CN100519783C - Technique for comprehensive utilization clean production of phosphorus block ore and extracting rare earth form the phosphorus block ore - Google Patents
Technique for comprehensive utilization clean production of phosphorus block ore and extracting rare earth form the phosphorus block ore Download PDFInfo
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- CN100519783C CN100519783C CNB2007100027112A CN200710002711A CN100519783C CN 100519783 C CN100519783 C CN 100519783C CN B2007100027112 A CNB2007100027112 A CN B2007100027112A CN 200710002711 A CN200710002711 A CN 200710002711A CN 100519783 C CN100519783 C CN 100519783C
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Abstract
The invention relates to a technology for carrying on comprehensive utilization and clean production of phosphorus rock mine and extracting rare earth from the phosphorus rock mine. By improving the existing technology for extracting phosphoric acid in wet method, the technology process of the invention can be carried on further treatment through the recovering and treating process of normal fluorine and silicon, thereby realizing precipitate of rare-earth microcosmic salt and achieving single rare-earth products by further normal treatment. Simultaneously, phosphogypsum in the existing technique is used through recycling and deep processing, thereby achieving the purpose of clean production. The invention has the advantages that the clean production can be achieved with relatively low cost, rare-earth element in mineral products is fully recycled, and the realization of industrial production and the deepening of the comprehensive utilization of the phosphogypsum are easily achieved.
Description
Technical field
The present invention relates to a kind of phosphorite ore deposit is fully utilized and clean the technology of producing and therefrom extracting rare earth.By the improvement that existing wet method is extracted phosphoric acid process, technical process of the present invention can be by further handling the fluorine of routine, the recycling process of silicon, thereby obtain the RE phosphate precipitation, obtain the single rare earth product through further conventional processing again, simultaneously to the waste material phosphogypsum of the prior art deep processing and utilization that circulates, thereby realize cleaning the purpose of production.
Background technology
Phosphorus be a kind of important, be difficult to the regenerated non-metallic mineral resource, also be one of most important element in the life, it not only has important use and is worth in many industry, and is also playing the part of important role at agricultural, medicine, biological field.China's phosphorus ore reserves occupy the third place in the world, verify about 16,800,000,000 tons of phosphate rock resource reserves at present, but the Mineral resources amount of really can utilizing that wherein can satisfy existing mining and produce required index request is that basic reserves only are 4,000,000,000 tons (signature ore deposits), and the industrial reserves of deducting again behind allowable loss amount and the mining loss amount then only is 2,100,000,000 tons.This shows that the real amount usable of China's phosphate rock resource is not abundant.The phosphate rock resource of China has several outstanding features.One, mid low grade phosphate rock be than great, in verifying the phosphate rock resource reserves, and high-grade ore (P
2O
530%) have only 10.7 hundred million tons, account for 8%; All the other overwhelming majority be in low-grade ore (P
2O
512%～30%), the ore reactive behavior is low, and the foreign matter content height belongs to typical difficulty and selects low activity phosphorus ore kind.Another characteristics are skewness, mainly concentrate on the less-developed relatively Yunnan of traffic, economy, Guizhou, Sichuan, Hubei and Hunan five provinces, and its reserves account for 92.2% of national total storage, and it is unfavorable that these characteristics have brought for the exploitation of phosphorus ore and utilization.In a word, the phosphor resource of China is very limited, and the crisis of potential phosphorus with influencing lasting, the high speed development of China's economy, therefore, must be shown great attention to the phosphorus crisis, guarantees the Sustainable development of phosphor resource industry with reasonable utilization.
Sulfuric acid is put forward the typical process of the technology of phosphorus as wet method extraction phosphoric acid; be widely used in the manufacturer of phosphorous chemical industry and phosphate fertilizer in China; in nearly decades, obtain constantly improving and improving; and formed the industry of mass-producing, but that wet method sulfuric acid is produced in the production process of phosphoric acid problem of complex utilization and problem of environmental pollution is also more outstanding.
Phosphogypsum is the sour waste residue that contains of discharging in the Wet-process Phosphoric Acid Production, 1 ton of P of common every production
2O
5Just produce 4.5～5.0 tons of phosphogypsums.The long-term stacking of phosphogypsum not only takies a large amount of soils, increase expense, also contaminate environment.According to estimates, about 300,000,000 tons of annual world phosphogypsum quantity discharged, China is about 2,200 ten thousand tons, and its processing and comprehensive utilization have become global problem, seek it and effectively utilize approach to be imminent.Phosphogypsum average utilization in the world's has only 2%～3% so far, and China is 3%～6%.Contain objectionable constituent such as a spot of phosphorus, fluorine in the phosphogypsum, cause the cost of regeneration higher, usually as waste discharge.Most of phosphogypsum adopts air storage and impouring sea dual mode to handle, and has only few part to obtain utilizing.On the one hand, the phosphogypsum air storage takies a large amount of soils, causes very big burden to enterprise; On the other hand, the phosphogypsum discharging causes serious environment pollution.According to estimates, China every year is with the P of phosphogypsum emission loss
2O
5Just reach 300,000 tons.From the sixties so far, many countries all are being devoted to the industrial applications research work of phosphogypsum, have all obtained many achievements in theory with in the practice.Current, phosphogypsum is mainly used in the following aspects: 1) make soil improvement agent; 2) make cement setting retarder; 3) produce plaster of Paris and gypsum cement; 4) system ammonium sulfate; 5) produce vitriolate of tartar; 6) preparation producing sulfuric acid and jointly cement.
