CN116119704A - Treatment method of raffinate from full wet molybdenum smelting - Google Patents
Treatment method of raffinate from full wet molybdenum smelting Download PDFInfo
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- raffinate
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 58
- 239000011733 molybdenum Substances 0.000 title claims abstract description 58
- 238000003723 Smelting Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000010440 gypsum Substances 0.000 claims abstract description 69
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 69
- 239000011575 calcium Substances 0.000 claims abstract description 54
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 50
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 50
- 239000002893 slag Substances 0.000 claims abstract description 44
- 239000011268 mixed slurry Substances 0.000 claims abstract description 39
- 239000007791 liquid phase Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 150000004683 dihydrates Chemical class 0.000 claims abstract description 27
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000000706 filtrate Substances 0.000 claims description 20
- 239000006228 supernatant Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 15
- 230000008719 thickening Effects 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 16
- 239000002253 acid Substances 0.000 description 13
- 238000002386 leaching Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 9
- 235000011941 Tilia x europaea Nutrition 0.000 description 9
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 9
- 239000004571 lime Substances 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 description 8
- 239000003546 flue gas Substances 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229940095672 calcium sulfate Drugs 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- -1 Cu 2+ Chemical class 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229940057307 dihydrate calcium sulfate Drugs 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- JXRVKYBCWUJJBP-UHFFFAOYSA-L calcium;hydrogen sulfate Chemical compound [Ca+2].OS([O-])(=O)=O.OS([O-])(=O)=O JXRVKYBCWUJJBP-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/466—Conversion of one form of calcium sulfate to another
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a treatment method of a full wet molybdenum smelting raffinate, which comprises the steps of adding a first calcium agent into the full wet molybdenum smelting raffinate, stirring and reacting at 40-50 ℃, and controlling the addition amount of the first calcium agent to enable the end-point pH value of a reaction system to be 1-1.5 so as to obtain a first mixed slurry; carrying out solid-liquid separation on the first mixed slurry to obtain dihydrate gypsum and a first liquid phase; adding a second calcium agent into the first liquid phase, stirring and reacting, and controlling the addition amount of the second calcium agent to enable the end point pH value of a reaction system to be 7-8, thereby obtaining second mixed slurry; and carrying out solid-liquid separation on the second mixed slurry to obtain gypsum slag and a second liquid phase. The method can produce two kinds of neutralization residues such as dihydrate gypsum and gypsum slag, wherein the produced dihydrate gypsum slag can be sold to produce economic value, and only a small amount of gypsum slag is produced for piling up, so that the method has good environmental protection and economic benefit.
Description
Technical Field
The invention relates to a method for treating raffinate from full wet molybdenum smelting, belonging to the field of nonferrous metallurgy.
Background
The traditional molybdenum smelting adopts a fire-wet method combined process, molybdenum concentrate is roasted to produce molybdenum calcine, and roasting flue gas adopts low-concentration SO 2 Preparing acid from flue gas or adding pyrite roasting flue gas, preparing acid from molybdenum calcine, and producing ammonium molybdate by ammonia leaching, purifying, acid precipitating and crystallizing 2 Low concentration, high acid production cost, high molybdenum content (Mo 5-8%) in ammonia leaching slag, low molybdenum leaching rate, poor purifying and impurity removing effects, unstable product quality and the like. In order to overcome the defects of the traditional molybdenum smelting technology, the full wet molybdenum smelting technology is increasingly popularized and applied, namely, molybdenum concentrate is subjected to the working procedures of oxygen pressure, alkaline leaching, extraction, acid precipitation crystallization and the like to produce ammonium molybdate, the method overcomes the defects of the traditional molybdenum smelting technology, has obvious technical advantages, and is characterized by no need of flue gas acid production, good environmental protection, low molybdenum content in alkaline leaching slag (Mo<1 percent), the leaching rate of molybdenum is high, and the quality of the product of extraction crystallization is good. The sulfur in the molybdenum concentrate is converted into sulfuric acid in the oxygen pressure process, the extraction is carried out under the acidic condition, and the produced raffinate contains sulfuric acid and heavy metal impurities, so that neutralization and impurity removal treatment are needed.
