CN111004932A - Six-tank continuous hydrochloric acid preferential dissolution method for monazite alkali cake - Google Patents
Six-tank continuous hydrochloric acid preferential dissolution method for monazite alkali cake Download PDFInfo
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000003513 alkali Substances 0.000 title claims abstract description 75
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 title claims abstract description 27
- 229910052590 monazite Inorganic materials 0.000 title claims abstract description 27
- 238000011978 dissolution method Methods 0.000 title claims abstract description 15
- 238000004090 dissolution Methods 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 38
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 18
- 229910052776 Thorium Inorganic materials 0.000 claims abstract description 16
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims abstract description 15
- 238000004537 pulping Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 230000001502 supplementing effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 26
- 239000002893 slag Substances 0.000 claims description 20
- -1 rare earth chloride Chemical class 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 16
- 238000009835 boiling Methods 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 12
- 229910052770 Uranium Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 230000002431 foraging effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 229910052705 radium Inorganic materials 0.000 claims description 3
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 150000002910 rare earth metals Chemical class 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000003723 Smelting Methods 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 208000035126 Facies Diseases 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- WEQHQGJDZLDFID-UHFFFAOYSA-J thorium(iv) chloride Chemical compound Cl[Th](Cl)(Cl)Cl WEQHQGJDZLDFID-UHFFFAOYSA-J 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Mechanical Engineering (AREA)
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Abstract
The invention belongs to the technical field of smelting of monazite of rare earth ore, and particularly relates to a six-tank continuous hydrochloric acid optimal dissolution method of monazite alkali cake. Taking an alkali cake as a raw material, adding thorium raffinate into an alkali cake pulping tank for pulping, transferring the slurry into an alkali liquor head tank, then transferring the slurry and hydrochloric acid in a hydrochloric acid head tank into a continuous optimal dissolution tank for dissolution reaction, controlling the pH value of the reaction residual acid in a third-stage tank body in a six-stage continuous optimal dissolution tank to be within 1.5-2.2, supplementing the initial alkali cake slurry into the tank body, and controlling the pH value of the residual acid in the sixth-stage tank body to be 3.8-4.5, thereby achieving the purpose of optimal dissolution of hydrochloric acid. The invention changes the prior common intermittent production mode into continuous production by creatively adopting the six-connected optimal hydrochloric acid dissolving tank, greatly improves the production efficiency, increases the batch stability of products, improves the heat utilization efficiency, reduces the energy consumption and reduces the consumption of hydrochloric acid.
Description
Technical Field
The invention belongs to the technical field of smelting of monazite of rare earth ore, and particularly relates to a six-tank continuous hydrochloric acid optimal dissolution method of monazite alkali cake.
Background
With the development of science and technology, rare earth elements are widely applied in various fields due to the special physical and chemical properties of the rare earth elements. Monazite is one of the most widely distributed and important rare earth minerals, is rich in rare earth, uranium, thorium and other precious resources, and has a chemical expression of (Ce, La and Th) PO4. Monazite concentrates have long been used mainly for the extraction of rare earth chlorides andphosphorus, most of the enterprises in monazite smelting production in China at present adopt a caustic soda digestion process, and the generated alkali cake enters a posterior-stage hydrochloric acid preferential dissolution process to be used for producing rare earth chloride. The excellent slag generated in the process can be subjected to radioactive element recovery treatment.
The monazite alkali cake is treated with hydrochloric acid preferential dissolution, and the existing process mostly adopts an intermittent reaction process, namely, the alkali cake and the hydrochloric acid are added into a reaction kettle, the pH value is adjusted, the mixture is heated for a certain time to carry out preferential dissolution, and then the mixture is boiled, aged and filtered. The process has the defects of low production efficiency, high energy consumption, high hydrochloric acid consumption and insufficient batch stability of the product, is only suitable for small workshop production, and cannot realize large-scale industrial production.
The method is dedicated to six-stage continuous preferential dissolution treatment of the alkali cake generated by decomposing monazite concentrate with alkali, and can improve the heat utilization efficiency, reduce the energy consumption, reduce the hydrochloric acid consumption and improve the batch stability of the product. Meanwhile, in the process, the method can improve the alkali cake dissolution rate and recover rare earth resources to the maximum extent, so that the yield of rare earth elements in the monazite alkali cake is more than or equal to 93%, and uranium, thorium, iron, zirconium, aluminum, silicon and other elements are left in the high-quality slag and enter the next uranium and thorium recovery process.