The emission problem of a large amount of phosphogypsums, perplexing the enterprise that wet-process phosphoric acid production plant is arranged all over the world always, since the forties in 20th century, the handling problem of phosphogypsum is being explored always by lot of domestic and foreign enterprises and scientific research institution, can be divided into two classes and handle thinking, be that end treatment method and source reduction pollute method (being cleaner production), the research that belongs to the end treatment method has: (1) ardealite storage yard addressing, antiseepage are handled, and quicken to solidify etc.(2) phosphogypsum that contains plurality of impurities of discharging is carried out purifying treatment after, be used to produce papermaking filler and building materials.Building materials comprise: cement, cement setting retarder, plastering, calcimine etc.Adopt the enterprise of this method to have: Chiba, Japan phosphoric acid factory, Japan little wild cement company, USSR (Union of Soviet Socialist Republics) have the factory of 400 kilotons/year phosphogypsum system plastering, many enterprises of Chinese northern Shandong group of enterprises and build up phosphogypsum system producing sulfuric acid and jointly cement works, Tongling Boluo material of construction company limited 400 kilotons/year purification phosphogypsum system Thistle board, the 100k of copper group ton/year producing cement from phosphor retardant.60,000 tons of/year cement plant of 7 40,000 tons of/year producing sulfuric acid and jointlies of cover that China has gone into operation can steady in a long-term be moved basically, throughput meets or exceeds designed capacity, yet be in operation and also have problems such as efficiency of dust collection is low, transformation efficiency is low, exhaust emissions is serious, cement pre-treatment intensity is low, and once investment is too big, to the requirement height of phosphogypsum.Some country and South Africa also once had phosphogypsum system producing sulfuric acid and jointly cement plant in Europe.(3) produce fertilizer vitriolate of tartar, sulfuric acid.(4) phosphogypsum is converted into lime carbonate and sulfur method, and promptly the Zhan Shi that is invented by the American James in recent years handles calcium sulfate technology.This novel process is done experiment in China hugeization group at present.This technology is leached sulfurated lime with rotary kiln reduction gypsum system sulfurated lime with hydrogen sulfide, can get 20% calcium sulfhydrate solution, again this calcium sulfhydrate solution carbonization is got hydrogen sulfide and lime carbonate, the circulation of a gained hydrogen sulfide part, and a part is recycled into sulphur through oxidation.Little test result is satisfactory, but owing to lack the pilot scale fund, thereby its economic feasibility remains to be proved that this technology budget investment is bigger.
Belong to and cut down the process (being cleaner production) that pollutes: in production process of phosphoric acid,, make the phosphogypsum outward appearance of output pure white, only contain trace impurity, therefore can replace the plaster of paris to be used for all trades and professions by changing technical process.This flow process significantly reduces the quantity discharged of waste residue in the phosphoric acid process process, and the phosphogypsum slag amount is 10%～40% of a former traditional technology.
Early 1990s has just begun similar The Study on New Technology work abroad.Having of document announcement: (the Phosphate Engineering ﹠amp of the phosphoric acid salt engineering of the U.S. and construction company; Construction CoMPany Inc., PECC) and Sa Sikaqiewan (Potash Cornerationof Saskatchewan, PCS) " producing the PECC/PCS novel process of phosphoric acid from low-grade phosphate ore " of exploitation, the Florida State Bromwell ﹠amp of the U.S.; Carrier company is also similarly studied, and the pure phosphogypsum that reclaims is used to produce cement and sulfuric acid, has proposed " the integrated project of mine, power station, cement mill and phosphoric acid saltworks ", can realize the zero release of " three wastes ".80% of its phosphogypsum is supplied with cement mill system sulfuric acid and cement with pure calcium sulfate, and 20% phosphogypsum and waste residue are filled the pit after exploiting.India enterprise also carried out the pilot scale work of " adopting low-grade phosphate ore to produce phosphoric acid and high purity gypsum ".China's some research institutions nearly 1～2 year this operational path that also begins one's study has been done the dynamic experiment of some phosphorolytic cleavage phosphorus ores, has proposed " technology of low-grade phosphate ore system phosphoric acid and pure gypsum ", but the report of further development is not arranged.Fig. 1 is the schema that present conventional wet method is extracted phosphoric acid process.
Some areas, Guizhou to contain heavy rare earths phosphorite ore deposit be based on collophanite, contain the complicated phosphorite ore deposit of heavy rare earth metal, rare earth is the associated minerals in this ore deposit, wherein heavy rare earths accounts for 45～50% of the contained total amount of rare earth of phosphorus deposit.Owing to contain valuable mineral and gangue mineral in the heavy rare earths phosphorite ore in this mineral deposit, disseminated grain size is evenly tiny, technological properties such as magnetic between them and proportion are very approaching, belong to difficulty and select polymetallic ore, main valuable mineral is rhombspar, collophanite, phosphatic rock etc. in this mineral deposit, mainly is calcite, rhombohedral iron ore, illite, kaolinite and pyrite in the gangue mineral.The rare earth element major part concentrates in collophanite and the phosphatic rock, according to the operational characteristic of ore, rationally utilizes Mineral resources, and suitable mineral clean treatment process, do not appear in the newspapers at present.