In various industrial production, a lime treatment method is often adopted to treat the sulfuric acid-containing waste liquid, but byproducts of the lime treatment method such as phosphogypsum, fluorgypsum, desulfurized gypsum and mirabilite gypsum are used, and further treatment is required to sell the product. For sulfur-containing flue gas or acid-containing wastewater, lime method is generally adopted for treatmentThe sulfur-containing flue gas is subjected to two steps of absorption and oxidation, and lime slurry and SO in the flue gas 2 The reaction is carried out, the absorption is converted into calcium sulfite or calcium bisulfate, then the air is introduced for oxidation and conversion into dihydrate gypsum, the dihydrate gypsum can be obtained by adopting a lime method to treat sulfur-containing flue gas and is used as a product for sale, and the lime method is adopted to treat acid-containing wastewater, lime slurry and H 2 SO 4 The reaction is converted into gypsum slag, and heavy metals are deposited in the gypsum slag in the neutralization process because the wastewater contains heavy metal impurities, and the gypsum slag cannot be sold as a product and can only be piled up. Thus, although the wastewater is treated, a large amount of solid waste with low utility value is generated, and a new problem is generated.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an environment-friendly and economical treatment method of the full wet molybdenum smelting raffinate.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the method for treating the raffinate from the full wet molybdenum smelting comprises the following steps:
s1, providing a full wet molybdenum smelting raffinate;
wherein the raffinate of the full wet molybdenum smelting contains [ MoO ] 2 (SO 4 ) 2 ] 2- 、H 2 SO 4 And impurity ions including Cu 2+ 、Fe 3+ 、Zn 2+ 、Al 3+ 、As 3+ One or more of the following;
s2, adding a first calcium agent into the full wet molybdenum smelting raffinate, stirring and reacting at 40-50 ℃, and controlling the addition amount of the first calcium agent to enable the end point pH value of a reaction system to be 1.1-1.6 to obtain first mixed slurry;
wherein the first calcium agent comprises CaO and CaCO 3 、Ca(OH) 2 One or more of the following;
s3, carrying out solid-liquid separation on the first mixed slurry to obtain dihydrate gypsum and a first liquid phase;
s4, adding a second calcium agent into the first liquid phase, stirring for reaction, and controlling the addition amount of the second calcium agent to enable the end-point pH value of a reaction system to be 7-8, thereby obtaining second mixed slurry;
wherein the second calcium agent comprises CaO and CaCO 3 、Ca(OH) 2 One or more of the following;
s5, carrying out solid-liquid separation on the second mixed slurry to obtain gypsum slag and a second liquid phase.
Thus, the first calcium agent is added into the raffinate, the reaction temperature and the pH value of the reaction end point are controlled, so that the acid in the raffinate is partially consumed, sulfate radical is converted into dihydrate gypsum, and meanwhile, cu can be effectively avoided by controlling the pH to be acidic 2+ 、Fe 3+ 、Zn 2+ 、Al 3+ The plasma metal ions are precipitated, so that the dihydrate gypsum with high purity is obtained, the dihydrate gypsum can be directly sold as a product, and the economic benefit is further improved; then, adding a second calcium agent into the first liquid phase after separating the dihydrate gypsum, controlling the end point pH value to 7-8, consuming the remaining acid, and converting sulfate radical into gypsum slag CaSO 4 At the moment, heavy metal ions are also precipitated along with gypsum slag, so that the concentration of the heavy metal ions in the liquid phase is reduced. Because a large amount of sulfate radical is produced in the form of the dihydrate gypsum which can be sold, only a small amount of sulfate radical is produced in the form of gypsum slag, the amount of the finally obtained waste slag can be greatly reduced, the stacking pressure of the waste slag can be effectively reduced, and the economic benefit can be effectively improved.
Further, in S1, H in the raffinate of the full wet molybdenum smelting 2 SO 4 The concentration is 25-35g/L, and further 28-32g/L.
Further, the average particle size of the first calcium agent is 280-350 mesh; the average particle size of the second calcium agent is 280-350 mesh.
Further, in S2, the end point pH is 1.2-1.5.
Further, in S2, the reaction is stirred at 42-48 ℃.
Further, in S2, the reaction time is 1 to 1.5 hours; in S4, the reaction time is 1-1.5h.