Disclosure of Invention
The invention aims to provide a six-tank continuous hydrochloric acid preferential dissolution method for monazite alkali cakes, which overcomes various defects of an intermittent reaction process adopted by the conventional monazite alkali cake hydrochloric acid preferential dissolution.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a six-tank continuous hydrochloric acid preferential dissolution method for monazite alkali cakes is characterized in that the alkali cakes are used as raw materials, thorium raffinate is added into an alkali cake pulping tank for pulping, slurry is conveyed to an alkali liquor head tank for transfer and then is conveyed into a continuous preferential dissolution tank together with hydrochloric acid in a hydrochloric acid head tank for dissolution reaction, the pH value of reaction residual acid in a third-stage tank body in the six-stage continuous preferential dissolution tank is controlled within the range of 1.5-2.2, initial alkali cake slurry is supplemented into the tank body, and the pH value of the residual acid in the sixth-stage tank body is controlled within the range of 3.8-4.5, so that the aim of preferential dissolution of hydrochloric acid is fulfilled.
The qualified alkali cake prepared in the alkali decomposition process is used as a raw material.
The initial concentration of hydrochloric acid was 6.5 mol/L.
Feeding the pH-adjusted hydrochloric acid dissolved ore slurry into a high-quality solution boiling tank, controlling the boiling time to be 1h, then feeding the solution into a high-quality solution ageing tank, and controlling the ageing time to be 8-12h so as to ensure that rare earth elements in the alkali cake enter a liquid phase, and uranium, thorium, iron, zirconium, aluminum and silicon are fully hydrolyzed to form insoluble substances; and (4) sending the aged optimal solution slurry to an optimal solution slag pulping tank, and sequentially sending the optimal solution slurry to a plate and frame filter for solid-liquid separation according to the filtration batch.
Transferring the filtrate into an excellent solution clear liquid tank, sending the filtrate into a removing and placing reactor according to a removing and placing reaction batch, adding a prepared barium chloride and sodium sulfide solution into the removing and placing reactor for removing and placing reaction, and removing trace radium in the solution by virtue of the carrying band sedimentation effect of barium sulfate; the slurry after the discharging reaction is sent into a discharging aging tank for aging reaction, so that the discharging reaction and the precipitation effect are further enhanced; feeding the material after the discharging and aging into a plate-and-frame filter for solid-liquid separation, removing the discharged slag from the filter residue which is rare earth chloride, and sealing and storing; the filtrate is a rare earth chloride solution, and is sequentially sent into rare earth chloride concentration crystallization equipment and an automatic weighing and packaging unit to prepare a rare earth chloride product meeting GB/T4148-2003; and (3) feeding the filter cake into an excellent-solubility slag pulping tank, adding washing water and acidified water of a full-solubility slag plate frame for size mixing, and feeding into a hydrochloric acid full-solubility process.
The initial temperature of hydrochloric acid dissolution is 90 ℃, the dissolution temperature is controlled to be 85-90 ℃, the reaction is carried out for 4-6h, and the pH value of the dissolved residual acid is controlled to be 1.5-2.2.
And adding alkali cake slurry with the addition amount of 10% of the initial alkali cake into the tank body.
The beneficial effects obtained by the invention are as follows:
the invention changes the prior common intermittent production mode into continuous production by creatively adopting the six-connected optimal hydrochloric acid dissolving tank, greatly improves the production efficiency, increases the batch stability of products, improves the heat utilization efficiency, reduces the energy consumption and reduces the consumption of hydrochloric acid. The invention can also accurately control the hydrochloric acid optimum-dissolution reaction of different facies minerals (alkali cakes) by controlling the retention time so as to improve the processing capacity of enterprises on the different facies minerals. The method can improve the dissolution rate of the alkali cake, and the yield of the rare earth elements in the monazite alkali cake is more than or equal to 93 percent.