Summary of the invention
At the distinctive heavy rare earths phosphorite ore deposit that contains of China's Guizhou province, and the phosphorite ore deposit realized cleaning production, the object of the present invention is to provide a kind of phosphorite ore deposit is fully utilized to clean the technology of producing and therefrom extracting rare earth.
Provided by the inventionly the phosphorite ore deposit is fully utilized to clean the technological process of producing and therefrom extract rare earth be (process flow sheet is referring to Fig. 2) that carries out according to the following steps:
(1) according to the technology of conventional wet method system phosphoric acid, the phosphorite green ore is obtained the phosphorite concentrate after ore dressing, generate raw phosphoric acid and phosphogypsum, obtain raw phosphoric acid and phosphogypsum after the filtration respectively with the vitriol oil and its generation acid decomposition reaction;
Wherein at first the phosphorite concentrate is pulverized, at 60 ℃～90 ℃, in liquid-solid mass ratio be the ratio of 4:1 to add concentration be that 20wt%～23wt% phosphoric acid reacts, the reaction times is 1～3 hour; Then add concentration again and be at least 97% vitriol oil and continue reaction, add-on is SO in liquid phase wherein
3Concentration is 35 ± 2g/L, and the reaction times is 0.5～6 hour, and temperature of reaction 20-80 ℃, the after-filtration that reacts completely obtains raw phosphoric acid and phosphogypsum;
Wherein, because the control vitriolization is divided phosphorus decomposing concentrate temperature (20-80 ℃), time (0.5-6h) and acidity ([H]: condition difference 1.0-3.0M), and the amount that makes rare earth enter in the raw phosphoric acid is different;
(2) with the raw phosphoric acid that obtains in the step (1) through pervaporation, concentrate, from escaping gas, reclaim fluorine, silicon through conventional treating processes, after obtaining the step of hydrogen fluoride, silicon-dioxide, reclaim the step of rare earth element, adjust the solution phosphorus acid content and reach 40%, make rare earth, calcium and strontium form phosphate mixt and separate out, rare earth exists with the form of calcium phosphate precipitation; Above-mentioned reaction product filtration is obtained phosphoric acid and RE phosphate precipitation.The phosphoric acid that an obtains part is adjusted concentration set by step 1) add-on returns sour decomposition process, a part enters into the become more meticulous processing and producing of phosphorous chemical industry process after using tributyl phosphate (TBP)-sulfonated kerosene solvent extraction further to purify again after the purification of routine;
Extracting and purifying phosphoric acid process condition is: 5 grades of 10 grades of fractionation extractions and half countercurrent reextractions wherein fractionation extraction comprise 5 grades of extractions, 5 grades of washings for 10 grades;
The purifying phosphoric acid chemical constitution that makes according to above technical parameter is as follows:
Chemical constitution: P
2O
5Ca
2+∑ Fe Mg
2+Al
3+SO
4 2-Cl
-F
-Content/(g/L): 123 0.005 0.015 0.002＜0.002-3.0-
Purifying phosphoric acid total recovery: 90%;
(3) with the phosphogypsum that obtains in the step (1) through with 1～5% sulfuric acid as leaching liquid, repeatedly leaching of the routine of leaching and washing step obtain leach liquor and " phosphorus CaSO
4Gypsum ", wherein the rare earth in the leach liquor is settled out with the form of RE phosphate through recycling, and the rest part of leach liquor can return sour decomposition process and recycles.
(4) " the phosphorus CaSO that obtains in the step (3)
4Gypsum " transform through conventional bicarbonate of ammonia and to obtain POV ammonium and thick lime carbonate, in this step with above-mentioned leaching and washing back " phosphorus CaSO
4Gypsum " and bicarbonate of ammonia be put in the reactor by mass ratio 1.3:1 and an amount of water or circulation washing lotion; stir and be heated to 50～75 ℃ of temperature, pressure 0.1～1.0MPa; the complete final vacuum suction filtration of stirring reaction; obtain ammoniumsulphate soln; filter cake washes with water and once carries out next step reaction or oven dry, and the washing lotion Returning reactor recycles;
(5) (the NH to obtaining in the step (4)
4)
2SO
4Solution carries out further ALP (triple effect evaporation) triple effect and concentrates, and obtains purity more than or equal to 99% ammonium sulfate;
(6) add ammoniacal liquor in after filtering the thick lime carbonate in step (4), carry out chlorination and obtain bicarbonate of ammonia and calcium chloride solution transition, the step of converting (4) that the bicarbonate of ammonia that obtains is returned phosphogypsum recycles;
(7) collect the RE phosphate precipitation that obtains in the step (2) and (3), mix RECl through producing behind alkaline process disaggregating treatment, washing, the dissolving with hydrochloric acid
3Solution;
(8) calcium chloride solution that obtains in the step (6) extracts then with the recovery rare earth element, thereby obtains rare earth chloride and calcium chloride crystal; Wherein extracting with the P507-sulfonated kerosene is extraction agent, and extraction system is RECl
3-HCl, the washing lotion of employing is 0.1～6.0N HCl, stripping solution is 1.5～6.0N HCl, finally obtains RECl
3Product, byproduct NH
4Cl returns step step (6) chlorination transition, and the calcium chloride solution of removing behind the rare earth element promptly gets CaCl through condensing crystal
2Product; Wherein P507 is 2-hexyl-hexyl sour single 2-hexyl-own ester of seeing, and the extraction mode is to be selected from one or more continuous cascade extraction modes that comprise fractionation extraction and heat up in a steamer the group of extraction, counter-current extraction and half counter-current extraction.
