CN115896478A - Method for recovering tin from tin-containing material - Google Patents
Method for recovering tin from tin-containing material Download PDFInfo
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- CN115896478A CN115896478A CN202211689542.5A CN202211689542A CN115896478A CN 115896478 A CN115896478 A CN 115896478A CN 202211689542 A CN202211689542 A CN 202211689542A CN 115896478 A CN115896478 A CN 115896478A
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- tin
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- filter residue
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- hydrochloric acid
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000004821 distillation Methods 0.000 claims abstract description 53
- 239000000706 filtrate Substances 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 238000002386 leaching Methods 0.000 claims abstract description 29
- 239000012528 membrane Substances 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229940071182 stannate Drugs 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 5
- 125000005402 stannate group Chemical group 0.000 claims abstract description 5
- OBZIAMMZYGOUSG-UHFFFAOYSA-N [Cl-].[NH4+].[Sn] Chemical compound [Cl-].[NH4+].[Sn] OBZIAMMZYGOUSG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical group CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000002184 metal Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 238000000605 extraction Methods 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 71
- 239000000243 solution Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 230000004907 flux Effects 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
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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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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of mineral metal recovery and extraction, and particularly relates to a method for recovering tin from tin-containing materials, which comprises the steps of 1) mixing the tin-containing materials with distilled hydrochloric acid, leaching and filtering to obtain primary filtrate and primary filter residue; 2) Mixing the primary filter residue with concentrated hydrochloric acid with the mass concentration of at least 35.5%, leaching, and filtering to obtain secondary filtrate and secondary filter residue; 3) Rinsing the secondary filter residue, and filtering to obtain a rinsing liquid and rinsed filter residue; 4) Performing ammonium chloride tin precipitation on the primary filtrate, the secondary filtrate and the rinsing liquid to obtain ammonium stannate chloride filter residue and filtrate; 5) Carrying out membrane distillation on the filtrate to obtain the distilled hydrochloric acid, and increasing the heating temperature during distillation and reducing the distillation pressure along with the increase of the concentration multiple during distillation, wherein the heating temperature during distillation is increased by 2-6 ℃ every time the concentration multiple is increased by 1 time; 6) Dissolving the ammonium stannate filter residue, and replacing to obtain metallic tin; the invention reduces the consumption of hydrochloric acid and the cost.
Description
Technical Field
The invention belongs to the technical field of mineral metal recovery and extraction, and particularly relates to a method for recovering tin from tin-containing materials.
Background
Hydrometallurgy is a metallurgical method in which solid materials such as ores and calcine are contacted with liquid, and through chemical reaction, valuable components in the materials enter a liquid phase, and then are separated and enriched, and finally recovered in the form of metal or compounds. The method comprises the following steps: leaching, liquid-solid separation, solution purification, target metal extraction, wastewater treatment and the like. Among them, leaching, extraction of target metals and wastewater treatment are the most critical processes, and these processes are associated with recovery rate, cost and environmental protection.
In the leaching link, acid liquor is usually used for leaching, the reaction of acid and solid materials such as ores and calcines is usually a double decomposition reaction, when the acid liquor is weak, the reaction is inactive, but when the acid liquor is strong, as the discharge of sewage needs to be close to neutrality, alkaline materials and water need to be added, and the cost and the environmental pressure are higher.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for recovering tin from a tin-containing material, so that the consumption of hydrochloric acid is reduced, and the cost is reduced.
