CN1240858C - Carbon reducting roast process of producing RE chloride with mixed RE concentrate - Google Patents
Carbon reducting roast process of producing RE chloride with mixed RE concentrate Download PDFInfo
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Abstract
The present invention relates to a carbon reducing roasting process for producing rare-earth chloride with mixed rare-earth concentrate, which belongs to the field of rare earth chemical industry. The technological process comprises the steps: chemical ore dressing, reduction roasting, solid activation, countercurrent washing, sub acid water washing, dissolving with hydrochloric acid, neutralizing to removing impurities, concentrating, crystallization and causticizing recovery. During roasting, cerium is reduced into a low-valent state, and fully dissolving effects of the hydrochloric acid is guaranteed, the comprehensive recovery of selection solution and washed solution is realized. The process of the present invention has the obviously advantages of zero release of exhaust gas and waste water in the technical process, resource recovery of industrial residues, low production cost, high recovery rate of rare earth.
Description
The present invention relates to a kind of method that rare earth concentrate carbon reducting roast is produced rare earth chloride of mixing, belong to the rare earth chemical field.
Mixed rare earth concentrate is that the inner mongolia baiyuneboite selects the iron byproduct, on rare earth market, the world, occupy the rare-earth mineral produce market share of half approximately, it also is unique mixed rare earth concentrate, mainly constitute by a hamartite and an only layer stone ore, the ratio of the two is about 9: 1-1: 1, the rare earth composition is based on light rare earths, and cerium content accounts for half.Mixed rare earth concentrate is because of the singularity of its mineral composition, and far from each other with the pre-treating technology of hamartite.The hamartite main product is in U.S.'s awns court of a feudal ruler Paasche (MountainPass), China's Sichuan Mianning, the Weishan, Shandong, ground such as Baotou, its treatment process mainly contains soda processes, the oxidizing roasting method, ammonium chloride methods etc. are (referring to " rare earth " first volumes such as Xu Guangxian, the 2nd edition, Chinese patent publication number CN1237539A, CN1236017A, CN1078498A, Cn1202460A, CN1240759A) the overrich sulfuric acid process once appearred in mixed rare earth concentrate, soda processes, the soda ash method, high-temperature chlorination, oxidizing roasting method etc., because of various reasons, domestic existing main vitriol oil method and two kinds of processing methodes of soda processes of adopting are handled mixed rare earth concentrate.Vitriol oil method and soda processes have been established the development foundation of China's rare-earth industry, made major contribution, but because of the reinforcement and the progress of science and technology of environmental protection is faced with serious challenge, the caustic soda genealogy of law adopts concentrated caustic (NaOH) pyrolytic decomposition concentrate to generate oxygen rare earth oxide slip, through impurity, the excellent molten re chlorides that gets of hydrochloric acid such as washing defluorination phosphorus, concentrate preparation rare earth chloride product through removal of impurities again, the greatest problem that this method exists is only suitable higher-grade concentrate, production cost is higher, discharged volume of industrial waste water is big, the pollution abatement costs height.The vitriol oil genealogy of law adopts vitriol oil roasting at high temperature to decompose mixed rare earth concentrate and generates water-solubility rare-earth vitriol, again through water logging, removal of impurities, abstraction and type-reverting or carbon ammonium precipitation through dissolving with hydrochloric acid, removal of impurities concentrate mixed chlorinated rare earth, the greatest problem that exists of this method is hydrogen fluoride (HF), the sulphur oxygen (SO that roasting process is discharged as everyone knows
x) tail gas pollution, control expense is high; The disposal of a large amount of low-activity water logging slags and the discharging of acidic and alkaline waste water etc.The soda ash rule is utilized Na
2CO
3Decompose concentrate, cerium is oxidized to tetravalence during roasting, and subsequent technique is set for carrying cerium.
The method that a kind of mixed rare earth concentrates carbon reducting roast that the objective of the invention is to provide at mixed rare earth concentrate the deficiencies in the prior art part is produced rare earth chloride.