In above-mentioned steps (3), the phosphorus concentrate obtains raw phosphoric acid and phosphogypsum after filtration after sulfuric acid decomposes.Contain impurity such as part acid in the phosphogypsum, in this process, must leach and wash to reduce phosphogypsum acidity, simultaneously elements such as recovery part phosphorus and rare earth.
The alkali decomposition process is 30～60% for adding NaOH alkali lye mass percent concentration to RE phosphate in the above-mentioned steps (7), reacts under 120～170 ℃ temperature of reaction 0.5～7.0 hour.
Washing step is the ratio of 1:3～1:10 for adopting solid and water volume ratio in the above-mentioned steps (7), adopts the mode of washing of 10 grades of continuous adverse currents, carries out under 40-90 ℃ wash temperature.Thereby sodium phosphate and excessive alkali liquid washing get off and reclaim in the rare-earth hydroxide after alkali decomposed, and the rare-earth hydroxide that washing is got well enters the dissolving with hydrochloric acid operation.In addition, can from the washings of final high concentrated phase, reclaim Na through concentrating
3PO
4
In the dissolving with hydrochloric acid operation, working concentration is to be not less than 30% hydrochloric acid in the above-mentioned steps (7), and temperature of reaction is 70～90 ℃, and the rare-earth chloride solution that finally obtains is about 200～290g/L for REO concentration, and the pH value is 4.0～4.5.
Phosphogypsum described in the present invention refers to the gypsum that contains than impurity such as Tripyrophosphoric acid after persulfuric acid decomposes; Phosphorus CaSO
4Gypsum refers to through containing the gypsum of a small amount of impurity after the leaching washing.
The of the present invention phosphorite ore deposit is fully utilized cleans the technology of producing and therefrom extract rare earth, be main chemical reagent with sulfuric acid, in producing the phosphating processes process, solved recycling and problem of complex utilization of various chemical industry auxiliary materials in the technological process.With lower technology cost, the further processing of phosphogypsum obtained Industrial products such as ammonium sulfate and calcium salt, the simultaneously comprehensive valuable elements such as the rare earth that is extracted in the occurring in nature resource scarcity, fluorine that reclaim, and making purifies after its enrichment again reclaims, and its cost is lower than pure fluorine ore deposit, the production cost of rare-earth mineral work flow.Bicarbonate of ammonia and the ammonium chloride that produces in the technological process recycles simultaneously; realized changing waste into resources and the commercialization in the technological process with lower running cost; realized that comprehensive utilization of resources and environment protection organically combine; reduce explained hereafter cost and environmental improvement cost, realized low-cost, oligosaprobic zero release and changing waste into resources and the commercialization that cleans production, waste water.
The invention has the advantages that the raw materials used equal reusable edible of whole process flow or make product that waste obviously reduces; Can realize cleaning production; The turnover ratio height, the product purity height; In high dissolubility weak acidic medium, CaCO
3The selection solvability is good, stable, repeating utilization factor is high; The comprehensive yield height of each element such as P, Ca, RE (rare earth element), F and Si, cost is low, quality good; Process spread is good, is fit to the needs that product structure is adjusted flexibly and fine chemistry industry develops; Economy, environmental benefit are bigger, meet the requirement of recycling economy and Sustainable development.
Description of drawings
Fig. 1 is the schema that present conventional wet method is extracted phosphoric acid process;
Fig. 2 is a process flow sheet of the present invention.
Embodiment
Below in conjunction with specific embodiment the present invention is described in detail, but these embodiment are used to illustrate of the present invention that and the present invention is not limited only to these embodiment.
Phosphorite ore deposit material composition used among the present invention is as shown in table 1.
Table 1. raw material major ingredient content
Used main auxiliary material is as shown in table 2.
Table 2.
If no special instructions, the percentage ratio that relates in following examples is mass percent.