The invention relates to a method for recovering tin from tin-containing materials, which comprises the following steps,
1) Mixing the tin-containing material and distilled hydrochloric acid, leaching and filtering to obtain primary filtrate and primary filter residue;
2) Mixing the primary filter residue with concentrated hydrochloric acid with the mass concentration of at least 35.5%, leaching, and filtering to obtain secondary filtrate and secondary filter residue;
3) Rinsing the secondary filter residue, and filtering to obtain a rinsing liquid and rinsed filter residue;
4) Performing ammonium chloride tin precipitation on the primary filtrate, the secondary filtrate and the rinsing liquid to obtain ammonium stannate chloride, and filtering to obtain ammonium stannate chloride filter residues and filtrate;
5) Carrying out membrane distillation on the filtrate to obtain the distilled hydrochloric acid, and increasing the heating temperature and reducing the distillation pressure when distilling along with the increase of the concentration multiple during distillation, wherein the heating temperature during distillation is increased by 2-6 ℃ when the concentration multiple is increased by 1 time;
5) And dissolving, replacing and casting the ammonium chlorostannate filter residue to obtain the metallic tin.
Preferably, the heating temperature during distillation is increased by 3-5 ℃ for every 1-fold increase in the concentration.
Preferably, the filtration is pressure filtration.
Specifically, the distillation temperature of the primary filtrate, the secondary filtrate and the rinsing liquid is 100 ℃ and the pressure value is 272mbar when membrane distillation is carried out on the primary filtrate, the secondary filtrate and the rinsing liquid; when the concentration multiple is 3 times, the heating temperature during distillation is 110 ℃, and the pressure value is 157mbar; the heating temperature during distillation is 116 deg.C and the pressure value is 117mbar when the concentration multiple is 5 times.
Preferably, the mass concentration of the distilled hydrochloric acid is 10-20%.
Preferably, in the step 1), the liquid-solid ratio of the distilled hydrochloric acid to the tin-containing material is 4-6:1, and stirring is carried out during the leaching process, wherein the stirring speed is 45-100r/min.
Preferably, in the step 1), during leaching, an oxidant is added or oxygen pressure leaching is carried out, wherein the oxidant is sodium chlorate or hydrogen peroxide, the addition amount of the sodium chlorate is 10-15 kg/ton, the addition amount of the hydrogen peroxide is 15-20 kg/ton, the pressure of the oxygen pressure leaching is 1.5MPa, and the oxygen partial pressure is 7.5MPa.
Preferably, in the step 2), the liquid-solid ratio of the concentrated hydrochloric acid to the primary filter residue is 3-6:1.
Preferably, in the step 2), a closed reaction kettle is adopted for leaching, and during filtering, a volatilization-proof liquid level covering ball is added on the liquid level.
Preferably, in the step 4), before tin precipitation is carried out on the primary filtrate, the secondary filtrate and the rinsing liquid, the pH is adjusted to be 0.7-0.8, and the adding amount of ammonium chloride is 3.5-3.8 times of the theoretical value. The reaction time is 30-40 minutes and the reaction is carried out at room temperature.
Preferably, the rinsed filter residue is reduced by a reduction furnace, and the concentrated solution obtained after membrane distillation in the step 5) is treated by adding zinc powder for replacement reaction to obtain metallic tin.
The method has the advantages that the volatilizable characteristic of hydrochloric acid is perfectly combined with the technological requirement of membrane distillation, the materials are leached for the first time by using the distilled hydrochloric acid, the treatment time and cost of subsequent leaching by using concentrated hydrochloric acid are reduced, and the problem of large increase of waste water difficult to treat caused by the traditional method of adding water for dilution is avoided; the method of reducing acidity by adding ineffective materials (such as magnesia) is also avoided, because the pH value is reduced by using substances such as magnesia and the like, the cost is wasted, and impurity elements are brought into the system.
The method recycles the leached leachate in a membrane distillation mode, and in order to achieve the best hydrochloric acid recycling effect of membrane distillation, the method controls the distillation temperature, increases the heating temperature during distillation along with the increase of the concentration multiple during distillation, specifically, increases the heating temperature during distillation by 2-6 ℃ every time the concentration multiple is increased by 1 time, can effectively improve the recycling efficiency, avoids the hydrochloric acid liquid from forming adhesion on the membrane surface, and improves the passing rate of membrane distillation.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a schematic diagram showing liquid amount distribution in the case of multiple membrane distillation.
