A kind of method that low acid consumption mixed rare earth concentrates concentrated sulfuric acid is decomposed
Technical field
The present invention relates to a kind of method that low acid consumption mixed rare earth concentrates concentrated sulfuric acid is decomposed, belong to field of hydrometallurgy.
Background technology
At present, 100,000 tons of Bayan Obo mixed rare earth concentrates are there are about every year(REO~50%;Referred to as " 50 concentrate ")Using
The treatment of concentrated sulfuric acid high-temperature roasting decomposition technique.In the technique, the concentrated sulfuric acid and 50 concentrate are 1.4 according to sour ore deposit weight ratio:1 mixing
Afterwards, it is calcined 2.5 ~ 3.0 hours under the conditions of 500~600 DEG C of temperature, is decomposed into sulfuric acid rare earth roasted ore.Wherein, radioactive nucleus
" thorium pyrophosphate " that element is fixed as being difficult to dissolve by high-temperature roasting.In the process, 30% or so the concentrated sulfuric acid is there are about with sulfuric acid acid
Mist, SO2And SO3Form enter mixing acid tail gas.Also the concentrated sulfuric acid is by some enterprises with the weight/mass percentage composition of tail gas recycle
70% sulfuric acid is according to 1:0.6 ratio mixing, then according to the concentrated sulfuric acid and 50 concentrate weight ratios be 1.2 with 50 concentrate:1 mixing roasting
Burn, now, the consumption of the sulfuric acid of 50 concentrate per ton distinguishes 1.2 tons of 92.5% concentrated sulfuric acid and 0.72 ton of 70% sulfuric acid.No matter
Which kind of mode, its sulfuric acid consumption, roasting energy consumption and tail gas recycle energy consumption are very high.
Zhao Zhihua etc. has invented " stepped sulfuric acid treatment and roasting process for decomposing Baotou RE ore concentrate "(Application number:
200510063032.7), the invention is by 1.1-1.4:After 1 concentrated sulfuric acid mixes with Baotou Iron Ore Concentrate, first under the conditions of 100-320 DEG C
Roasting 1-7 hours, tail gas spray-absorption;Then it is solid is boring under the conditions of 600-680 DEG C, it is calcined 1-4 hours, the tail of generation
Gas is absorbed with the concentrated sulfuric acid of 80-92%, and residual gas is absorbed with cool water shower again.This invention is well by the roasting of concentrated sulfuric acid low temperature
Burning is combined with the advantage of high-temperature roasting.The problem of presence is after concentrate mixes with sulfuric acid, to enter in two stoves respectively
OK, two sets of tail gas absorbing systems have been respectively adopted, and sulfuric acid acid consumption is higher, overall energy consumption is higher, and tail gas substep is formed after absorbing
Sulfuric acid and fluosilicic acid byproduct purity than relatively low.Horse jade-like stone etc. has invented a kind of " rare earth ore concentrate concentrated sulfuric acid low-temperature bake point
Solution technique "(Application number:02144405.6), the invention is that concentrate and the concentrated sulfuric acid are compared into 1.1-1.7 with weight:1 ratio mixing,
In 150-330 DEG C of roasting.Roasted ore goes out through water logging, filters, and obtains infusion and water logging slag, and the thorium in infusion is through extract and separate
Obtain thorium product.The technology realizes the extraction of Rare Earth Mine under cryogenic, but acid consumption is higher, and water logging liquid acidity is higher, radiation
The protection level of the abstraction purification process of property thorium is high, and the storage difficulty of pure thorium product is big.
The content of the invention
During aiming to solve the problem that mixed rare earth concentrates and concentrated sulfuric acid roasting it is an object of the invention to provide one kind, energy is calcined
Consumption, concentrated sulfuric acid consumption and radiothorium dissolution whether contradictory problems, make sulfuric acid consumption close to the low acid consumption mixing of theoretical amount
The method that the rare earth ore concentrate concentrated sulfuric acid is decomposed.