The objective of the invention is to take following measure to realize:
A kind of mixed rare earth concentrates carbon reducting roast is produced the method for rare earth chloride, this technology comprises that chemical mineral processing, reducing roasting, solid-state activation, countercurrent washing, rare-acid water are washed, hydrochloric acid is molten entirely, in and removal of impurities, condensing crystal and causticization reclaim, concrete processing method is as follows:
(1) chemical mineral processing
The ore deposit of mixing of mixed rare earth concentrate---hamartite thing and monazite mineral, before roasting, implement chemical mineral processing selectively, grade 〉=60% concentrate directly batching carries out roasting, the concentrate of grade 50-60% is selected this operation, latter's concrete steps are: rare earth ore concentrate is selected in the liquid by the dilute hydrochloric acidization that solid-to-liquid ratio 1: 4-6 joins acidity 2-3mol/L, under 30-50 ℃ of condition of liquid temperature stirring reaction 1-1.5 hour, in the making ore dressing CaO content reach≤2%, carry out solid-liquid separation, it is stand-by to change the ore dressing filter cake, and filtrate adds sulfuric acid reaction again and reclaims hydrochloric acid, and gained has the calcium sulfate slag and reclaims liquid, reclaim liquid and select liquid to return usefulness through doing of allotment, the calcium sulfate slag is standby;
(2) reducing roasting
The Na of the rare earth ore concentrate of change ore dressing or concentrate grade 〉=60% and the 15-35% of dried ore deposit weight
2CO
3With the carbonaceous reducing agent of the 4-12% of dried ore deposit weight, thorough mixing is even, in the roasting alms bowl of packing into and add a cover, places kiln, carries out carbon reduction under temperature 900-1000 ℃, and concentrate is decomposed in roasting, and insulation roasting 1-3 hour is cooled to discharging below 400 ℃ then.The main chemical reactions that takes place in the roasting process is:
Reaction formula (6) is that carbon directly reduces CeO
2Be Ce
2O
3Main reaction, should reaction take place more than 900 ℃ according to thermomechanical analysis, with 700 ℃ of cerium dioxides reduction that generated in the past.The roasting result shows: concentrate decomposes fully, CeO in the calcining
2Content≤2%, process are only discharged CO
2Gas;
(3) solid-state activation
The NaOH of the 5-15% of roasting gained calcining and its weight is made into the 50-70% high alkali liquid and uses, and thorough mixing is in the roasting alms bowl of packing into and add a cover and put in the industrial furnace, temperature 140-180 ℃ of insulation activation 1-1.5 hour down; Its process main chemical reactions is:
This reaction is with new life's phosphorus cerium sodium stone (Na
3(Ce, La, Nd) [PO
4]
2, Vitusite) phosphorus in the mineral is converted into the water-soluble phosphoric acid trisodium, overcome roasting and directly washed the low problem of dephosphorization, same problem also is present in the soda roasting method;
(4) countercurrent washing
Solid-state activatory calcining is poured in the rinse bath, adds water and removes fluorine phosphorus through the washing of 4-5 stage countercurrent, and control condition is water temperature 60-70 ℃, solid-to-liquid ratio 1: 7-8, churning time 1-1.5 hour, settling time 0.5-2 hour, the washing terminal point goes out water ph value 7-9, and calcining adds in the sour fluid bowl stand-by through counter flow washing.The causticization operation is sent in the washing water outlet, and the fluorine tp removal rate of this operation all is higher than 95%;
Fast because of the calcining settling velocity, clarification can realize countercurrent washing easily, and it is slow to have overcome soda processes slip washing clarification, and washing times is many, is difficult for realizing the shortcoming of countercurrent washing;
(5) rare-acid water is washed
Do not change in advance choosing 〉=60% rare earth concentrate calcining carries out this operation, concrete steps are: through sizing mixing, in pickling tank, by solid-to-liquid ratio 1: 5-7, under the water temperature 40-60 ℃ of condition, the excellent molten calcium of dilute hydrochloric acid that slowly adds 2-3mol/L while stirring, pH value control 3.5-5 adds the acid amount and is advisable with control deliming rate about 50%;
(6) hydrochloric acid is molten entirely
Add in pickling tank that rare-acid water is washed or the calcining of countercurrent washing, after adding water and sizing mixing, add concentrated hydrochloric acid while stirring, in the time of temperature 50-95 ℃, dissolved 1-2 hour, rare earth is all dissolvings then, and the residual acid with 0.2-0.3mol/L HCl in hydro-oxidation rare earth or carbonated rare earth or used calcining or other alkali finishes filtration to PH1-1.5;
(7) in and removal of impurities
Because the present invention adopts the complete molten calcining of hydrochloric acid, cause Fe in the solution
2O
3Concentration is up to 5-30g/l, as adopts traditional Fe (OH)
3Neutralisation is no longer suitable, and this mainly is because Fe (OH)
3The sedimentation strainability worsen due to.Spray pyrrhosiderite (FeO (OH)) removes iron processes, and this method is because of the good sedimentation strainability of pyrrhosiderite, and the present invention can be realized smoothly.
