CN103382532B - Comprehensive utilization method for extraction separation of dolomite in rare earth - Google Patents
Comprehensive utilization method for extraction separation of dolomite in rare earth Download PDFInfo
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Abstract
A comprehensive utilization method for extraction separation of dolomite in rare earth is disclosed, and by taking dolomite as a raw material, a bicarbonate magnesium solution is prepared for extraction separation of rare earth and comprehensive recovery of calcium and magnesium. The method comprises: roasting dolomite to obtain a powder containing calcium oxide and magnesium oxide, mixing the powder with a solution of magnesium chloride or magnesium nitrate for a reaction to prepare magnesium hydroxide and a by-product calcium chloride or calcium nitrate and further to realize calcium-magnesium separation; performing slurry mixing on magnesium hydroxide, introducing carbon dioxide gas for a carbonization reaction to prepare the bicarbonate magnesium solution, mixing and extracting with acidic organic extraction agents such as P507, P204, naphthenic acid, C272 and the like to obtain a load organic phase containing magnesium and a saponification water phase; pre-extracting the magnesium-containing load organic phase with a solution of rare earth chlorides or rare earth nitrates to obtain a load organic phase containing rare earth ions and a raffinate water phase containing magnesium chloride or magnesium nitrate; applying the load organic phase to extraction separation of a mixed rare earth feed liquid to prepare a singular rare earth compound; and cycling one portion of the raffinate water phase to prepare magnesium hydroxide, and performing evaporating and drying on one portion of the raffinate water phase to produce magnesium chloride or magnesium nitrate.
Description
Technical field
The present invention relates to a kind of method of rhombspar comprehensive utilization.Taking rhombspar as raw material, prepare pure magnesium bicarbonate solution specifically, for extracting and separating mishmetal feed liquid, comprehensive calcium and the magnesium products of reclaiming simultaneously, belongs to rhombspar comprehensive utilization field.
Background technology
Rhombspar is the natural mineral that calcium carbonate is combined with magnesiumcarbonate, is generally white in color, canescence, yellow.Chemical molecular formula is CaMg (CO
3)
2, the molar ratio of theoretical calcium and magnesium is roughly 1:1; Separately contain a small amount of calcite CaCO
3and the quartzy SiO of minute quantity
2deng.China's dolomite resources is very abundant, distribute wide, the each province that spreads all over the country, the place of production, the main place of production in Shandong, the ground such as Liaoning, Shanxi, Hebei and Hubei and Hunan Provinces, 82.2 hundred million tons of retained reserves, raw material is cheaply easy to get.
Rhombspar purposes is very extensive, can be for every field such as refining magnesium industry, refractory materials, building material industry, glass-ceramic, agricultural, environmental protection, chemical industry.Because rhombspar is a kind of containing magnesium carbonate ore deposit, be the main existence form in magnesium ore deposit, therefore mainly adopt carborization, acid hydrolyzation, double decomposition etc. for the production of magnesium basic carbonate, magnesium oxide, magnesium hydroxide, containing calcium-magnesium ratio compound products such as magnesium calcium carbonate, magnesium sulfate, calcium sulfate in chemical industry.Wherein carborization production technique mainly contains rhombspar direct carborization and bittern-two kinds of lime-carbonated methods, prepares the serial magnesium compound such as magnesiumcarbonate and magnesium oxide, and concrete technology is as described below:
(1) rhombspar carborization: first rhombspar is calcined in limestone kiln and generated light dolomite, then the digestion generation that adds water contains Mg (OH)
2and Ca (OH)
2ash breast, grey breast is delivered to and in carbonating tower, carried out carbonization, reaction generates magnesium bicarbonate solution and calcium carbonate solid, remove after filtration containing the mother liquor after magnesium calcium carbonate (containing magnesium approximately 11% left and right) and be called heavy magnesium water, and then produce magnesiumcarbonate product, then pass through baked for producing magnesium oxide product through pyrolysis, filtration.The subject matter that this technique exists: 1. produce a large amount of low value-addedly containing magnesium calcium carbonate, if do not reclaim the forming paste (nearly 10 tons of waste residues) containing magnesium calcium carbonate and discharging of 5.5 tons of net weight of having an appointment of light magnesium oxide per ton, must cause environmental pollution.2. in rhombspar carborization gained heavy magnesium water, content of magnesia is on the low side, only has 7g/L left and right, and water loss is large, causes pyrolysis energy consumption to account for the more than 40% of total energy consumption, and production cost is high.As Chinese invention patent 201010149986.0 discloses a kind of method of utilizing producing high purity magnesium oxide with dolomite, Chinese invention patent 20061003154.1 discloses multi-stage spray carbonization, dissolved salt is separated out and prepared high-purity nano magnesia technique, is all to adopt rhombspar carborization to produce meticulous magnesium Chemicals.
(2) bittern-lime-carbonated method: during seawater or bittern and refining milk of lime (Dolomite milk) are delivered to and still generate Mg (OH)
2precipitation, after filtration, washing, Mg (OH) will wet
2add water after adjustment, deliver to carbonating tower, carry out carbonization with lime-kiln gas and obtain magnesium bicarbonate solution, then remove impurity after filtration, produce magnesiumcarbonate product, then pass through baked for producing magnesium oxide product through pyrolysis, filtration.The subject matter that this technique exists: if 1. do not observe specific deposition condition, the magnesium hydroxide making is separated out and (is conventionally less than 1 μ m), the extremely difficult sedimentation of slip and filtering separation becoming the very tiny colloid of crystallization; And strainability is poorer, bath water amount just the more.At present, by controlling reaction conditions, circulating seed crystal method obtains the magnesium hydrate precipitate of certain particle size, then with additive coagulations such as PAM to improve its strainability, but there is complex technical process, the defect such as product energy consumption is high, throughput is low.As Chinese invention patent 200310117851.6 discloses a kind of processing method of light dolomite concentrated seawater preparing magnesium hydroxide, in the time that light dolomite digests, add and contain a certain amount of magnesium hydroxide crystal seed, to improve the strainability of follow-up magnesium hydroxide.2. bittern is except containing MgCl
2outside composition, also contain the SO of dissolubility
4 2-, CO
3 2-, HCO
3 -, B (OH)
4 -, Fe
2+, Al
3+, Mn
2+, Ni
2+and organism, the silt particle etc. of non-dissolubility, conventionally need add ash charge breast, CaCl
2solution carries out decarburization and desulfurization pre-treatment, and then filters and be purified bittern, and this process not only technique is loaded down with trivial details, and produces a large amount of waste residues and pollute.3. because whole technique is single process, need to consume two kinds of resources of rhombspar and bittern, be unfavorable for industrial layout; Even if adopt industrial hex-ammoniate to substitute bittern, also can be because material cost is high, and cannot realize scale operation.Producing Magnesium Carbonate Light 41-45 and method of magnesium oxide as Chinese invention patent 200810053967.0 discloses dolomite sea water bittern, is to adopt bittern carborization to produce magnesium salts product.