Drawings
FIG. 1 is a flow chart of a six-tank continuous hydrochloric acid preferential dissolution method of monazite alkali cake.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
As shown in figure 1, the six-tank continuous hydrochloric acid preferential dissolution method of the monazite alkali cake comprises the following steps: taking qualified alkali cakes prepared in an alkali decomposition procedure as raw materials, adding thorium raffinate (containing a small amount of hydrochloric acid) into an alkali cake pulping tank for pulping, transferring slurry into an alkali liquor head tank, then delivering the slurry and hydrochloric acid in a hydrochloric acid head tank into a continuous optimum dissolution tank for dissolution reaction, controlling the initial acidity to be 6.5mol/L, controlling the pH value of reaction residual acid in a third-stage tank body in the continuous optimum dissolution tank to be 1.5-2.2, supplementing alkali cake slurry with the initial alkali cake adding amount of about 10% into the tank body, and controlling the pH value of residual acid in a sixth-stage tank body to be about 4.5 so as to achieve the purpose of optimum dissolution of hydrochloric acid.
The major component solubility products are shown in table 1:
TABLE 1 pH and solubility product of precipitation of major components
As can be seen from Table 1, the pH value is controlled to be about 4.5, and thorium, iron, uranium and rare earth can be well separated.
The hydrochloric acid dissolved ore pulp with the adjusted pH is sent into a solution boiling tank, the boiling time is controlled to be 1h, then the solution is sent into a solution aging tank (according to specific conditions, the solution can also be aged in the boiling tank), and the aging time is controlled to be 8-12h, so that the rare earth elements in the alkali cake are ensured to enter a liquid phase, and other elements such as uranium, thorium, iron, zirconium, aluminum, silicon and the like are fully hydrolyzed to form insoluble substances (solution slag). And (4) sending the aged optimal solution slurry to an optimal solution slag pulping tank, and sequentially sending the optimal solution slurry to a plate and frame filter for solid-liquid separation according to the filtration batch.
Transferring the filtrate into an excellent solution clear liquid tank, sending the filtrate into a removing and placing reactor according to a removing and placing reaction batch, adding a prepared barium chloride and sodium sulfide solution into the removing and placing reactor for removing and placing reaction, and removing trace radium in the solution by virtue of the carrying band sedimentation effect of barium sulfate; and feeding the slurry after the discharging reaction into a discharging aging tank for aging reaction, and further strengthening the discharging reaction and precipitation effect. Feeding the material after the discharging and aging into a plate-and-frame filter for solid-liquid separation, removing the discharged slag from the filter residue which is rare earth chloride, and sealing and storing; the filtrate is a rare earth chloride solution, and is sequentially sent into rare earth chloride concentration crystallization equipment (complete equipment) and an automatic weighing and packaging unit to prepare a rare earth chloride product meeting GB/T4148-.
And (3) feeding the filter cake into an excellent-solubility slag pulping tank, adding washing water and acidified water of a full-solubility slag plate frame for size mixing, and feeding into a hydrochloric acid full-solubility process.
The main reaction of the preferential dissolving process of the hydrochloric acid is as follows:
RE(OH)3+3HCl＝RECl3+3H2O…………………………………(1)
Th(OH)4+4HCl＝ThCl4+4H2O…………………………………(2)
Fe(OH)3+3HCl＝FeCl3+4H2O…………………………………(3)
in the hydrochloric acid dissolution process, Na2U2O7Is also decomposed by hydrochloric acid, with U4+And UO2 2+The form exists in solution.
It can be seen from the above figure that the key point of the invention is to use six consecutive dissolving tanks, add excessive hydrochloric acid into the first-stage tank body to fully dissolve the alkali cake, then add alkali cake slurry into the third-stage dissolving tank to reversely adjust, raise the pH to the pH of the sixth-stage dissolving tank to 4.5, make all rare earth elements dissolve in the liquid phase, and make other elements enter the solid phase (bottom slurry), thus achieving the purpose of recovering rare earth elements.