Full dissolved rare earth filtrate adds small amounts agent, Oxidation of Fe
2+Be Fe
3+After again with in and slip in the desired rare earth filtrate of the pH value controlled variable of neutralization reaction with in and slip the two Theoretical Calculation mass rate ratio spray or be instilled in and receiver, stirring reaction, 70-90 ℃ of control liquid temperature, pH value 3-4, reinforced finishing transferred pH value to 4.5 with weak ammonia or carbon ammonium again, adds a small amount of BaCl simultaneously
2Remove SO
4 2-Ion, clarification is filtered.In and slip be rare earth hydrate or weak ammonia or the two collocation;
(8) condensing crystal
Qualified go up the scarfing cinder condensing crystal or with other technology streets connect all can, be operating as supernatant liquor put into enamel reactor, heating concentrating under reduced pressure crystallisation by cooling, the mixed chlorinated rare earth crystallization of REO 〉=45%;
(9) causticization reclaims
The countercurrent washing final outflow water is added in the causticizing tank, add CaO (excessive) causticization Na wherein
2CO
3, NaF, Na
3PO
4And form corresponding calcium precipitation, and 80-90 ℃ of causticization temperature, churning time 1-1.5 hour, reaction finished and promptly filters, and concentrating filter liquor is to about 50%NaOH high alkali liquid, and filter residue is collected stand-by.Causticizing reaction is as follows:
Carbonaceous reducing agent in the reducing roasting refers to a kind of material in coal dust, Graphite Powder 99, coke powder, the powdered carbon.Use former dose of reduction of carbonaceous cerium dioxide CeO in the carbon reducting roast
2Be sesquialter cerium oxide Ce
2O
3, in and removal of impurities in oxygenant be meant hydrogen peroxide or Sodium Nitrite.In and in the removal of impurities spray pyrrhosiderite remove iron processes and will contain Fe
2O
3For adopting spray mode or instillation mode, the re chloride of 5-30 grams per liter adds in the solution acceptor, at Fe
3+Under the extremely low state of degree, add thermo-neutrality and form pyrrhosiderite FeO (OH) precipitation.Solid-state activation utilization NaOH decomposes or conversion is adding Na
2CO
3New life's phosphorus ore thing Na during roasting
3RE (PO
4)
2Or other phosphorus containg substances and generate water-soluble phosphoric acid trisodium Na
3PO
4
The effect of invention
Its effect of method of the mixed rare earth concentrate carbon reducting roast production chlorination rare earth that the present invention proposes is: rare earth total recovery 〉=90%; Production cost is lower than existing method; Waste gas waste water has been realized zero release; Calcium sulfate slag and causticization slag can be sold, and iron thorium slag can further extract rare earth and prepare thorium nitrate 99.99004323A8urity etc. or dispose.