Further, in S3, the first mixed slurry is firstly subjected to thickening treatment to obtain a first section of neutralization residue and a first section of supernatant; centrifuging and filtering the first-stage neutralized slag to obtain dihydrate gypsum and first filtrate; the first filtrate and a supernatant are combined as a first liquid phase.
Further, in S5, the second mixed slurry is firstly subjected to thickening treatment to obtain second-stage neutralization residue and second-stage supernatant; carrying out filter pressing treatment on the second-stage neutralization slag to obtain gypsum slag and second filtrate; the second filtrate and the second supernatant are combined as a second liquid phase.
Further, the second liquid phase is returned to the oxygen pressure leaching process of the full wet molybdenum smelting.
Further, in the full wet molybdenum smelting raffinate, according to the concentration of Mo, [ MoO ] 2 (SO 4 ) 2 ] 2- The concentration of (2) is 0.01-0.3g/L; cu (Cu) 2+ The concentration of (2) is 1-5g/L; fe (Fe) 3+ The concentration of (2) is 1-5g/L; zn (zinc) 2+ The concentration of (2) is 0.1-1g/L; al (Al) 3+ The concentration of (2) is 0.1-1g/L; as As 3+ The concentration of (2) is 0.1-1mg/L; h 2 SO 4 The concentration of (C) is 25-35g/L.
Further, the total wet molybdenum smelting raffinate also contains ReO 4 - ，ReO 4 - (converted to Re concentration) of 0.001-0.2mg/L. Wherein Re refers to the element rhenium.
The invention adopts a two-stage lime treatment method, takes calcium carbonate as a calcium agent as an example, and the main reaction of S2 is as follows:
CaCO 3 +H 2 SO 4 →CaSO 4 ·0.5H 2 O+0.5H 2 O+CO 2 ↑ (1)
CaSO 4 ·0.5H 2 O+1.5H 2 O→CaSO 4 ·2H 2 O (2)
the second stage controls the end point pH 7-8 to generate gypsum slag, and the main reaction of S4 is as follows:
CaCO 3 +H 2 SO 4 →CaSO 4 +H 2 O+CO 2 ↑ (3)
compared with the prior art, the invention has the following beneficial effects:
(1) In the invention, in S2, the pH end point is controlled under the weak acid condition, thereby creating favorable conditions for generating semi-hydrated gypsum, and simultaneously, heavy metal ions are kept in a liquid phase and do not enter a slag phase, so that the obtained dihydrate gypsum product has high quality, and the purity of the dihydrate gypsum is more than 90 percent;
(2) The full wet molybdenum smelting raffinate has a certain residual heat, the reaction temperature in S2 is controlled to be 40-50 ℃, the semi-hydrated gypsum is heated to be dissolved in water to generate dihydrate gypsum, the transition of gypsum crystal forms can be completed by utilizing the self heat of the full wet molybdenum smelting raffinate, the heat utilization efficiency is high, and the energy consumption is saved;
(3) S4, controlling the pH value to 7-8, and converting the residual acid and most heavy metals in the raffinate into gypsum slag, so that the reduction of the waste slag is realized; the neutralized liquid returns to the front-stage oxygen pressure leaching process for cyclic utilization;
(4) Compared with the traditional one-stage lime method for treating acid-containing wastewater to only produce gypsum slag, the method provided by the invention can produce two kinds of neutralization slag such as dihydrate gypsum and gypsum slag, wherein the produced dihydrate gypsum slag is large, can be sold to produce economic value, only produces a small amount of gypsum slag, can be deposited for treatment, and has good environmental protection and economic benefit.
Drawings
FIG. 1 is a flow chart of a method for treating an all-wet molybdenum smelting raffinate according to the present invention.
Detailed Description
The present invention will be described in detail with reference to examples. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. The relevant percentages refer to mass percentages unless otherwise indicated.
Example 1
The method for treating the raffinate from the full wet molybdenum smelting comprises the following steps:
s1, providing a full wet molybdenum smelting raffinate;
wherein the raffinate of the full wet molybdenum smelting contains [ MoO ] 2 (SO 4 ) 2 ] 2- 、Cu 2+ 、Fe 3+ 、Zn 2+ 、Al 3+ 、ReO 4 - 、As 3+ And H 2 SO 4 The ion concentrations are shown in Table 1.