Summary of the invention
The present invention, improving on the basis of rhombspar carbonization technique, prepares pure magnesium bicarbonate solution, for extracting and separating mishmetal feed liquid, and then the calcium producing in process and magnesium is all converted into high value added product.Both realized in extracting and separating rear earth process and having discharged without ammonia nitrogen, realized again the comprehensive utilization of rhombspar, there is good economic and social benefit.
After the present invention is light-burned by rhombspar, obtain containing calcium oxide and magnesium oxide powder (light dolomite) directly with magnesium chloride or magnesium nitrate solution hybrid reaction, generate magnesium hydroxide solid and calcium chloride or ca nitrate soln, realize the separation of calcium magnesium; Obtain calcium chloride or nitrocalcite product containing calcium solution through concentrated, crystallization, filtration, oven dry, or through concentrated, again with sulfuric acid reaction, prepare crystal of calcium sulfate, hydrochloric acid or nitric acid product; After magnesium hydroxide is sized mixing, pass into carbon dioxide and carry out carburizing reagent and prepare magnesium bicarbonate solution; Magnesium bicarbonate solution obtains containing magnesium-supported organic phase and saponification water for the acid organic extractant of saponification, and wherein saponification water is cycled to used in magnesium hydroxide and sizes mixing; Extract in advance with earth solution again containing magnesium-supported organic phase, obtain containing the load organic phases of difficult extraction rare earth ion with containing magnesium raffinate water through clarification, load organic phases is further used for the extracting and separating of mishmetal feed liquid, raffinate aqueous portion is cycled to used in prepares magnesium hydroxide, and part is prepared magnesium chloride or magnesium nitrate product.Whole technical process realizes recycle, does not substantially produce the three wastes, belongs to cleaning procedure.Taking chlorination system as example, primitive reaction formula is as follows:
CaOMgO+MgCl
2+ 2H
2o==2Mg (OH)
2+ CaCl
2------reaction formula 1
CaCl
2+ H
2sO
4==CaSO
4↓+2HCl------reaction formula 2
Mg (OH)
2+ 2CO
2==Mg (HCO
3)
2------reaction formula 3
CaCl
2+ Mg (OH)
2+ CO
2==CaCO
3↓+2MgCl
2+ H
2o------reaction formula 4
Ca (OH)
2+ CO
2==CaCO
3↓+H
2o------reaction formula 5
CaCO
3+ CO
2+ H
2o==Ca (HCO
3)
2------reaction formula 6
Mg (HCO
3)
2+ 2HA==MgA
2+ 2CO
2↑+2H
2o------reaction formula 7
3MgA
2+ 2RE
acl
3==2RE
aa
3+ 3MgCl
2------reaction formula 8
RE
aa
3+ RE
bcl
3==RE
ba
3+ RE
acl
3------reaction formula 9
Wherein, HA represents acidic extractant, RE
arepresent difficult extraction rare earth element, RE
brepresent Yi Cui rare earth element
In the magnesium hydrate precipitate that filtration obtains, can carry a small amount of calcium chloride solution secretly, because the existence of calcium chloride can affect the carbonization efficiency (seeing reaction formula 4) of magnesium hydroxide, in magnesium hydrate precipitate, also can contain micro-impurity Ca (OH) simultaneously
2therefore to, through washing deliming, make CaO/MgO molar ratio in filter cake be less than 5%, and by the strict pH value of controlling in carbonization process, can ensure that calcium cpd generates Calcium Carbonate Filtration and removes (seeing reaction formula 4,5), can effectively avoid carbonization like this and generate calcium bicarbonate solution; If calcium contents is too high in magnesium hydroxide filter cake, easily there is carbonization and generated calcium bicarbonate solution (seeing reaction formula 6) in the calcium carbonate of fresh generation.
The concrete technical scheme of the present invention is as follows:
The present invention proposes the method for comprehensive utilization of a kind of rhombspar in rare earth extraction separates, it is characterized in that, taking rhombspar as raw material, preparing magnesium bicarbonate solution for extracting and separating rear earth, and comprehensively reclaim the method for calcium and magnesium, the method at least comprises the steps:
(1) digestion alkali turns
After rhombspar is light-burned, obtain containing calcium oxide and magnesian powder and rich carbonated kiln gas, will containing calcium oxide and magnesian powder directly with 0.1～2.5mol/L magnesium chloride or magnesium nitrate solution hybrid reaction, then carry out solid-liquid separation and obtain magnesium hydroxide filter cake and calcium chloride or calcium nitrate filtrate, filtrate is prepared calcium cpd product for reclaiming;
(2) carbonization of sizing mixing
Magnesium hydroxide filter cake washes with water after calcium, then water sizes mixing, and controlling MgO content in slurries is 1～30g/L, then carries out carbonization to passing into carbon dioxide in magnesium hydroxide slurry, and reaction process dividing potential drop is 0～0.8MPa, and partial pressure of carbon dioxide ≠ 0; Control carburizing reagent terminal pH=6.5～7.5, obtain after filtration magnesium bicarbonate solution, its concentration is counted 1～25g/L with MgO;
(3) extracting and separating rear earth
Adopt magnesium bicarbonate solution to carry out saponification to organic extractant, obtain containing magnesium-supported organic phase and saponification water and carbon dioxide; Extract in advance with earth solution containing magnesium-supported organic phase again, obtain containing rare earth loaded organic phase with containing magnesium raffinate water, the extracting and separating containing rare earth loaded organic phase for mishmetal feed liquid, reclaims and prepares magnesium compound product containing magnesium raffinate water.
