washing lotion that obtains and leach liquor are mixed into receives the chromium reaction, and the batching as phosphate fertilizer or composite fertilizer after the revolution kiln dry of the leached mud after the washing is used;
4) washing lotion and leach liquor earlier precipitate receipts chromium with milk of lime, sink nickel reactant and heavy reactive magnesium with milk of lime more afterwards.
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 receipts chromium reaction is as follows: pH is at 3.5-4.5 in the control reaction, control temperature and reaction times, when receiving chromium, remove Al, Si and a spot of Fe impurity in the leach liquor, after separating, the reaction slurry filtration obtains liquid and chromium slag behind the dechromisation, the chromium slag washs with reuse water in pressure filter, and the slag washing water that obtains enters one section heavy nickel reactant.
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 nickel reactant is as follows: add milk of lime behind the dechromisation in the liquid and carry out one section heavy nickel reactant, pH is at 7.5-8.5 in control, filtration obtains liquid behind one section nickel hydroxide slag and the one section heavy nickel, one section nickel hydroxide slag washs with tap water or steam condensate, washing lotion enters two sections heavy nickel workshop sections, and the one section nickel hydroxide slag acid after the washing is molten, acid solution is prepared cobalt nickel product through the extracting refining process; Add milk of lime behind one section heavy nickel in the liquid and carry out two sections heavy nickel reactants, pH is at 8.5-9.5 in control, filters to obtain liquid behind two sections nickel hydroxide slags and the two sections heavy nickel, returns after this part two sections nickel hydroxide slag is sized mixing with reuse water and leaches reaction.
4. the method for comprehensive utilization low-grade phosphate ore stone according to claim 3, it is characterized in that, the detailed process of described heavy reactive magnesium is as follows: add milk of lime behind two sections heavy nickel in the liquid and sink reactive magnesium, pH is at 10.0-11.0 in control, filtration obtains liquid behind magnesium hydroxide and the heavy magnesium, magnesium hydroxide is with tap water or vapor condensation water washing after-filtration, and filtrate effluxes, and filter residue oven dry back is as magnesium products; Be mainly the calcium chloride composition in the liquid behind the heavy magnesium, liquid returns former process as reuse water behind most of heavy magnesium, as leaching process size mixing water, leach slag washing water, milk of lime preparation water, high chromium wash heat and wash water and the two sections heavy nickel slags water of sizing mixing and use, realize the circulation enrichment of calcium chloride; Unnecessary reuse water is opened a way to evaporation concentration, rotary kiln oven dry workshop section production anhydrous chlorides of rase calcium product, and the water of condensation that evaporation concentration produces uses as the interpolation water of one section nickel hydroxide slag of washing and magnesium hydroxide slag.
5. the method for comprehensive utilization low-grade phosphate ore stone according to claim 1 is characterized in that, the mineral aggregate particle diameter of the red soil nickel ore behind the ball milling and low-grade phosphate ore stone at 100 orders with interior ratio 〉=95%.
6. 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 so that the Fe concentration of leach liquor is down to below the 1g/L.
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| CN103482784A (en) * | 2013-09-17 | 2014-01-01 | 孔建美 | Method for processing waste water of acid leaching and deironing of potassium feldspar |
| CN106044824A (en) * | 2016-07-25 | 2016-10-26 | 成都市新都化工股份有限公司 | Method for treating yellow calcium nitrate liquid |
| CN106086409A (en) * | 2016-08-03 | 2016-11-09 | 中国恩菲工程技术有限公司 | The method of liquid after the heavy nickel cobalt of process |
| CN106987728A (en) * | 2017-03-28 | 2017-07-28 | 中南大学 | A kind of normal pressure phosphoric acid from lateritic nickel ore leaches nickel cobalt and the method for synchronously preparing ferric phosphate |
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| CN103436717A (en) * | 2013-08-30 | 2013-12-11 | 紫金矿业集团股份有限公司 | Method for enriching gallium and comprehensively utilizing potassium and aluminum from alunite |
| CN103482784A (en) * | 2013-09-17 | 2014-01-01 | 孔建美 | Method for processing waste water of acid leaching and deironing of potassium feldspar |
| CN103482784B (en) * | 2013-09-17 | 2015-05-20 | 青岛中平电子科技有限公司 | Method for processing waste water of acid leaching and deironing of potassium feldspar |
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| CN106086409B (en) * | 2016-08-03 | 2018-05-11 | 中国恩菲工程技术有限公司 | The method of liquid after the heavy nickel cobalt of processing |
| CN106086409A (en) * | 2016-08-03 | 2016-11-09 | 中国恩菲工程技术有限公司 | The method of liquid after the heavy nickel cobalt of process |
| CN106987728A (en) * | 2017-03-28 | 2017-07-28 | 中南大学 | A kind of normal pressure phosphoric acid from lateritic nickel ore leaches nickel cobalt and the method for synchronously preparing ferric phosphate |
| 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 |
| CN107841627A (en) * | 2017-10-19 | 2018-03-27 | 姚元勋 | The method of disposal of hazardous waste coexists in a kind of more metals |
| CN108987749A (en) * | 2018-08-28 | 2018-12-11 | 深圳市德方纳米科技股份有限公司 | The method of ferric phosphate, the preparation method of iron manganese phosphate for lithium and lithium iron phosphate positive material are prepared by phosphorus ore |
| CN111471856A (en) * | 2020-05-06 | 2020-07-31 | 中南大学 | Method for one-step acid leaching of laterite-nickel ore and co-production of lithium iron phosphate positive active material |
| CN111471856B (en) * | 2020-05-06 | 2021-06-22 | 中南大学 | Method for one-step acid leaching of laterite-nickel ore and co-production of lithium iron phosphate positive active material |
| CN113604656A (en) * | 2021-07-12 | 2021-11-05 | 四川顺应动力电池材料有限公司 | Method for producing high-grade iron ore concentrate by leaching laterite-nickel ore under normal pressure and high pressure |
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