Embodiment:
Embodiment 1:
It is as follows that the mixed rare earth concentrate of selecting for use is formed (%):
TREO TFe F P
2O
5 CaO
54.30 3.12 6.13 10.54 7.48
(1) chemical mineral processing
Taking by weighing 1 kilogram of dried concentrate is added in 5 liters of beakers that fill 4 liters of 2.6mol/L hydrochloric acid dilute solutions, drip a small amount of sulfuric acid, open and stir, controlled temperature 30-50 ℃, 1 hour reaction times, leave standstill suction filtration after clarification half an hour, filtrate 1.84mol/L HCl adds 160 gram vitriol oil stirring reactions 2 hours again, left standstill supernatant liquor [H 16 hours
+] 2.5mol/L, CaO 2.3g/l can return the next timeization selection operation;
(2) reducing roasting
Change ore dressing filter cake (CaO 0.91%) and 110 grams, 80 order pulverized anthracites, 270 gram soda ash thorough mixing, reinstall in the roasting alms bowl and add a cover, put in the electric furnace, every stove is once adorned 4 alms bowls, amounts to 4 kilograms of dried concentrate.Be warming up to 950 ℃, insulation roasting 2 hours, CeO in the calcining is surveyed in the cooling back
20.3%;
(3) solid-state activation
60% alkali lye that is made into 20 gram NaOH in the steel alms bowl of packing into of calcining in every alms bowl is mixed, mixes thoroughly in the roasting alms bowl of packing into and add a cover, in drying oven in 160 ℃ of insulations 1 hour down, 4 kilograms of every stove processing;
(4) countercurrent washing
The condition of washing control is water temperature 60-70 ℃, and solid-to-liquid ratio 1: 8 stirred 1 hour at every turn, clarified 1 hour.With 43 liters of beakers, every alms bowl material divides 4 equal portions to be respectively charged into 4 beakers, finishes 4 stage countercurrents washings with the calcining of the dried concentrate of 4Kg, and getting 8 liters altogether, should to take out water stand-by.Washing back calcining analytical results: fluorine removes 97.8%, and phosphorus removes 95.2%.Material sedimentation clarification performance is good;
(5) hydrochloric acid is molten entirely
Get the countercurrent washing calcining of 1 kilogram of concentrate, put into 5 liters of beakers, adding water sizes mixing, add concentrated hydrochloric acid while stirring, finish, finish, survey remaining acidity 0.3mol/L HCl in the dissolving in 1 hour of 80-90 ℃ of following insulated and stirred, add standby rare earth hydrate slip and be neutralized to pH value 1-1.5, leave standstill suction filtration after half an hour, filter cake adds less water drip washing, collects filtrate and predicts REO 182g/l.Rare earth is dissolved as 98.2% (in solution middle-weight rare earths total amount);
(6) in and removal of impurities
Sour lixiviation liquid is put into beaker, add a small amount of hydrogen peroxide oxidation ferrous ion, splash into acceptance cup in the stirring simultaneously with the rare earth hydrate slip then, controlled temperature 80-85 ℃, pH value 3.5, reaction finishes and adds weak ammonia and transfer pH value 4.5, adds a small amount of BaCl
2Remove SO
4 2-Ion, solid-liquid separation get rare earth feed liquid and iron thorium slag.Result: rare earth yield 96%.Pyrrhosiderite iron thorium slag is heavy clear fast, easily filters, and filtrate is as clear as crystal, REO 162g/l, Fe
2O
3＜0.1g/l;
(7) condensing crystal
The accept condensing crystal is got rare earth chloride 1088 grams, and measurement result is: REO 45.2%, Fe
2O
30.032%, CaO 1.9%, SO
4 2-＜0.01%, PO
4 3-＜0.01%, NH
4Cl 2.9%, HB＜0.3%.Rare earth total recovery 90.6%;
(8) causticization reclaims
8 emersion water of countercurrent washing are put into metal bucket, add lime 300 grams, be warming up to 80-90 ℃, stirred 1.5 hours, natural filtration, filter residue are the causticization slag, and filtrate contains NaOH 38g/l, it is concentrated into 51.4% high alkali liquid in the concentrating pan heating, amounts to solid caustic soda 304 grams.
Embodiment 2:
Select for use the mixed type concentrate to form (%):
TREO TFe CaO F P
62.2 2.12 5.04 6.41 3.68
Take by weighing 500 gram (giving money as a gift) concentrate and 150 gram soda ash, 40 gram 80 order Graphite Powder 99s abundant mixings, put into the roasting alms bowl and add a cover 940-960 ℃ of insulation roasting 2 hours down, CeO in the back survey calcining is taken out in cooling
2Be 0.42%, add 55%NaOH solution 92 gram then, the mixing roasting alms bowl of packing into adds and is placed on 160-170 ℃ of insulation reaction 1 hour in loft drier, takes out and pours in the beaker 50-70 ℃ of washing 4 times down, and terminal point PH is 8-9.