TABLE 1 Main Components of raffinate from molybdenum smelting by Total wet method
S2, direction 10m 3 Adding a first calcium agent into the full wet molybdenum smelting raffinate, stirring and reacting for 1h at 40 ℃, and controlling the adding amount of the first calcium agent to enable the end-point pH value of a reaction system to be 1.3 to obtain first mixed slurry;
wherein the first calcium agent is calcium carbonate powder (CaO content is 53%, average particle size is 320 mesh); the total addition amount of the first calcium agent is 245kg;
s3, carrying out solid-liquid separation on the first mixed slurry to obtain 468kg (with the water content of 10%) of gypsum dihydrate and 9.95m of a first liquid phase 3 ；
S4, adding a second calcium agent into the first liquid phase, stirring and reacting for 1h, and controlling the adding amount of the second calcium agent to enable the end point pH value of a reaction system to be 7, thereby obtaining second mixed slurry;
wherein the second calcium agent is calcium carbonate powder (CaO content is 53%, average granularity is 320 meshes) and total addition amount is 62kg;
s5, carrying out solid-liquid separation on the second mixed slurry to obtain 104kg of gypsum slag (the water content is 20%) and 9.93m of a second liquid phase 3 。
S3, performing thickening treatment on the first mixed slurry to obtain a first section of neutralization residue and a first section of supernatant; centrifuging and filtering the first-stage neutralized slag to obtain dihydrate gypsum and first filtrate; the first filtrate and a supernatant are combined as a first liquid phase.
S5, performing thickening treatment on the second mixed slurry to obtain second-stage neutralization residue and second-stage supernatant; carrying out filter pressing treatment on the second-stage neutralization slag to obtain gypsum slag and second filtrate; and combining the second filtrate and the second-stage supernatant to obtain a second liquid phase, and returning to the oxygen pressure leaching process of the full wet molybdenum smelting.
Through detection, the content of calcium sulfate (calculated on a dry basis) in the obtained dihydrate gypsum reaches the requirement of GB/T37785-2019 on the secondary dihydrate calcium sulfate.
Example 2
The method for treating the raffinate from the full wet molybdenum smelting comprises the following steps:
s1, providing a full wet molybdenum smelting raffinate;
wherein the raffinate of the full wet molybdenum smelting contains [ MoO ] 2 (SO 4 ) 2 ] 2- 、Cu 2+ 、Fe 3+ 、Zn 2+ 、Al 3+ 、ReO 4 - 、As 3+ And H 2 SO 4 The ion concentrations are shown in Table 2.
TABLE 2 Main Components of raffinate from molybdenum smelting by Total wet method
S2, direction 10m 3 Adding a first calcium agent into the full wet molybdenum smelting raffinate, stirring and reacting for 1.2 hours at 50 ℃, and controlling the adding amount of the first calcium agent to enable the end-point pH value of a reaction system to be 1.5 to obtain first mixed slurry;
wherein the first calcium agent is calcium carbonate powder (CaO content is 53%, average particle size is 320 mesh); the total addition amount of the first calcium agent is 306kg;
s3, carrying out solid-liquid separation on the first mixed slurry to obtain 585kg of dihydrate gypsum (with the water content of 10%) and 9.94m of a first liquid phase 3 ；
S4, adding a second calcium agent into the first liquid phase, stirring and reacting for 1.2 hours, and controlling the adding amount of the second calcium agent to enable the end point pH value of a reaction system to be 8, so as to obtain second mixed slurry;
wherein the second calcium agent is calcium carbonate powder (CaO content is 53%, average granularity is 320 meshes) and total addition amount is 64kg;
s5, solidifying the second mixed slurryLiquid separation to obtain 106kg of gypsum residue (water content 20%) and 9.92m of a second liquid phase 3 。
S3, performing thickening treatment on the first mixed slurry to obtain a first section of neutralization residue and a first section of supernatant; centrifuging and filtering the first-stage neutralized slag to obtain dihydrate gypsum and first filtrate; the first filtrate and a supernatant are combined as a first liquid phase.
S5, performing thickening treatment on the second mixed slurry to obtain second-stage neutralization residue and second-stage supernatant; carrying out filter pressing treatment on the second-stage neutralization slag to obtain gypsum slag and second filtrate; and combining the second filtrate and the second-stage supernatant to obtain a second liquid phase, and returning to the oxygen pressure leaching process of the full wet molybdenum smelting.