The six-connected preferential dissolving tank is creatively adopted, so that the acid dissolving reaction and the production are continuous. In the six-stage continuous hydrochloric acid preferential dissolution reaction, excessive hydrochloric acid is added into a first-stage reaction kettle, so that the hydrochloric acid dissolution reaction is sufficient, and the dissolution rate of the alkali cake is improved. And adding a certain amount of alkali cake slurry into the third-stage reaction kettle to adjust the pH of the post-stage reaction, so that the pH of the material in the sixth-stage reaction kettle is controlled within the range of 3.8-4.5. Through the later stage boiling process, the rare earth elements enter the liquid phase, and other elements such as uranium, thorium, iron, zirconium, aluminum, silicon and the like are fully left in the excellent slag. Adding excessive hydrochloric acid at the beginning, wherein the initial concentration of the hydrochloric acid is 6.5mol/L, the initial temperature for dissolving the hydrochloric acid is 90 ℃, controlling the dissolving temperature to be 85-90 ℃, reacting for 4-6h, controlling the pH value of the residual acid after dissolving to be 1.5-2.2, and then fully dissolving. In the third-stage optimum dissolution tank, the reverse adjustment proportion of the alkali cake is about 10 percent of the amount of the initially added alkali cake (can be adjusted according to specific conditions), the residual acid after dissolution, namely the pH value of the material in the sixth tank body is 3.8-4.5, the material is boiled for 1h, and is aged for 8-12h, and then the plate-and-frame filtration is carried out. And (3) filtering the aging solution by using a plate-and-frame filter, and repeatedly filtering the filter residue after acid washing and water washing so as to fully recover the rare earth elements.
[ example 1 ]
As required by the previous specific scheme, the method comprises the following steps: alkali cake → six-stage continuous hydrochloric acid optimum solution → solution adjustment → boiling → aging → solid-liquid separation → multi-stage washing → optimum solution slag; dissolving filtrate in water → radioactivity elimination → solid-liquid separation → evaporation concentration → cooling crystallization → rare earth chloride product. Continuously pumping an alkali cake prepared in an alkali decomposition procedure and hydrochloric acid into a first-level tank of a six-level tank through a pump, ensuring that the hydrochloric acid is excessive (controlling the pH value of materials in a third-level optimum dissolution tank to be within 1.5-2.0), adding the alkali cake to reversely adjust the pH value, controlling the pH value of the materials in the sixth-level optimum dissolution tank to be 4.5, reacting for 4-6h, boiling for 1h, and aging for 8-12h to ensure that rare earth elements in the alkali cake enter a liquid phase, fully hydrolyzing other elements such as uranium, thorium, iron, zirconium, aluminum, silicon and the like to form insoluble substances (optimum dissolution slag), and filtering through a plate frame (in the process, performing filter residue pickling and water washing and then filtering again) to obtain rare earth chloride products and optimum dissolution slag. The yield of the rare earth chloride in the alkali cake is 94% by analysis.
[ example 2 ]
The process is completely the same as example 1, only the third stage optimum dissolution tank is added with alkali cake for reverse adjustment, and the pH of the material in the sixth stage optimum dissolution tank is 4.2. The yield of the rare earth chloride in the alkali cake is 93 percent by analysis.
[ example 3 ]
The process is completely the same as example 1, only the third stage optimum dissolution tank is added with alkali cake for reverse adjustment, and the pH of the material in the sixth stage optimum dissolution tank is 4.1. The analysis shows that the yield of the rare earth chloride in the alkali cake is 94%.
The invention provides a method for continuously dissolving monazite alkali cake (obtained by decomposing caustic soda) with hydrochloric acid, which is characterized in that a six-connected-body hydrochloric acid dissolving tank is creatively adopted. The invention changes the existing common intermittent production mode into continuous production, and has the advantages of greatly improving the production efficiency, increasing the batch stability of the product, improving the heat utilization efficiency, reducing the energy consumption and reducing the consumption of hydrochloric acid. The invention has another great advantage that the hydrochloric acid optimum-dissolution reaction of different grade phase minerals (alkali cakes) can be accurately controlled by controlling the retention time so as to improve the processing capacity of enterprises on the different grade phase minerals. The process control point (KPI) of the invention is that the initial acid dissolution pH value is controlled to be 1.5-2.2, the acid dissolution rear section and boiling process pH value are controlled to be 3.8-4.5, the continuous acid dissolution temperature is controlled to be 85-90 ℃, the acid dissolution retention time is controlled to be 4-6h, the boiling time is 1h, and the aging is carried out for 8-12h after boiling. The method can improve the dissolving rate of the alkali cake, so that the yield of the rare earth elements in the monazite alkali cake is more than or equal to 93 percent, and elements such as uranium, thorium, iron, zirconium, aluminum, silicon and the like are left in the excellent dissolving slag and enter the next uranium and thorium recovery process.