Operate according to following steps:
Step (1) is according to the technology of conventional wet method system phosphoric acid, get phosphorite concentrate 10Kg, be crushed to 100 orders, under 80 ± 5 ℃ temperature of reaction, is that 20wt%～23wt% phosphoric acid reacts in liquid-solid ratio (mass ratio) for the ratio of 4:1 adds 40kg concentration, and the reaction times is 2 hours; Then add concentration again and be at least 97% vitriol oil and continue reaction, add-on is SO in liquid phase wherein
3Concentration is 35 ± 2g/L, and the reaction times is 5 hours, and the after-filtration that reacts completely obtains raw phosphoric acid and phosphogypsum.Make raw phosphoric acid strength of solution (P through reaction
2O
5) be 29%; The concentrate rate of decomposition is 98%; P
2O
5Extraction yield is 96%; The rare earth oxide extraction yield is 43.5%.
(2) with the raw phosphoric acid that obtains in the step (1) through pervaporation, concentrate, from escaping gas, reclaim fluorine, silicon through conventional treating processes, obtain the step of hydrogen fluoride, silicon-dioxide after, reclaim the step of rare earth element, wherein P in the raw phosphoric acid solution
2O
5Content is about 160.7g/L, and REO content is about 0.217g/L.When the solution phosphorus acid content reached 40%, rare earth, calcium and strontium formed phosphate mixt and separate out, and rare earth exists with the form of calcium phosphate precipitation.Above-mentioned reaction product filtration is obtained phosphoric acid and RE phosphate precipitation, is 23% at this RE phosphate middle-weight rare earths oxide content.A phosphoric acid part that obtains is returned sour decomposition process, a part is through the TBP-of routine sulfonated kerosene solvent extraction purification, rare earth oxide extraction yield from settling is 99.4%, enters into the become more meticulous processing and producing of phosphorous chemical industry process after further purifying then.The processing condition of extracting and purifying phosphoric acid are: with TBP-sulfonated kerosene solvent is extraction agent, 10 grades of fractionation extractions (extract 5 grades, wash 5 grades), 5 grades of back extractions (half adverse current).The purifying phosphoric acid total recovery is 90%.
The purifying phosphoric acid chemical constitution that makes according to above technical parameter is as follows:
| Chemical constitution | P 2O 5 | Ca 2+ | ∑Fe | Mg 2+ | Al 3+ | SO 4 2- | Cl - | F - |
| Content/(g/L) | 123 | 0.005 | 0.015 | 0.002 | <0.002 | - | 3.0 | - |
(3) phosphogypsum that obtains in the step (1) is leached and washing step through routine, the sulfuric acid with 1～5% is as leaching liquid, and 7 leachings obtain leach liquor and phosphorus CaSO
4Gypsum.Wherein the rare earth in the leach liquor (REO) concentration is 1.0g/l, obtains the RE phosphate precipitation through recycling, and REO content is about 27%.Phosphogypsum middle-weight rare earths leaching yield is 60.1%, P in the phosphogypsum
2O
5The rate of recovery is 67%, and the F rate of recovery is 50% in the phosphogypsum.And can returning sour decomposition course, the rest part of leach liquor recycles.
(4), " the phosphorus CaSO that obtains in (5) step (3)
4Gypsum " obtain POV ammonium and thick lime carbonate through conventional bicarbonate of ammonia conversion.In this step with above-mentioned leaching and the wet phosphorus CaSO in washing back
4Gypsum and bicarbonate of ammonia are pressed phosphorus CaSO
4Gypsum: bicarbonate of ammonia=1.3:1 (mass ratio) and an amount of water (or circulation washing lotion) are put in the reactor, stir and are heated under 75 ℃, the pressure of 1.0MPa, stirring reaction 1.0h.Vacuum filtration obtains ammoniumsulphate soln then, and filter cake washes with water and once carries out next step reaction or oven dry, and the washing lotion Returning reactor recycles.The ammoniumsulphate soln concentration that makes is 30%, obtains crystal ammonium sulfate product (chemical pure), SO through the three-effect evaporation and condensation crystallization
4 2-Transformation efficiency is 〉=99%, the purity of byproduct lime carbonate 〉=83%.
(6) add ammoniacal liquor in the thick lime carbonate that obtains after filtering in step (4), carry out chlorination and obtain bicarbonate of ammonia and calcium chloride solution transition, the step of converting (4) that the bicarbonate of ammonia that obtains is returned phosphogypsum recycles.
In this step, the byproduct lime carbonate (purity 〉=83%) that the phosphogypsum conversion reaction generates can further transform, with the byproduct ammonium chloride that reclaims in the Rare Earth Separation process is transforming agent, add certain amount of ammonia water, control pH reacts in the scope of 7-9, preparation calcium chloride and recovery bicarbonate of ammonia, and impurity is less in the calcium chloride that obtains.Bicarbonate of ammonia directly returns to be realized in the technological process recycling.
(7) collect the RE phosphate precipitation that obtains in the step (2) and (3), through producing mixed chlorinated rare earth solution behind alkaline process disaggregating treatment, washing, the dissolving with hydrochloric acid;
Wherein alkali decomposition process is 30% for adding NaOH alkali lye mass percent concentration to above-mentioned blended rare-earth chloride solution, and reaction is 7.0 hours under 120 ℃ temperature of reaction.Thereby change the RE phosphate decomposition into rare-earth hydroxide.Then the rare-earth hydroxide that obtains is washed, wherein solid-to-liquid ratio is 1:10 (volume ratio), adopts the mode of washing of 10 grades of continuous adverse currents, carries out under 90 ℃ wash temperature.Thereby sodium phosphate and excessive alkali liquid washing get off and reclaim in the rare-earth hydroxide after alkali decomposed, and the rare-earth hydroxide that washing is got well enters the dissolving with hydrochloric acid operation.