Through detection, the content of calcium sulfate (calculated on a dry basis) in the obtained dihydrate gypsum is 92%, and the requirement of GB/T37785-2019 on the secondary dihydrate calcium sulfate is met.
Comparative example 1
The method for treating the raffinate from the full wet molybdenum smelting comprises the following steps:
s1, providing a full wet molybdenum smelting raffinate;
wherein the total wet molybdenum smelting raffinate was the same as in example 1.
S2, direction 10m 3 The first calcium agent is added into the full wet molybdenum smelting raffinate, the mixture is stirred and reacted for 1H at the temperature of 40 ℃, and the end point H of a reaction system is realized by controlling the addition amount of the first calcium agent 2 SO 4 After 15g/L, a first mixed slurry was obtained;
wherein the first calcium agent is calcium carbonate powder (CaO content is 53%, average particle size is 320 mesh); the total addition amount of the first calcium agent is 122kg;
s3, carrying out solid-liquid separation on the first mixed slurry to obtain 254kg (water content 10%) of gypsum and 9.97m of a first liquid phase 3 ；
S4, adding a second calcium agent into the first liquid phase, stirring and reacting for 1h, and controlling the adding amount of the second calcium agent to enable the end point pH value of a reaction system to be 7 so as to obtain second mixed slurry;
wherein the second calcium agent is calcium carbonate powder (CaO content is 53%, average granularity is 320 mesh), and total addition amount is 186kg;
s5, carrying out solid-liquid separation on the second mixed slurry to obtain 312kg of gypsum slag (with the water content of 20%) and 9.91m of a second liquid phase 3 。
S3, performing thickening treatment on the first mixed slurry to obtain a first section of neutralization residue and a first section of supernatant; centrifugally filtering the first-stage neutralization residue to obtain gypsum residue and a first filtrate; the first filtrate and a supernatant are combined as a first liquid phase.
S5, performing thickening treatment on the second mixed slurry to obtain second-stage neutralization residue and second-stage supernatant; carrying out filter pressing treatment on the second-stage neutralization slag to obtain gypsum slag and second filtrate; and combining the second filtrate and the second-stage supernatant to obtain a second liquid phase, and returning to the oxygen pressure leaching process of the full wet molybdenum smelting.
It can be seen that S2 employs stronger acid conditions (endpoint H 2 SO 4 15 g/L) of gypsum in water (CaSO) 4 ·nH 2 O), the gypsum can be further converted into the dihydrate gypsum by heating and dehydrating by a hydrothermal method or an autoclaved method, so that the energy consumption of the dehydration process is increased.
The calcium sulfate content (on a dry basis) of the obtained gypsum dehydrate was 85% by detection.
Comparative example 2
The method for treating the raffinate from the full wet molybdenum smelting comprises the following steps:
s1, providing a full wet molybdenum smelting raffinate;
wherein the total wet molybdenum smelting raffinate was the same as in example 2.
S2, direction 10m 3 Adding a first calcium agent into the full wet molybdenum smelting raffinate, stirring and reacting for 1.2 hours at 50 ℃, and controlling the adding amount of the first calcium agent to enable the end-point pH value of a reaction system to be 8 to obtain first mixed slurry;
wherein the first calcium agent is calcium carbonate powder (CaO content is 53%, average particle size is 320 mesh); the total addition amount of the first calcium agent is 367kg;
s3, for the firstConcentrating the mixed slurry, centrifugally filtering to obtain 555kg of gypsum residue (water content 10%) to obtain a first liquid phase 9.95m 3 Returning to wet molybdenum smelting.
As can be seen, the S2 is in alkaline condition (end point pH 8) to produce gypsum slag, so that the dihydrate gypsum can not be obtained, and the heavy metal contained in the gypsum slag can only be piled up.
The calcium sulfate content (on a dry basis) in the gypsum residue obtained was found to be 76%.
Comparative example 3
Comparative example 1 was repeated, with the only difference that: in S2, the addition amount of the first calcium agent is 180kg so as to control the end point pH value of the reaction system to be 0.9, and a first mixed slurry is obtained.