When the described control of step (1) react, pH value is 9.8～12.0, and concentrating filter liquor, crystallization, filtration, oven dry obtain calcium chloride or nitrocalcite product, or through concentrating, again with sulfuric acid reaction, prepare crystal of calcium sulfate and hydrochloric acid or nitric acid product.
The molar ratio of magnesium oxide amount in calcium oxide content and magnesium chloride or magnesium nitrate solution in light dolomite described in step (1): CaO/MgO=90～110%, in the time reclaiming calcium magnesium products, if obtain the high purity magnesium compound that purity is high as far as possible, CaO/MgO ratio should be less than 100%, can control alkali and turned time, pH value is 9.8～10.4, in gained magnesium hydroxide solid, calcium hydroxide content is extremely low when ensureing that alkali turns, and carbonization process is easy to control Calcium hydrogen carbonate content; If obtain high-purity calcium cpd in order to reclaim, CaO/MgO ratio should be greater than 100%, add excessive light dolomite, magnesium chloride or magnesium nitrate can be converted into magnesium hydrate precipitate completely when ensureing that alkali turns, in calcium chloride or ca nitrate soln, Mg content is extremely low, can prepare like this calcium chloride or nitrocalcite or calcium sulfate product that purity is higher.
The temperature of the roasting of the rhombspar described in step (1) is 900～1200 DEG C; The time of roasting is 1～12, makes containing calcium oxide and magnesium oxide powder and rich carbonated kiln gas.
The described magnesium hydroxide filter cake of step (2) washes with water after calcium, and in filter cake, CaO/MgO molar ratio is less than 5%, is optimized for 1%.
The carbon dioxide that the blank organic extractant saponification of the carbonated kiln gas of richness of step (1) gained and step (3) produces, returns for step (2) magnesium hydroxide slurry carbonization and prepares magnesium bicarbonate solution.
Described pure magnesium bicarbonate solution preparation method is as follows for step (2): water sizes mixing magnesium hydroxide filter cake to 5～25g/L(MgO meter), gas concentration lwevel is 30～100V%, partial pressure of carbon dioxide is 0～0.4MPa, temperature of reaction is controlled at 0～50 DEG C, reaction times is 10～60min, control carbonization terminal pH=7.0～7.5, obtain after filtration pure magnesium bicarbonate solution.
The described saponification water of step (3) returns in step (2), sizes mixing for magnesium hydroxide filter cake.It is magnesium chloride or magnesium nitrate solution that pre-extraction obtains raffinate water, and pH value is 3～4, takes out and magnesium chloride or the magnesium nitrate of step (1) equimolar amount, returns in step (1), and contains calcium oxide and magnesium oxide powder hybrid reaction and prepares magnesium hydroxide; Residue magnesium chloride containing or magnesium nitrate raffinate water obtain magnesium chloride or magnesium nitrate product, its MgCl through concentrated, crystallization, filtration, oven dry
26H
2o or Mg (NO
3)
26H
2o content > 98%, quality reaches GB chemical reagent standard.
The described organic extractant of step (3) is containing one or more acidic extractants in P507, P204, naphthenic acid, C272, and with organic solvent diluting, extractant concentration is 0.2～1.7mol/L.
The described earth solution of step (3) is the raffinate containing one or more difficult extraction rare earth elements that rare earth extraction segregation section obtains, and its rare earth REO concentration is 0.2～1.7mol/L; Described rare earth feed liquid is mixed chlorinated rare earth solution, mixeding acid rare-earth solution, mixing rare earth sulfate solution or its mixing solutions that contains at least 2 kinds of rare earth elements, and its rare earth concentration is 0.2～1.7mol/L.。
Advantage of the present invention is:
(1) containing calcium oxide and magnesium oxide powder directly and magnesium chloride or magnesium nitrate solution hybrid reaction prepare magnesium hydroxide, not only omit containing calcium oxide and magnesium oxide powder digestive process, simplify technique, can effectively improve the concentration of by-product calcium chloride or nitrocalcite simultaneously, save heating concentrated cost; And in light dolomite powder, MgO digestion forms Mg in magnesium hydroxide adsorbent solution
2+and promotion nucleus growth obviously improves the strainability of magnesium hydroxide.
(2) magnesium bicarbonate solution of preparing, for extracting and separating rear earth, not only substitutes ammoniacal liquor saponification organic, has eliminated the pollution of ammonia nitrogen waste water to environment from source; And saponification water can be cycled to used in magnesium hydroxide and sizes mixing, raffinate aqueous portion is cycled to used in and prepares magnesium hydroxide simultaneously, part is for the preparation of magnesium chloride or magnesium nitrate product, realize the recycle of waste water and magnesium chloride or magnesium nitrate solution, and in Rare Earths Countercurrent Extraction Process, realized the comprehensive utilization to magnesium resource in rhombspar.
(3) high concentration carbon dioxide that is rich in carbonic acid gas kiln gas and the organic generation of saponification that rhombspar roasting produces, after treated and collecting, can return for magnesium hydroxide slurry carbonization, realizes carbon dioxide recycling, has realized low-carbon emission.
(4) in whole technical process, dolomite resources is fully utilized, and particularly, when preparation liquid soaps agent-magnesium bicarbonate solution is used for extracting and separating rear earth, has comprehensively reclaimed calcium and magnesium products, unharmful waste sludge discharge, economy and environment benefit is very remarkable.
(5) in whole technical process, magnesium calcium byproduct quality is good, and especially magnesium chloride or magnesium nitrate product reach GB chemical reagent standard, and added value of product is large, has wide market outlook.