Rare-acid water is washed: washing back calcining by 1: 5 thin up of solid-to-liquid ratio, be warming up to 50-60 ℃, open and stir and slow dropping 2mol/L dilute hydrochloric acid, PH is controlled at 〉=3.5, leaves standstill clarification when adding 180 milliliters of diluted acids.CaO 2.8% in the sampling and measuring calcining, washes calcium 52%, REO 1.2g/l in the washing lotion.
Add water again after supernatant liquor is discharged and size mixing, it is molten entirely at 80-90 ℃ of following hydrochloric acid to add concentrated hydrochloric acid, insulated and stirred 1.5 hours, add residual acidity that standby rare-acid water washes the calcining neutralization solution to pH value 1-1.5, filter, filter cake drip washing is once standby, survey filtrate REO163g/l, rare earth dissolution rate 98.2%.Filtrate adds a little Sodium Nitrite iron protoxide ion, is neutralized to PH4.5 clarification 8 hours with ammoniacal liquor again, and siphon supernatant liquor, sedimentation and filtration, filter residue are iron thorium slag, and supernatant liquor and filtrate merging get 629 gram rare earth chlorides, rare earth total recovery 91% through condensing crystal.The gained rare earth chloride meets national standard.
Claims (6)
1, a kind of mixed rare earth concentrates carbon reducting roast is produced the method for rare earth chloride, it is characterized in that, this technology comprises that chemical mineral processing, reducing roasting, solid-state activation, countercurrent washing, rare-acid water are washed, hydrochloric acid is molten entirely, in and removal of impurities, condensing crystal and causticization reclaim, concrete processing method is as follows:
(1) chemical mineral processing
At mixed rare earth concentrate---the ore deposit of mixing of hamartite thing and monazite mineral, implement chemical mineral processing before roasting selectively: grade 〉=60% concentrate directly batching carries out roasting; The concentrate of grade 50-60% is selected this operation, latter's concrete steps are: rare earth ore concentrate is selected in the liquid by the dilute hydrochloric acidization that solid-to-liquid ratio 1: 4-6 joins acidity 2-3mol/L, under 30-50 ℃ of condition of liquid temperature stirring reaction 1-1.5 hour, in the making ore dressing CaO content reach≤2%, carry out solid-liquid separation, it is stand-by to change the ore dressing filter cake, filtrate adds sulfuric acid reaction again and reclaims hydrochloric acid, gained has the calcium sulfate slag and reclaims liquid, reclaims liquid and selects liquid to return usefulness through doing of allotment, and the calcium sulfate slag is standby;
(2) reducing roasting
The Na of the rare earth ore concentrate of change ore dressing or concentrate grade 〉=60% and the 15-35% of dried ore deposit weight
2CO
3With the carbonaceous reducing agent of the 4-12% of dried ore deposit weight, thorough mixing is even, in the roasting alms bowl of packing into and add a cover, places kiln, carries out carbon reduction under temperature 900-1000 ℃, and concentrate is decomposed in roasting, and insulation roasting 1-3 hour is cooled to discharging below 400 ℃ then;
(3) solid-state activation
The NaOH of the 5-15% of roasting gained calcining and its weight is made into the 50-70% high alkali liquid and uses, thorough mixing, in the roasting alms bowl of packing into and add a cover and put in the industrial furnace, temperature 140-180 ℃ of insulation activation 1-1.5 hour down:
(4) countercurrent washing
Solid-state activatory calcining is poured in the rinse bath, adds water and removes fluorine phosphorus through the washing of 4-5 stage countercurrent, and control condition is water temperature 60-70 ℃, solid-to-liquid ratio 1: 7-8, and churning time 1-1.5 hour, settling time 0.5-2 hour, the washing terminal point went out water ph value 7-9;
(5) rare-acid water is washed
Do not change in advance choosing 〉=60% rare earth ore concentrate calcining carries out this operation, concrete steps are: the calcining through washing adds in the pickling tank, at solid-to-liquid ratio 1: 5-7, under the water temperature 40-60 ℃ of condition, the excellent molten calcium of dilute hydrochloric acid that slowly adds 2-3mol/L while stirring, pH value control 3.5-5 adds the acid amount and is advisable with control deliming rate about 50%;