In addition, can from the washings of final high concentrated phase, reclaim Na through concentrating
3PO
4
In the dissolving with hydrochloric acid operation, the hydrochloric acid that uses is technical grade, and temperature of reaction is 90 ℃, and the rare-earth chloride solution that finally obtains is about 200～290g/L for REO concentration, and the pH value is 4.0～4.5.
(8) calcium chloride solution that obtains in the filtration step (6) extracts then with the recovery rare earth element, thereby obtains rare earth chloride and calcium chloride crystal.In the multi-stage solvent extraction mode of fractionation extraction, be extraction agent with the P507-sulfonated kerosene wherein, extraction system is RECl
3-HCl, the washing lotion of employing is 0.5NHCl, anti-liquid (stripping solution) is 4.5NHCl, finally obtains RECl
3Solution, byproduct NH
4Cl returns step (6) chlorination step transition.Calcium chloride solution after the removal of impurities promptly gets CaCl through condensing crystal
2Product.In this process, rare earth yield is 99.5%; CaCl
2The rate of recovery of (technical pure) is 91%.
The RECl that obtains
3Solution, currently known methods routinely, through removal of impurities, purifying, precipitation, crystallization, concentrate, aftertreatment means such as calcination, screening, can obtain serial simplification compounds such as La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Y.
Embodiment 2
Operate according to following steps:
Step (1) is according to the technology of conventional wet method system phosphoric acid, get phosphorite concentrate 20Kg, be crushed to 100 orders, under 80 ℃ temperature of reaction, react for 21wt% phosphoric acid for the ratio adding 80kg concentration of 4:1 in liquid-solid ratio (mass ratio), the reaction times is about 2 hours; Then add concentration again and be at least 97% vitriol oil and continue reaction, add-on is SO in liquid phase wherein
3Concentration is 35 ± 2g/L, and the reaction times is about 5 hours, and the after-filtration that reacts completely obtains raw phosphoric acid and phosphogypsum.Make raw phosphoric acid strength of solution (P through reaction
2O
5) be 27.5%; The concentrate rate of decomposition is 98%; P
2O
5Extraction yield is 96%; The rare earth oxide extraction yield is 43.1%.
(2) with the raw phosphoric acid that obtains in the step (1) through pervaporation, concentrate, from escaping gas, reclaim fluorine, silicon through conventional treating processes, obtain the step of hydrogen fluoride, silicon-dioxide after, reclaim the step of rare earth element, wherein P in the raw phosphoric acid solution
2O
5Content is about 160.1g/L, and REO content is about 0.213g/L.When the solution phosphorus acid content reached 40%, rare earth, calcium and strontium formed phosphate mixt and separate out, and rare earth exists with the form of calcium phosphate precipitation.Above-mentioned reaction product filtration is obtained phosphoric acid and RE phosphate precipitation, is 21.5% at this RE phosphate middle-weight rare earths oxide content.A phosphoric acid part that obtains is returned sour decomposition process, a part is through the TBP-of routine sulfonated kerosene solvent extraction purification, rare earth oxide extraction yield from settling is 99.0%, enters into the become more meticulous processing and producing of phosphorous chemical industry process after further purifying then.The processing condition of extracting and purifying phosphoric acid are: with TBP-sulfonated kerosene solvent is extraction agent, 10 grades of fractionation extractions (extract 5 grades, wash 5 grades), 5 grades of back extractions (half adverse current).The purifying phosphoric acid total recovery is 90%.
The purifying phosphoric acid chemical constitution that makes according to above technical parameter is as follows:
| Chemical constitution | P 2O 5 | Ca 2+ | ∑Fe | Mg 2+ | Al 3+ | SO 4 2- | Cl - | F - |
| Content/(g/L) | 125 | 0.005 | 0.015 | 0.002 | <0.002 | - | 3.0 | - |
(3) phosphogypsum that obtains in the step (1) is leached and washing step through routine, the sulfuric acid with 1～5% is as leaching liquid, and 7 leachings obtain leach liquor and phosphorus CaSO
4Gypsum.Wherein the rare earth in the leach liquor (REO) concentration is 0.97g/l, is settled out through the form of recycling with RE phosphate, and REO content is about 27%.Phosphogypsum middle-weight rare earths leaching yield is 60.1%, P in the phosphogypsum
2O
5The rate of recovery is 67.2%, and the F rate of recovery is 51% in the phosphogypsum.And can returning sour decomposition course, the rest part of leach liquor recycles.