Brief description of the drawings:
Fig. 1 is the process flow sheet of the inventive method.Protection domain of the present invention is not subject to the restriction of process flow sheet.
Embodiment
With embodiment, method of the present invention and application thereof are described further below.Protection domain of the present invention is not subject to the restriction of these embodiment, and protection domain of the present invention is determined by claims.
As shown in Figure 1, after rhombspar roasting, obtain containing calcium oxide and magnesium oxide powder (being light dolomite) and rich carbonated kiln gas.Light dolomite refilters after directly mixing with magnesium chloride solution and digest alkali and turn containing calcium oxide and magnesium oxide powder, and the filter cake obtaining is Mg (OH)
2; Filtrate is CaCl
2can directly prepare calcium chloride product (CaCl
2product), or and sulfuric acid reaction, prepare crystal of calcium sulfate (CaSO
4product) and hydrochloric acid (HCl) product.Mg (OH)
2filter cake obtains Mg (HCO through sizing mixing, after carbonization and filtration
3)
2solution.Mg (HCO
3)
2solution carries out saponification (organic referred to as saponification in Fig. 1) to organic extractant, obtains containing magnesium-supported organic and saponification waste-water and CO
2gas, wherein, saponification waste-water returns sizes mixing in operation, sizes mixing for magnesium hydroxide; CO
2the kiln gas obtaining after gas and rhombspar roasting returns in carbonation process after purification, distribution, for magnesium hydroxide carbonization; Mix in advance and extract containing magnesium-supported organic part raffinate obtaining with mishmetal feed liquid extracting and separating again, obtain containing rare earth loaded organic phase with containing magnesium raffinate water, can return to the alkali order of changing a job containing magnesium raffinate water and prepare magnesium hydroxide, also can obtain MgCl through concentrated, crystallization, filtration, oven dry
2product; Extracting and separating containing rare earth loaded organic phase for mishmetal feed liquid, obtains single rare earth compound.
embodiment 1
Rhombspar is obtained containing calcium oxide and magnesium oxide powder at 1000 DEG C of roasting 4h, get 915g(CaO/MgO molar ratio in 1.05 left and right), slowly join in the magnesium chloride solution of 2mol/L of 5L, the molar ratio CaO/MgO=98% of magnesium oxide amount in calcium oxide content and magnesium chloride solution in the powder adding, the pH value of reaction is 10.4, clarification filtration, filtration time is 10 minutes, then washing obtains magnesium hydroxide filter cake 2198g and calcium chloride filtrate, concentrating filter liquor, crystallization, filtration, oven dry obtain Calcium dichloride dihydrate byproduct 1368g, with CaCl
2meter content is 69.3%, reaches technical grade salable product.
Magnesium hydroxide filter cake washes with water after calcium, CaO/MgO molar ratio 0.8% in filter cake after tested, water is sized mixing to 12g/L(MgO meter), then pass into 80V% carbon dioxide (the mixed C O of kiln gas and the organic generation of saponification under magnesium hydroxide slurry normal pressure
2gas) to dividing potential drop be 0.3MPa, controlling carburizing reagent terminal pH is 7.0, temperature of reaction is 20 DEG C, the reaction times is 20min, obtains after filtration pure magnesium bicarbonate solution 11.5g/L(MgO meter) 62L.
Adopt 62L magnesium bicarbonate solution to carry out saponification to 66.3L 1.5mol/LP204 organic phase, obtain containing magnesium-supported organic, wherein magnesium ion content is 0.26mol/L; After the clarification of saponification water, return for magnesium hydroxide filter cake and size mixing.To extract in advance containing magnesium-supported organic and 7.8L lanthanum chloride solution (1.46mol/L), and obtain containing lanthanum load organicly, its concentration is 0.17mol/L, for the extracting and separating of mixed rare earth of lanthanum and cerium feed liquid; Raffinate water MgCl
2content is 2.19mol/L, and pH value is 3.0, takes out 4.6L and returns to alkali and go to step as magnesium chloride raw material, and residue 3.3L obtains analytical pure magnesium chloride product through further concentrated, crystallization, filtration, oven dry.Concrete analysis the results are shown in Table 1.
The mass analysis of table 1 magnesium chloride product
Comparative example
Rhombspar is obtained containing calcium oxide and magnesium oxide powder at 1000 DEG C of roasting 4h, getting 915g(CaO/MgO molar ratio is 1.05), add 5L water to digest, then add 5L magnesium chloride solution (2mol/L), the molar ratio CaO/MgO=98% of magnesium oxide amount in calcium oxide content and magnesium chloride solution in the powder adding, the pH value of reaction is 10.4, clarification filtration, filtration time is 40 minutes, then washing obtains magnesium hydroxide filter cake 2258g and calcium chloride filtrate, concentrating filter liquor, crystallization, filtration, oven dry obtain Calcium dichloride dihydrate byproduct 1390g, with CaCl
2meter content is 70.1%, reaches technical grade salable product.
embodiment 2
Rhombspar is obtained containing calcium oxide and magnesium oxide powder 420.0kg(CaO/MgO molar ratio in 1.05 left and right at 1150 DEG C of roasting 4h), slowly join 4.17m
3the magnesium chloride solution of 1.2mol/L in, the molar ratio CaO/MgO=90% of magnesium oxide amount in calcium oxide content and magnesium chloride solution in the powder adding, the pH value of reaction is 9.8, then filter, wash and obtain magnesium hydroxide filter cake 1262kg and calcium chloride filtrate, filtrate concentrates and obtains Calcium dichloride dihydrate byproduct 628kg through heating, with CaCl
2meter content is 60.5%.
Magnesium hydroxide filter cake washes with water after calcium, CaO/MgO molar ratio 0.1% in filter cake after tested, water is sized mixing to 25g/L(MgO meter), then pass into 50V% carbon dioxide (the mixed C O of kiln gas and the organic generation of saponification to magnesium hydroxide slurry
2gas) to dividing potential drop be 0.4MPa, controlling carburizing reagent terminal pH is 7.5, temperature of reaction is 32 DEG C, the reaction times is 40min, obtains after filtration pure magnesium bicarbonate solution 23.7g/L(MgO meter) 13.5m
3.