Technical thought of the invention:
(1)In same stove, the extension low-temperature bake section time, shorten the high temperature calcination section time, according to relatively low sour ore deposit weight
Ratio adds the concentrated sulfuric acid.In low-temperature bake section, sintering temperature is added close less than even much lower than 338 DEG C of sulfuric acid decomposition temperature
The concentrated sulfuric acid of theoretical amount, the control concentrated sulfuric acid effectively decomposes rare earth ore concentrate and itself does not decompose.Treat mineral REO resolution ratios >=
92% and sulfuric acid consumption totally, sulfuric acid consumption it is more thorough when, material into high-temperature region be calcined.In high temperature calcination section, front reaction
The phosphoric acid that the relative quantity of generation is big is further dehydrated into pyrophosphoric acid, normal thorium sulfate fast reaction generation " the burnt phosphorus small with relative quantity
The indissoluble thing such as sour thorium ".Further, since during low-temperature bake sulfuric acid consumption totally, and material is short in the residence time of high temperature section,
The volatile quantity and decomposition amount of sulfuric acid are all very low.Realize quick thorium admittedly and decompose the purpose of sulfuric acid on a small quantity so that whole process tail gas
Sulfuric acid content in absorbing liquid is declined to a great extent, and sulfuric acid availability is improved.
(2)Sulfuric acid and the mixed acid solution of fluosilicic acid that tail gas is reclaimed through spray, for pre-processing next group mischmetal essence
Ore deposit, main chemical reactions formula is:
3H2SO4+2REFCO3=RE2(SO4)3+2H2O+2CO2↑+2HF
3H2SO4+Ca3(PO4)2=3CaSO4↓+2H3PO4
4H2SO4+CaCe2(CO3)3F2=CaSO4+Ce2(SO4)3+2HF++3H2O+3CO2↑
3H2SO4+Fe2O3=Fe2(SO4)3+3H2O
2HF+REFCO3=REF3+2H2O+2CO2↑
2HF+Fe2(SO4)3= H2SO4+ FeF3↓
6HF+ RE2(SO4)3=3H2SO4+2REF3↓
6HF+ Ce2(SO4)3 =3H2SO4+2CeF3↓
Make full use of the impurity such as the stronger sulfuric acid of a small amount of acidity in nitration mixture and fluorine from minerals carbonate, iron to react, generate dioxy
Change the phosphoric acid of carbon, water, ferric flouride and denier, excessive hydrofluoric acid precipitates back the rare earth of dissolution in mineral again.Both it is abundant
Sulfuric acid is make use of, mineral have been purified again, reduce the consumption to sulfuric acid when mineral are calcined.Remaining acid solution is returned using vacuum distillation
Receive hydrofluoric acid.
The process step of the invention:
(1)Baking tail gases are absorbed into acid with REO weight/mass percentage compositions for 45% ~ 65% mixed rare earth concentrates mix immersion, is soaked
Temperature is 20-60 DEG C, and the time is 30-60min;After separation of solid and liquid, the concentrate after immersion carries out sulfuric acid baking, and filtrate is depressurized
Distillation recovery hydrofluoric acid;
(2)Moisture in concentrate after immersion is 8 ~ 12at%, and dry ore deposit weight is the 90-110% before immersion, by concentrate and matter after immersion
Amount percentage composition is 0.9 ~ 1.1 according to the dry ore deposit weight and concentrated sulfuric acid part by weight of concentrate for 90 ~ 99% concentrated sulfuric acid:1.0 mixing
Roasting;At 160 ~ 300 DEG C, the holdup time is 120-300min to control roasting head temperature, and after front end is terminated, concentrate REO is decomposed
Rate >=92%;At 500 ~ 600 DEG C, the holdup time is 15-30min to control rear end temperature, after roasted ore is through water logging, removal of impurities, is put
Penetrating property waste residue and sulfuric acid rare earth immersion liquid, after spraying and dedusting, counter-current absorption, the tail gas absorption acid of formation is for soaking new one for tail gas
The mixed rare earth concentrates criticized.