The results were: the first mixed slurry was subjected to solid-liquid separation to obtain 356kg (10% water content) of gypsum dehydrate, and the content of calcium sulfate (on a dry basis) in the gypsum dehydrate was detected to be 87%.
Comparative example 4
The comparison of comparative example 1 was repeated with the only difference that: in S2, the addition amount of the first calcium agent is 260kg so as to control the end point pH value of the reaction system to be 2.0, and a first mixed slurry is obtained.
The results were: the first mixed slurry was subjected to solid-liquid separation to obtain 505kg (10% water content) of gypsum dehydrate, and the content of calcium sulfate (on a dry basis) in the gypsum dehydrate was detected to be 81%.
The foregoing examples are set forth in order to provide a more thorough description of the present invention, and are not intended to limit the scope of the invention, since modifications of the invention in various equivalent forms will occur to those skilled in the art upon reading the present invention, and are within the scope of the invention as defined in the appended claims.
Claims (9)
1. The method for treating the raffinate from the full wet molybdenum smelting is characterized by comprising the following steps:
s1, providing a full wet molybdenum smelting raffinate;
wherein the raffinate of the full wet molybdenum smelting contains [ MoO ] 2 (SO 4 ) 2 ] 2- 、H 2 SO 4 And miscellaneous (miscellaneous)A plasmonic ion, the impurity ion including Cu 2+ 、Fe 3+ 、Zn 2+ 、Al 3+ 、As 3+ One or more of the following;
s2, adding a first calcium agent into the full wet molybdenum smelting raffinate, stirring and reacting at 40-50 ℃, and controlling the addition amount of the first calcium agent to enable the end point pH value of a reaction system to be 1.1-1.6 to obtain first mixed slurry;
wherein the first calcium agent comprises CaO and CaCO 3 、Ca(OH) 2 One or more of the following;
s3, carrying out solid-liquid separation on the first mixed slurry to obtain dihydrate gypsum and a first liquid phase;
s4, adding a second calcium agent into the first liquid phase, stirring for reaction, and controlling the addition amount of the second calcium agent to enable the end-point pH value of a reaction system to be 7-8, thereby obtaining second mixed slurry;
wherein the second calcium agent comprises CaO and CaCO 3 、Ca(OH) 2 One or more of the following;
s5, carrying out solid-liquid separation on the second mixed slurry to obtain gypsum slag and a second liquid phase.
2. The process of claim 1, wherein in S1, H is present in the total wet molybdenum smelting raffinate 2 SO 4 The concentration is 25-35g/L.
3. The process of claim 1 wherein the first calcium agent has an average particle size of 280-350 mesh; the average particle size of the second calcium agent is 280-350 mesh.
4. The process of claim 1, wherein in S2 the end point pH is 1.2 to 1.5.
5. The process according to claim 1, wherein in S2, the reaction is carried out with stirring at 42-48 ℃.
6. The process according to claim 1, wherein in S2 the reaction time is 1 to 1.5 hours; in S4, the reaction time is 1-1.5h.
7. The method according to claim 1, wherein in S3, the first mixed slurry is first subjected to thickening treatment to obtain a first-stage neutralized slag and a first-stage supernatant; centrifuging and filtering the first-stage neutralized slag to obtain dihydrate gypsum and first filtrate; the first filtrate and a supernatant are combined as a first liquid phase.
8. The method according to claim 1, wherein in S5, the second mixed slurry is first subjected to thickening treatment to obtain a second-stage neutralization residue and a second-stage supernatant; carrying out filter pressing treatment on the second-stage neutralization slag to obtain gypsum slag and second filtrate; the second filtrate and the second supernatant are combined as a second liquid phase.
9. The process of any one of claims 1 to 8, wherein [ MoO ] is calculated as the concentration of Mo in the all-wet molybdenum smelting raffinate 2 (SO 4 ) 2 ] 2- The concentration of (2) is 0.01-0.3g/L; cu (Cu) 2+ The concentration of (2) is 1-5g/L; fe (Fe) 3+ The concentration of (2) is 1-5g/L; zn (zinc) 2+ The concentration of (2) is 0.1-1g/L; al (Al) 3+ The concentration of (2) is 0.1-1g/L; as As 3+ The concentration of (2) is 0.1-1mg/L; h 2 SO 4 The concentration of (C) is 25-35g/L.
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