Flow velocity by magnesium bicarbonate solution with 1.9L/min, 1.42mol/L P507 organic phase adds in 4 grades of extraction tanks and carries out common stream pre-treatment with the flow velocity of 4L/min, obtains containing magnesium-supported organic, and wherein magnesium ion content is 0.27mol/L; After the clarification of saponification water, return for magnesium hydroxide filter cake and size mixing.To add and in 6 grades of extraction tanks, carry out adverse current and extract in advance with the flow velocity of 0.9L/min containing magnesium-supported organic and praseodymium chloride solution (0.79mol/L), obtain containing praseodymium load organicly, its concentration be 0.18mol/L, for the extracting and separating of praseodymium neodymium mixed rare-earth feed liquid; Raffinate water MgCl
2content is 1.19mol/L, and pH value is 4.0, takes out 4.2m
3return to alkali and go to step as magnesium chloride raw material, residue 2.4m
3obtain the pure magnesium chloride product of top grade through concentrated, crystallization, filtration, oven dry, concrete analysis the results are shown in Table 1.
embodiment 3
Rhombspar is obtained containing calcium oxide and magnesium oxide powder at 950 DEG C of roasting 10h, get 1367g(CaO/MgO molar ratio in 1.05 left and right) with the magnesium chloride solution hybrid reaction of the 1.95mol/L of 7.692L, the molar ratio CaO/MgO=96% of magnesium oxide amount in calcium oxide content and magnesium chloride solution in the powder adding, the pH value of reaction is 10.2, then filter, wash and obtain magnesium hydroxide filter cake 3662g and calcium chloride filtrate, filtrate concentrates and obtains Calcium dichloride dihydrate byproduct 2011g through heating, with CaCl
2meter content is 69.0%, reaches technical grade salable product.
Magnesium hydroxide filter cake washes with water after calcium, CaO/MgO molar ratio 0.5% in filter cake after tested, water is sized mixing to 9.1g/L(MgO meter), magnesium hydroxide slurry being passed into 35V% carbon dioxide (rhombspar roasting kiln gas) to dividing potential drop is 0.3MPa again, controlling carburizing reagent terminal pH is 7.0, temperature of reaction is 15 DEG C, and the reaction times is 15min, obtains after filtration pure magnesium bicarbonate solution 8.7g/L(MgO meter) 120L.
Flow velocity by magnesium bicarbonate solution with 7.9L/min, 1.5mol/L P507 organic phase adds in 8 grades of extraction tanks and carries out common stream pre-treatment with the flow velocity of 6L/min, obtains containing magnesium-supported organic, and wherein magnesium ion content is 0.28mol/L; After the clarification of saponification water, return for magnesium hydroxide filter cake and size mixing.To add and in 6 grades of extraction tanks, carry out adverse current and extract in advance with the flow velocity of 0.82L/min containing magnesium-supported organic and terbium chloride solution (1.37mol/L), obtain containing terbium load organicly, its concentration be 0.18mol/L, for the extracting and separating of terbium dysprosium mishmetal feed liquid; Raffinate water MgCl
2content is 2.05mol/L, and pH value is 3.5, and taking-up 7.32L returns to alkali and goes to step as magnesium chloride raw material, and residue 5.13L obtains analytical pure magnesium chloride product through concentrated, crystallization, filtration, oven dry.
embodiment 4
Rhombspar is obtained containing calcium oxide and magnesium oxide powder, getting 69kg(CaO/MgO molar ratio in 1.05 left and right at 1050 DEG C of roasting 6h) slowly join 1m
3the magnesium chloride solution of 0.80mol/L in, the molar ratio CaO/MgO=94% of magnesium oxide amount in calcium oxide content and magnesium chloride solution in the powder adding, the pH value of reaction is 10.3, then filter, wash and obtain magnesium hydroxide filter cake 145.3kg and calcium chloride filtrate, filtrate concentrates and obtains Calcium dichloride dihydrate byproduct 103.8kg through heating, with CaCl
2meter content is 68.4%, reaches technical grade salable product.
Magnesium hydroxide filter cake washes with water after calcium, CaO/MgO molar ratio 0.3% in filter cake after tested, water is sized mixing to 15g/L(MgO meter), then will under magnesium hydroxide slurry normal pressure, pass into the 93V% carbon dioxide (CO of the organic generation of saponification
2gas), controlling carburizing reagent terminal pH is 7.2, temperature of reaction is 23 DEG C, the reaction times is 30min, obtains after filtration pure magnesium bicarbonate solution 14.2g/L(MgO meter) 3.8m
3.
By 3.8m
3magnesium bicarbonate solution and 5m
30.7mol/L naphthenic acid joins 12m simultaneously
3reactive tank in be uniformly mixed 50 minutes, clarify 20 minutes, by saponification aqueous phase separation, clarification after, return for magnesium hydroxide filter cake and size mixing.Then add 0.70m
3yttrium chloride solution (1.24mol/L), is uniformly mixed 15 minutes, through clarification in 30 minutes, obtains the load organic phases containing yttrium, and its concentration is 0.17mol/L, for the extracting and separating of rich yttrium mixed rare earth feed liquid; Raffinate water MgCl
2content is 1.86mol/L, and pH value is 3.5, and taking-up 425L returns to alkali and goes to step as magnesium chloride raw material, and residue 287L obtains analytical pure magnesium chloride product through concentrated, crystallization, filtration, oven dry.
embodiment 5
Rhombspar is obtained containing calcium oxide and magnesium oxide powder at 920 DEG C of roasting 12h, get 170g(CaO/MgO molar ratio in 1.05 left and right) with the magnesium chloride solution hybrid reaction of the 2.2mol/L of 0.8L, the molar ratio CaO/MgO=100% of magnesium oxide amount in calcium oxide content and magnesium chloride solution in the powder adding, the pH value of reaction is 10.8, then filter, wash and obtain magnesium hydroxide filter cake 343g and calcium chloride filtrate, concentrating filter liquor, crystallization, filtration, oven dry obtain Calcium dichloride dihydrate byproduct 252g, with CaCl
2meter content is 69.5%, reaches technical grade salable product.