Effect of the invention:During mixed rare earth concentrates concentrated sulfuric acid roasting, ensureing the premise of radiothorium not dissolution
Under, roasting energy consumption and concentrated sulfuric acid consumption are fully reduced, using new approaches treatment tail gas absorption acid, reduce production cost.
Brief description of the drawings
Fig. 1 is process chart.
Specific embodiment
Embodiment one
Baking tail gases are absorbed into acid and mixes immersion with the mixed rare earth concentrates that the REO weight/mass percentage compositions of 100g are 52%, normal temperature,
100min.After separation of solid and liquid, the concentrate after immersion carries out sulfuric acid baking, and filtrate carries out vacuum distillation and reclaims hydrofluoric acid.
Moisture in concentrate after immersion is 9.6 at %, and it is 102.6g to do ore deposit weight, according to dry ore deposit weight and the dense sulphur of concentrate
Sour part by weight is 1:0.95 addition 97.5g weight/mass percentage composition be 98% the concentrated sulfuric acid it is baking mixed.Head temperature is 240
DEG C, the holdup time is 180min, after front end is terminated, concentrate REO resolution ratio >=92%.Rear end temperature is controlled at 500 DEG C, during delay
Between be 20min.After roasted ore is through water logging, removal of impurities, obtain emissive industrial waste residue with always than unconventional and unrestrained target sulfuric acid rare earth immersion liquid.Tail gas is passed through
After spray-absorption, dedusting, for soaking new batch of mixed rare earth concentrates.
Embodiment two
Baking tail gases are absorbed into acid and mixes immersion with the mixed rare earth concentrates that the REO weight/mass percentage compositions of 100g are 64%, normal temperature,
40min.After separation of solid and liquid, the concentrate after immersion carries out sulfuric acid baking, and filtrate carries out vacuum distillation and reclaims hydrofluoric acid.
Moisture in concentrate after immersion is 8.6 at %, and it is 96.2g to do ore deposit weight, according to the dry ore deposit weight and the concentrated sulfuric acid of concentrate
Part by weight is 1:1.05 addition 101g weight/mass percentage composition be 98% the concentrated sulfuric acid it is baking mixed.Head temperature at 180 DEG C,
Holdup time is 210min, after front end is terminated, concentrate REO resolution ratio >=92%.At 550 DEG C, the holdup time is control rear end temperature
20min.After roasted ore is through water logging, removal of impurities, obtain emissive industrial waste residue with always than unconventional and unrestrained target sulfuric acid rare earth immersion liquid.Tail gas is through spray
After absorption, dedusting, for soaking new batch of mixed rare earth concentrates.
Embodiment three
Baking tail gases are absorbed into acid and mixes immersion, 50 with the mixed rare earth concentrates that the REO weight/mass percentage compositions of 100g are 45.2%
DEG C, 60min.After separation of solid and liquid, the concentrate after immersion carries out sulfuric acid baking, and filtrate carries out vacuum distillation and reclaims hydrofluoric acid.
Moisture in concentrate after immersion is 10.7 at %, and it is 105.2g to do ore deposit weight, according to dry ore deposit weight and the dense sulphur of concentrate
Sour part by weight is 1.1:1 addition 116g weight/mass percentage composition be 98% the concentrated sulfuric acid it is baking mixed.Head temperature at 260 DEG C,
Holdup time is 270min, after front end is terminated, concentrate REO resolution ratio >=92%.At 550 DEG C, the holdup time is control rear end temperature
30min.After roasted ore is through water logging, removal of impurities, obtain emissive industrial waste residue with always than unconventional and unrestrained target sulfuric acid rare earth immersion liquid.Tail gas is through spray
After absorption, dedusting, for soaking new batch of mixed rare earth concentrates.