(4), " the phosphorus CaSO that obtains in (5) step (3)
4Gypsum " obtain POV ammonium and thick lime carbonate through conventional bicarbonate of ammonia conversion.In this step with above-mentioned leaching and the wet phosphorus CaSO in washing back
4Gypsum and bicarbonate of ammonia are pressed phosphorus CaSO
4Gypsum: bicarbonate of ammonia=1.3:1 (mass ratio) and an amount of water (or circulation washing lotion) are put in the reactor, stir and are heated under 50 ℃, the pressure of 0.1MPa, stirring reaction 7h.Vacuum filtration obtains ammoniumsulphate soln then, and filter cake washes with water and once carries out next step reaction or oven dry, and the washing lotion Returning reactor recycles.The ammoniumsulphate soln concentration that makes is 30%, obtains crystal ammonium sulfate product (chemical pure), SO through the three-effect evaporation and condensation crystallization
4 2-Transformation efficiency is 〉=99%, the purity of byproduct lime carbonate 〉=83%.
(6) add ammoniacal liquor in after filtering the thick lime carbonate in step (4), carry out chlorination and obtain bicarbonate of ammonia and calcium chloride solution transition, the step of converting (4) that the bicarbonate of ammonia that obtains is returned phosphogypsum recycles.
In this step, the byproduct lime carbonate (purity 〉=83%) that the phosphogypsum conversion reaction generates can further transform, with the byproduct ammonium chloride that reclaims in the Rare Earth Separation process is transforming agent, add ammoniacal liquor, control pH reacts in the scope of 7-9, preparation calcium chloride and recovery bicarbonate of ammonia, bicarbonate of ammonia directly return to be realized in the technological process recycling.
(7) collect the RE phosphate precipitation that obtains in the step (2) and (3), through producing mixed chlorinated rare earth solution behind alkaline process disaggregating treatment, washing, the dissolving with hydrochloric acid;
Wherein alkali decomposition process is 30% for adding NaOH alkali lye mass percent concentration to above-mentioned blended rare-earth chloride solution, and reaction is 7.0 hours under 120 ℃ temperature of reaction.Thereby change the RE phosphate decomposition into rare-earth hydroxide.
Then the rare-earth hydroxide that obtains is washed, wherein solid-to-liquid ratio is 1:3 (volume ratio), adopts the mode of washing of 10 grades of continuous adverse currents, carries out under 40 ℃ wash temperature.Thereby sodium phosphate and excessive alkali liquid washing get off and reclaim in the rare-earth hydroxide after alkali decomposed, and the rare-earth hydroxide that washing is got well enters the dissolving with hydrochloric acid operation.
In addition, can from the washings of final high concentrated phase, reclaim Na through concentrating
3PO
4
In the dissolving with hydrochloric acid operation, the hydrochloric acid that uses is technical grade, and temperature of reaction is 90 ℃, and the rare-earth chloride solution that finally obtains is about 200～290g/L for REO concentration, and the pH value is 4.0～4.5.
(8) calcium chloride solution that obtains in the filtration step (5) extracts then with the recovery rare earth element, thereby obtains rare earth chloride and calcium chloride crystal.Wherein extracting the multi-stage solvent extraction mode with fractionation extraction, is extraction agent with the P507-sulfonated kerosene, and extraction system is RECl
3-HCl, the washing lotion of employing is 0.5N HCl, anti-liquid is 4.5N HCl, finally obtains RECl
3Product, byproduct NH
4Cl returns step (6) chlorination step transition.Calcium chloride solution after the removal of impurities promptly gets CaCl through condensing crystal
2Product.In this process, rare earth yield is 99.5%; CaCl
2The rate of recovery of (technical pure) is 91%.
Claims (4)
1, a kind of phosphorite ore deposit is fully utilized cleans the technology of producing and therefrom extracting rare earth, and it may further comprise the steps:
(1) according to the technology of conventional wet method system phosphoric acid, the phosphorite green ore is obtained the phosphorite concentrate after ore dressing, generate raw phosphoric acid and phosphogypsum, obtain raw phosphoric acid and phosphogypsum after the filtration respectively with the vitriol oil and its generation acid decomposition reaction;
Wherein at first the phosphorite concentrate is pulverized, at 60 ℃～90 ℃, in liquid-solid mass ratio be the ratio of 4:1 to add concentration be that 20wt%～23wt% phosphoric acid reacts, the reaction times is 1～3 hour; Then add concentration again and be at least 97% vitriol oil and continue reaction, add-on is SO in liquid phase wherein
3Concentration is 35 ± 2g/L, and the reaction times is 0.5-6 hour, and the temperature of reaction 20-80 ℃ of after-filtration that reacts completely obtains raw phosphoric acid and phosphogypsum;
(2) with the raw phosphoric acid that obtains in the step (1) through pervaporation, concentrate, from escaping gas, reclaim fluorine, silicon through conventional treating processes, after obtaining the step of hydrogen fluoride, silicon-dioxide, reclaim the step of rare earth element, adjust the solution phosphorus acid content and reach 40%, make rare earth, calcium and strontium form phosphate mixt and separate out, rare earth exists with the form of calcium phosphate precipitation; Filter then and obtain phosphoric acid and RE phosphate precipitation, with the phosphoric acid that an obtains part adjust concentration set by step (1) add-on return sour decomposition process, a part enters into phosphorous chemical industry process become more meticulous processing and production after further purifying with tributyl phosphate-sulfonated kerosene solvent extraction again after the purification of routine;