Magnesium hydroxide filter cake washes with water after calcium, CaO/MgO molar ratio 2.0% in filter cake after tested, water is sized mixing to 10g/L(MgO meter), be 0.1MPa to passing into 97V% carbon dioxide (the CO2 gas of the organic generation of saponification) to dividing potential drop under magnesium hydroxide slurry normal pressure again, controlling carburizing reagent terminal pH is 7.5, temperature of reaction is 40 DEG C, and the reaction times is 35min, obtains after filtration pure magnesium bicarbonate solution 9.8g/L(MgO meter) 13.5L.
Adopt 13.5L magnesium bicarbonate solution to carry out saponification to 12.6L 1.35mol/LP507 organic phase, obtain containing magnesium-supported organic, wherein magnesium ion content is 0.26mol/L; After the clarification of saponification water, return for magnesium hydroxide filter cake and size mixing.To extract in advance containing magnesium-supported organic and 2.1L lanthanum chloride solution (0.99mol/L), and obtain containing lanthanum load organicly, its concentration is 0.17mol/L, for the extracting and separating of mixed rare earth of lanthanum and cerium feed liquid; Raffinate water MgCl
2content is 1.48mol/L, and pH value is 3.0, takes out 1.2L and returns to alkali and go to step as magnesium chloride raw material, and residue 1L obtains magnesium chloride product, wherein MgCl through further concentrated, crystallization, filtration, oven dry
26H
2o content 97.8%, Ca content is 0.1%.
embodiment 6
Rhombspar is obtained containing calcium oxide and magnesium oxide powder at 1200 DEG C of roasting 1h, get 2940.0g(CaO/MgO molar ratio in 1.05 left and right) directly join in the magnesium chloride solution of 1.5mol/L of 20L, the molar ratio CaO/MgO=105% of magnesium oxide amount in calcium oxide content and magnesium chloride solution in the powder adding, the pH value of reaction is 11.2, then filter, wash and obtain calcium magnesium filter cake 7112g and calcium chloride filtrate, concentrating filter liquor, crystallization, filtration, oven dry obtain Calcium dichloride dihydrate byproduct 4189g, with CaCl
2meter content is 72.3%, reaches technical grade acceptable end product.
Calcium magnesium filter cake water is repeatedly washed after calcium, CaO/MgO molar ratio 4.5% in filter cake after tested, water is sized mixing to 7.5g/L(MgO meter, disregards calcium hydroxide part), then magnesium hydroxide slurry is passed into 75V% carbon dioxide (the mixed C O of kiln gas and the organic generation of saponification
2gas) to dividing potential drop be 0.2MPa, controlling carburizing reagent terminal pH is 7.1, temperature of reaction is 45 DEG C, the reaction times is 25min, obtains after filtration Magnesium hydrogen carbonate/calcium solution 6.4g/L(MgO meter) 300L.
Flow velocity by magnesium bicarbonate solution with 10.8L/min, 1.48mol/L P507 organic phase adds in 4 grades of extraction tanks and carries out common stream pre-treatment with the flow velocity of 6L/min, obtains containing magnesium-supported organic, and wherein magnesium ion content is 0.28mol/L; After the clarification of saponification water, return for magnesium hydroxide filter cake and size mixing.To add and in 4 grades of extraction tanks, carry out adverse current and extract in advance with the flow velocity of 4.2L/min containing magnesium-supported organic and neodymium chloride solution (0.255mol/L), obtain containing neodymium load organicly, its concentration be 0.18mol/L, for the extracting and separating of neodymium samarium mishmetal feed liquid; Raffinate water MgCl
2content is 0.38mol/L, and pH value is 3.3, and taking-up 78.4L returns to alkali and goes to step as magnesium chloride raw material, and residue 42.7L obtains magnesium chloride product, wherein MgCl through concentrated, crystallization, filtration, oven dry
26H
2o content 96.5%, Ca content is 0.5%.
embodiment 7
Rhombspar is obtained containing calcium oxide and magnesium oxide powder 1044g(CaO/MgO molar ratio in 1.05 left and right at 1100 DEG C of roasting 3h), directly in the magnesium chloride solution of the excessive 2.5mol/L that joins 4L, the molar ratio CaO/MgO=110% of magnesium oxide amount in calcium oxide content and magnesium chloride solution in the powder adding, the pH value of reaction is 11.8, then filter, washing obtains calcium magnesium filter cake 3124g and calcium chloride filtrate, concentrating filter liquor obtains 3.15L to 3mol/L, add 6mol/L sulfuric acid 1.58L, after reaction, filter, washing, oven dry obtains Crystallization of Gypsum 1628.5g(with CaSO
42H
2o meter content is greater than 98%) and the 4.2mol/L salt acid product of 4.5L.
Magnesium hydroxide filter cake water is repeatedly washed after calcium, CaO/MgO molar ratio 5% in filter cake after tested, water is sized mixing to 8g/L(MgO meter, disregards calcium hydroxide part), then pass into 60V% carbon dioxide (the mixed C O of kiln gas and the organic generation of saponification under magnesium hydroxide slurry normal pressure
2gas) to dividing potential drop be 0.1MPa, controlling carburizing reagent terminal pH is 7.3, temperature of reaction is 5 DEG C, the reaction times is 30min, obtains after filtration Magnesium hydrogen carbonate/calcium solution 7.0g/L(MgO meter) 100L.