Claims (7)
1. A six-tank continuous hydrochloric acid preferential dissolution method of monazite alkali cake is characterized in that: taking an alkali cake as a raw material, adding thorium raffinate into an alkali cake pulping tank for pulping, transferring the slurry into an alkali liquor head tank, then transferring the slurry and hydrochloric acid in a hydrochloric acid head tank into a continuous optimal dissolution tank for dissolution reaction, controlling the pH value of the reaction residual acid in a third-stage tank body in a six-stage continuous optimal dissolution tank to be within 1.5-2.2, supplementing the initial alkali cake slurry into the tank body, and controlling the pH value of the residual acid in the sixth-stage tank body to be 3.8-4.5, thereby achieving the purpose of optimal dissolution of hydrochloric acid.
2. The six-tank continuous hydrochloric acid preferential dissolution method of monazite alkali cakes as claimed in claim 1, characterized in that: the qualified alkali cake prepared in the alkali decomposition process is used as a raw material.
3. The six-tank continuous hydrochloric acid preferential dissolution method of monazite alkali cakes as claimed in claim 1, characterized in that: the initial concentration of hydrochloric acid was 6.5 mol/L.
4. The six-tank continuous hydrochloric acid preferential dissolution method of monazite alkali cakes as claimed in claim 1, characterized in that: feeding the pH-adjusted hydrochloric acid dissolved ore slurry into a high-quality solution boiling tank, controlling the boiling time to be 1h, then feeding the solution into a high-quality solution ageing tank, and controlling the ageing time to be 8-12h so as to ensure that rare earth elements in the alkali cake enter a liquid phase, and uranium, thorium, iron, zirconium, aluminum and silicon are fully hydrolyzed to form insoluble substances; and (4) sending the aged optimal solution slurry to an optimal solution slag pulping tank, and sequentially sending the optimal solution slurry to a plate and frame filter for solid-liquid separation according to the filtration batch.
5. The six-tank continuous hydrochloric acid preferential dissolution method of monazite alkali cakes as claimed in claim 4, characterized in that: transferring the filtrate into an excellent solution clear liquid tank, sending the filtrate into a removing and placing reactor according to a removing and placing reaction batch, adding a prepared barium chloride and sodium sulfide solution into the removing and placing reactor for removing and placing reaction, and removing trace radium in the solution by virtue of the carrying band sedimentation effect of barium sulfate; the slurry after the discharging reaction is sent into a discharging aging tank for aging reaction, so that the discharging reaction and the precipitation effect are further enhanced; feeding the material after the discharging and aging into a plate-and-frame filter for solid-liquid separation, removing the discharged slag from the filter residue which is rare earth chloride, and sealing and storing; the filtrate is a rare earth chloride solution, and is sequentially sent into rare earth chloride concentration crystallization equipment and an automatic weighing and packaging unit to prepare a rare earth chloride product meeting GB/T4148-2003; and (3) feeding the filter cake into an excellent-solubility slag pulping tank, adding washing water and acidified water of a full-solubility slag plate frame for size mixing, and feeding into a hydrochloric acid full-solubility process.
6. The six-tank continuous hydrochloric acid preferential dissolution method of monazite alkali cakes as claimed in claim 1, characterized in that: the initial temperature of hydrochloric acid dissolution is 90 ℃, the dissolution temperature is controlled to be 85-90 ℃, the reaction is carried out for 4-6h, and the pH value of the dissolved residual acid is controlled to be 1.5-2.2.
7. The six-tank continuous hydrochloric acid preferential dissolution method of monazite alkali cakes as claimed in claim 1, characterized in that: and adding alkali cake slurry with the addition amount of 10% of the initial alkali cake into the tank body.
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