(6) hydrochloric acid is molten entirely
Add in pickling tank that rare-acid water is washed or the calcining of countercurrent washing, after adding water and sizing mixing, add concentrated hydrochloric acid while stirring, in the time of temperature 50-95 ℃, dissolved 1-2 hour, rare earth is all dissolvings then, and the residual acid with 0.2-0.3mol/L HCl in hydro-oxidation rare earth or carbonated rare earth or used calcining or other alkali finishes filtration to PH1-1.5;
(7) in and removal of impurities
Full dissolved rare earth filtrate adds small amounts agent, Oxidation of Fe
2+Be Fe
3+After again with in and slip in the desired rare earth filtrate of the pH value controlled variable of neutralization reaction with in and slip the two Theoretical Calculation mass rate ratio spray or be instilled in and receiver, stirring reaction, 70-90 ℃ of control liquid temperature, pH value 3-4, reinforced finishing transferred pH value to 4.5 with weak ammonia or carbon ammonium again, adds a small amount of BaCl simultaneously
2Remove SO
4 2-Ion, clarification is filtered, in and slip be rare earth hydrate or weak ammonia or the two collocation;
(8) condensing crystal
Qualified feed liquid is squeezed into enamel reactor, and the programmed heating concentrating under reduced pressure gets mixed chlorinated rare earth routinely;
(9) causticization reclaims
The countercurrent washing final outflow water is added in the causticizing tank, add excess amount of Ca O causticization Na wherein
2CO
3, NaF, NaPO
4And form corresponding calcium precipitation, and 80-90 ℃ of causticization temperature, churning time 1-1.5 hour, reaction finished and promptly filters, and concentrating filter liquor is to about 50%NaOH high alkali liquid, and filter residue is collected stand-by.
2, the method for a kind of mixed rare earth concentrates carbon reducting roast production rare earth chloride according to claim 1, it is characterized in that: the carbonaceous reducing agent in the reducing roasting refers to a kind of material in coal dust, Graphite Powder 99, coke powder, the powdered carbon.
3, a kind of mixed rare earth concentrates carbon reducting roast according to claim 1 is produced the method for rare earth chloride, it is characterized in that: in the carbon reducting roast with carbonaceous reducing agent reduction cerium dioxide CeO
2Be sesquialter cerium oxide Ce
2O
3
4, a kind of mixed rare earth concentrates carbon reducting roast according to claim 1 is produced the method for rare earth chloride, it is characterized in that: in and the oxygenant in the removal of impurities be meant hydrogen peroxide or Sodium Nitrite.
5, a kind of mixed rare earth concentrates carbon reducting roast according to claim 1 is produced the method for rare earth chloride, it is characterized in that: in and in the removal of impurities spray pyrrhosiderite remove iron processes and will contain Fe
2O
3For adopting spray mode or instillation mode, the re chloride of 5-30 grams per liter adds in the solution acceptor, at Fe
3+Under the extremely low state of concentration, add thermo-neutrality and form pyrrhosiderite FeO (OH) precipitation.
6, the method for a kind of mixed rare earth concentrates carbon reducting roast production rare earth chloride according to claim 1, it is characterized in that: solid-state activation utilization NaOH decomposes or conversion is adding Na
2CO
3New life's phosphorus ore thing Na during roasting
3RE (PO
4)
2Or other phosphorus containg substances and generate water-soluble phosphoric acid trisodium Na
3PO
4
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|---|---|---|---|
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| CN112941304B (en) * | 2021-01-27 | 2022-07-15 | 赣州求真科技有限公司 | Rare earth roasting method |
| CN117821783B (en) * | 2024-03-05 | 2024-05-31 | 矿冶科技集团有限公司 | Green exploitation method of ionic rare earth ore |
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2001
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100532595C (en) * | 2006-11-16 | 2009-08-26 | 北京方正稀土科技研究所有限公司 | Method for decomposing hamartite |
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