Adopt 100L magnesium bicarbonate solution to carry out saponification to 125L 0.75mol/LP204 organic phase, obtain containing magnesium-supported organic, wherein magnesium ion content is 0.14mol/L; After the clarification of saponification water, return for magnesium hydroxide filter cake and size mixing.To extract in advance containing magnesium-supported organic and 16.7L solution of cerium chloride by oxidation (0.675mol/L), and obtain containing cerium load organicly, its concentration is 0.09mol/L, for the extracting and separating of cerium praseodymium mishmetal feed liquid; Raffinate water MgCl
2content is 1.01mol/L, and pH value is 4.0, takes out 9.88L and returns to alkali and go to step as magnesium chloride raw material, and residue 7.28L obtains analytical pure magnesium chloride product, wherein MgCl through further concentrated, crystallization, filtration, oven dry
26H
2o content 93.8%, Ca content is 1.5%.
embodiment 8
Rhombspar is obtained containing calcium oxide and magnesium oxide powder 190.0kg(CaO/MgO molar ratio in 1.05 left and right at 1000 DEG C of roasting 5h), slowly join 4m
3the magnesium chloride solution of 0.5mol/L in, the molar ratio CaO/MgO=102% of magnesium oxide amount in calcium oxide content and magnesium chloride solution in the powder adding, the pH value of reaction is 11.0, then filter and obtain calcium chloride filtrate, concentrating filter liquor, crystallization, filtration, oven dry obtain calcium chloride byproduct 279.3kg, with CaCl
2meter content is 71.4%, reaches technical grade acceptable end product; After filter cake adds water and sizes mixing, more slowly add the magnesium chloride solution of 0.5mol/L, the pH value of controlling reaction is that 9.9 terminations add, and then filters, washs and obtain magnesium hydroxide filter cake 415.1kg.
Magnesium hydroxide filter cake further washes with water after calcium, CaO/MgO molar ratio 0.1% in filter cake after tested, water is sized mixing to 10g/L(MgO meter), then pass into 99.8V% carbon dioxide (technical grade CO under magnesium hydroxide slurry normal pressure
2gas), controlling carburizing reagent terminal pH is 7.5, temperature of reaction is 15 DEG C, the reaction times is 30min, obtains after filtration pure magnesium bicarbonate solution 9.9g/L(MgO meter) 15m
3.
Flow velocity by magnesium bicarbonate solution with 6L/min, 1.48mol/L P507 organic phase adds in 6 grades of extraction tanks and carries out common stream pre-treatment with the flow velocity of 5.5L/min, obtains containing magnesium-supported organic, and wherein magnesium ion content is 0.266mol/L; After the clarification of saponification water, return for magnesium hydroxide filter cake and size mixing.To add and in 6 grades of extraction tanks, carry out adverse current and extract in advance with the flow velocity of 0.62L/min containing magnesium-supported organic and praseodymium chloride solution (1.55mol/L), obtain containing praseodymium load organicly, its concentration be 0.175mol/L, for the extracting and separating of praseodymium neodymium mixed rare-earth feed liquid; Raffinate water MgCl
2content is 2.33mol/L, and pH value is 3.5, takes out 0.86m
3return to alkali and go to step as magnesium chloride raw material, residue 0.71m
3obtain analytical pure magnesium chloride product through concentrated, crystallization, filtration, oven dry.
embodiment 9
Rhombspar is obtained containing calcium oxide and magnesium oxide powder at 1100 DEG C of roasting 3h, get 1330g(CaO/MgO molar ratio in 1.05 left and right) with the magnesium nitrate solution hybrid reaction of the 1.00mol/L of 15L, the molar ratio CaO/MgO=95% of magnesium oxide amount in calcium oxide content and magnesium nitrate solution in the powder adding, the pH value of reaction is 10.1, then filter, wash and obtain magnesium hydroxide filter cake 1598g and calcium nitrate filtrate, filtrate concentrates and obtains four water-calcium nitrate byproduct 3195g through heating, with Ca (NO
3)
24H
2o meter content is 99.0%, reaches technical grade acceptable end product.
Magnesium hydroxide filter cake washes with water after calcium, CaO/MgO molar ratio 0.4% in filter cake after tested, water is sized mixing to 18.0g/L(MgO meter), then magnesium hydroxide slurry is passed into the 97V% carbon dioxide (CO of the organic generation of saponification
2gas) to dividing potential drop be 0.2MPa, controlling carburizing reagent terminal pH is 7.0, temperature of reaction is 10 DEG C, the reaction times is 50min, obtains after filtration pure magnesium bicarbonate solution 17.3g/L(MgO meter) 60L.
Flow velocity by magnesium bicarbonate solution with 2.9L/min, 1.5mol/L P507 organic phase adds in 3 grades of extraction tanks and carries out adverse current pre-treatment with the flow velocity of 4.5L/min, obtains containing magnesium-supported organic, and wherein magnesium ion content is 0.275mol/L; After the clarification of saponification water, return for magnesium hydroxide filter cake and size mixing.To add and in 2 grades of extraction tanks, carry out adverse current and extract in advance with the flow velocity of 0.81L/min containing magnesium-supported organic and lanthanum nitrate hexahydrate (1.00mol/L), obtain containing lanthanum load organic, its concentration is 0.179mol/L, for the extracting and separating of lanthanum cerium mixeding acid rare-earth feed liquid, through 65 grades of fractionation extractions, obtain the cerous nitrate that purity is 99.99% lanthanum nitrate and 99.95%; Pre-extraction raffinate water MgCl
2content is 1.50mol/L, and pH value is 3.0, and taking-up 10L returns to alkali and goes to step as magnesium nitrate raw material, and residue 7.07L obtains analytical pure magnesium nitrate product through concentrated, crystallization, filtration, oven dry.