Extracting and purifying phosphoric acid process condition is: 5 grades of 10 grades of fractionation extractions and half countercurrent reextractions wherein fractionation extraction comprise 5 grades of extractions, 5 grades of washings for 10 grades;
(3) with the phosphogypsum that obtains in the step (1) through with 1～5% sulfuric acid as leaching liquid, repeatedly leaching of the routine of leaching and washing step obtain leach liquor and " phosphorus CaSO
4Gypsum ", wherein the rare earth in the leach liquor is settled out with the form of RE phosphate through recycling, and the rest part of leach liquor can return sour decomposition process and recycles;
(4) " the phosphorus CaSO that obtains in the step (3)
4Gypsum " obtain POV ammonium and thick lime carbonate through conventional bicarbonate of ammonia conversion; In this step with above-mentioned leaching and washing back " phosphorus CaSO
4Gypsum " and bicarbonate of ammonia be put in the reactor by mass ratio 1.3:1 and an amount of water or circulation washing lotion; stir and be heated to 50～75 ℃ of temperature, pressure 0.1～1.0MPa; the complete final vacuum suction filtration of stirring reaction; obtain ammoniumsulphate soln; filter cake washes with water and once carries out next step reaction or oven dry, and the washing lotion Returning reactor recycles;
(5) (the NH to obtaining in the step (4)
4)
2SO
4Solution carries out further three-effect evaporation and condensation, obtains purity and is not less than 99% ammonium sulfate;
(6) add ammoniacal liquor in after filtering the thick lime carbonate in step (4), carry out chlorination and obtain bicarbonate of ammonia and calcium chloride solution transition, the step of converting (4) that the bicarbonate of ammonia that obtains is returned phosphogypsum recycles;
(7) collect the RE phosphate precipitation that obtains in the step (2) and (3), mix RECl through producing behind alkaline process disaggregating treatment, washing, the dissolving with hydrochloric acid
3Solution;
(8) calcium chloride solution that obtains in the step (6) extracts then with the recovery rare earth element, thereby obtains rare earth chloride and calcium chloride crystal; Wherein extracting with the P507-sulfonated kerosene is extraction agent, and extraction system is RECl
3-HCl, the washing lotion of employing is 0.1～6.0N HCl, stripping solution is 1.5～6.0N HCl, finally obtains RECl
3Product, byproduct NH
4Cl returns step step (6) chlorination transition, and the calcium chloride solution of removing behind the rare earth element promptly gets CaCl through condensing crystal
2Product.
2, technology as claimed in claim 1 is characterized in that, adds ammoniacal liquor control pH value 7～9 in the step (6).
3, technology as claimed in claim 1 is characterized in that, the alkaline process disaggregating treatment is 30～60% for adding NaOH alkali lye mass percent concentration to RE phosphate in the step (7), reacts under 120～170 ℃ temperature of reaction 0.5～7.0 hour;
Washing step is the ratio of 1:3～1:10 for adopting solid and water volume ratio in the above-mentioned steps (7), adopts the mode of washing of 10 grades of continuous adverse currents, carries out under 40-90 ℃ wash temperature;
In the dissolving with hydrochloric acid operation, working concentration is to be not less than 30% hydrochloric acid in the above-mentioned steps (7), and temperature of reaction is 70～90 ℃, and the rare-earth chloride solution that finally obtains is 200～290g/L for REO concentration, and the pH value is 4.0～4.5.
4, the technology described in claim 1 is characterized in that, the used extraction mode of step (8) is to be selected from one or more continuous cascade extraction modes that comprise fractionation extraction and heat up in a steamer the group of extraction, counter-current extraction and half counter-current extraction.
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| RU2504593C1 (en) * | 2012-10-25 | 2014-01-20 | Общество с ограниченной ответственностью Минерал "Нано-Технология" | Method of processing phosphogypsum |
| CN103274378B (en) * | 2013-06-13 | 2014-12-17 | 四川商舟实业有限公司 | Electric calcination furnace and application of electric calcination furnace in preparing industrial-grade phosphoric acid |
| CN104278164B (en) * | 2014-09-29 | 2016-05-18 | 乐山盛和稀土股份有限公司 | Grade is at the fluorine carbonated rare earth ore deposit of 62%-72% treatment process |
| CN104357663B (en) * | 2014-11-10 | 2016-06-15 | 德阳三汇太阳能发电设备有限公司 | A kind of ardealite Application way |
| CN105859167B (en) * | 2015-01-21 | 2019-04-23 | 中国科学院过程工程研究所 | A method of Gao Bai, high-pure anhydrous calcium sulfate are prepared by ardealite |
| CN106044828B (en) * | 2016-07-19 | 2018-06-19 | 中化化肥有限公司成都研发中心 | The method of extraction deep purifying ardealite |
| CN106978531B (en) * | 2017-03-15 | 2018-12-14 | 包头稀土研究院 | The method that soda acid joint decomposes mixed rare earth concentrate |
| CN111270092B (en) * | 2020-02-07 | 2022-08-05 | 包头稀土研究院 | Method for decomposing mixed rare earth ore |
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