Claims (13)
1. the method for comprehensive utilization of rhombspar in rare earth extraction separates, is characterized in that, taking rhombspar as raw material, preparing magnesium bicarbonate solution for extracting and separating rear earth, and comprehensively reclaims the method for calcium and magnesium, and the method at least comprises the steps:
(1) digestion alkali turns
After rhombspar roasting, obtain containing calcium oxide and magnesian powder and rich carbonated kiln gas, will containing calcium oxide and magnesian powder directly with 0.5～2.5mol/L magnesium chloride or magnesium nitrate solution hybrid reaction, while reaction, pH value is 9.8～12.0, then carry out solid-liquid separation and obtain magnesium hydroxide filter cake and calcium chloride or calcium nitrate filtrate, filtrate is prepared calcium cpd product for reclaiming;
(2) carbonization of sizing mixing
The magnesium hydroxide filter cake that step (1) is obtained washes with water after calcium, in filter cake, CaO/MgO molar ratio is less than 5%, water is sized mixing again, controlling MgO content in slurries is 1～30g/L, carries out carbonization to passing into carbon dioxide in magnesium hydroxide slurry, and reaction process dividing potential drop is 0～0.8MPa, and partial pressure of carbon dioxide ≠ 0, and control carburizing reagent terminal pH=6.5～7.5, and obtaining after filtration magnesium bicarbonate solution, its concentration is counted 1～25g/L with MgO;
(3) extracting and separating rear earth
The magnesium bicarbonate solution that adopts step (2) to obtain carries out saponification to organic extractant, obtains containing magnesium-supported organic phase and saponification water and carbon dioxide; Extract in advance with earth solution again containing magnesium-supported organic phase, obtain containing rare earth loaded organic phase with containing magnesium raffinate water, extracting and separating containing rare earth loaded organic phase for mishmetal feed liquid, be magnesium chloride or magnesium nitrate solution containing magnesium raffinate water, magnesium chloride or the magnesium nitrate of taking-up and step (1) equimolar amount, return in step (1) with containing calcium oxide and magnesian powder hybrid reaction and prepare magnesium hydroxide; Residue magnesium chloride containing or magnesium nitrate raffinate water obtain high pure magnesium chloride or magnesium nitrate product through concentrated, crystallization, filtration, oven dry.
2. the method for comprehensive utilization of a kind of rhombspar according to claim 1 in rare earth extraction separates, it is characterized in that: in step (1), carrying out in solid-liquid separation, concentrating filter liquor, crystallization, filtration, oven dry obtain calcium chloride or nitrocalcite product, or through concentrated, again with sulfuric acid reaction, prepare crystal of calcium sulfate and hydrochloric acid or nitric acid product.
3. the method for comprehensive utilization of a kind of rhombspar according to claim 1 in rare earth extraction separates, it is characterized in that: in step (1), the molar ratio containing magnesium oxide amount in the calcium oxide content in calcium oxide and magnesian powder and magnesium chloride or magnesium nitrate solution: CaO/MgO=90～110%.
4. the method for comprehensive utilization of a kind of rhombspar according to claim 1 in rare earth extraction separates, is characterized in that: the temperature of the roasting of the rhombspar described in step (1) is 900～1200 DEG C; The time of roasting is 1～12h.
5. the method for comprehensive utilization of a kind of rhombspar according to claim 1 in rare earth extraction separates, is characterized in that: described magnesium hydroxide filter cake washes with water after calcium, and in filter cake, CaO/MgO molar ratio is less than 1%.
6. the method for comprehensive utilization of a kind of rhombspar according to claim 1 in rare earth extraction separates, is characterized in that: the carbon dioxide that the carbonated kiln gas of richness that step (1) produces and step (3) organic extractant saponification produce is for the carburizing reagent of step (2).
7. the method for comprehensive utilization of a kind of rhombspar according to claim 1 in rare earth extraction separates, it is characterized in that: sizing mixing in carbonization process step (2) Suo Shu, magnesium hydroxide filter cake washes with water after calcium, water is sized mixing again, control MgO content to 5～25g/L in slurries, partial pressure of carbon dioxide is 0～0.4MPa, and partial pressure of carbon dioxide ≠ 0 control carbonization terminal pH=7.0～7.5.
8. the method for comprehensive utilization of a kind of rhombspar according to claim 1 in rare earth extraction separates, is characterized in that: sizing mixing in carbonization process step (2) Suo Shu, the gas concentration lwevel using is 30～100V%; Be controlled at 0～50 DEG C to the carbonation reaction temperature that passes into carbon dioxide in magnesium hydroxide slurry, the reaction times is 10～60min.
9. the method for comprehensive utilization of a kind of rhombspar according to claim 1 in rare earth extraction separates, is characterized in that: the described saponification water of step (3) returns in step (2), sizes mixing for magnesium hydroxide filter cake.
10. the method for comprehensive utilization of a kind of rhombspar according to claim 1 in rare earth extraction separates, it is characterized in that: the described organic extractant of step (3) is containing one or more acidic extractants in P507, P204, naphthenic acid, C272, and with organic solvent diluting, this organic extraction agent concentration is 0.2～1.7mol/L.
The method of comprehensive utilization of 11. a kind of rhombspars according to claim 1 in rare earth extraction separates, it is characterized in that: the described earth solution of step (3) is the raffinate containing one or more difficult extraction rare earth elements that rare earth extraction segregation section obtains, and its rare earth concentration is 0.2～1.7mol/L.
The method of comprehensive utilization of 12. a kind of rhombspars according to claim 1 in rare earth extraction separates, it is characterized in that: the described rare earth feed liquid of step (3) is mixed chlorinated rare earth solution, mixeding acid rare-earth solution, mixing rare earth sulfate solution or its mixing solutions that contains at least 2 kinds of rare earth elements, and its rare earth concentration is 0.2～1.7mol/L.
The method of comprehensive utilization of 13. a kind of rhombspars according to claim 1 in rare earth extraction separates, is characterized in that: MgCl in high pure magnesium chloride prepared by magnesium chloride containing or magnesium nitrate raffinate water or magnesium nitrate product
26H
2o or Mg (NO
3)
26H
2o content > 98%, quality reaches GB chemical reagent standard.
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| CN102259898A (en) * | 2011-06-30 | 2011-11-30 | 武汉钢铁(集团)公司 | Method for preparing magnesium hydroxide utilizing light-burned dolomite powder |
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| CN101781706A (en) * | 2009-01-15 | 2010-07-21 | 有研稀土新材料股份有限公司 | Process for separating rare-earth element by extraction |
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