Fig. 3 is a photograph of different waters.
Fig. 4 is a photograph of the appearance of the concentrate and the produced water. Wherein, (a) is concentrated water, and (b) is produced water.
FIG. 5 is a photograph showing the wetting of the membrane with the raw water and the concentrated water. Wherein, (a) is raw water, and (b) is concentrated water.
FIG. 6 is a graph of single effect membrane flux versus concentration factor.
Detailed Description
Example 1
As shown in FIG. 1, the process flow of the invention is as follows:
1) The tin-containing material is leached out for one time by hydrochloric acid (namely dilute hydrochloric acid in figure 1, namely distilled hydrochloric acid) with the mass concentration of 15 percent, which is distilled out from the membrane, the leaching time is 2 hours, the liquid-solid ratio is 5:1, the temperature is normal, and the stirring speed is 80 revolutions per minute. To make full use of hydrochloric acid, the final acid (acid content after completion of the reaction) is kept within 1%, preferably neutral at pH 7.
2) And (3) carrying out liquid-solid separation on the materials subjected to primary leaching by using a filter press, directly discharging filter residues into a reaction kettle or a pulping kettle subjected to secondary leaching, and discharging filtrate into a filtrate storage tank to obtain dilute leaching solution.
3) Adding concentrated hydrochloric acid with concentration of more than 35.5% into the secondary reaction kettle, and leaching the material for the second time, wherein the liquid-solid ratio is 4:1, and the reaction kettle is preferably a closed reaction kettle because the acidity is very high and the volatility of the hydrochloric acid is very strong.
4) The secondary filter pressing is carried out by using a special filter press with an air draft system and preventing gas volatilization, the volatility of filtrate is very strong due to the concentrated hydrochloric acid leaching, and the liquid level of a storage tank needs to be covered with a ball by using the liquid level of volatilization prevention, so that secondary filtrate (concentrated leaching solution) and secondary filter residue are obtained.
5) Rinsing the secondary filter residue with clear water to ensure that the acid content in the rinsed filter residue is lower than 0.5 percent, and then carrying out filter pressing. And (3) conveying the filter residue to a reduction furnace, recovering valuable metals such as lead, silver and the like in the filter residue by reduction smelting, and pumping the filtrate to a storage tank to obtain rinsing liquid.
6) The filtrates with different acidity are respectively placed in different storage tanks.
7) Mixing the above dilute extractive solution, concentrated extractive solution and rinsing solution. Ammonium chloride was added, and tetravalent tin had a maximum value at pH =0.8, and was formed in the system at pH < 0.8 (NH) 4 ) 2 SnCL 6 Solid precipitate of Sn 4+ Sharply decreases, and the reaction formula is SnCl 4 +2NH 4 Cl＝(NH 4 ) 2 SnCL 6 . Specifically, before the ammonium chloride is used for tin precipitation, the pH value of the filtrate is adjusted to 0.7, and the addition amount of the ammonium chloride is 3.8 times of the theoretical value. The reaction is carried out for 30-40 minutes at room temperature, and after the tin is precipitated by ammonium chloride, the tin residue and the filtrate are obtained by filtration. And adding hydrochloric acid into the tin slag to dissolve the tin slag, and adding zinc powder for replacement to obtain a tin ingot. The filtrate was subjected to membrane distillation.
The membrane distillation process sets different distillation temperatures and pressures according to different acidity and concentration ratio of the filtrate. The specific settings are shown in table 1.
TABLE 1 concentration times and distillation temperatures, pressure gauge
| Multiple of concentration | Setting temperature of | Set pressure (mbar) |
| 1 times of | 100 | 272 |
| 3 | 110 | 157 |
| 5 | 116 | 117 |
7) For recovering tin from tin-containing materials, snCl is used 4 Has a boiling point of 114 ℃ and AsCl 3 The boiling point of (b) is 130 ℃ and SbCl 3 The boiling point of (A) is 220 ℃, and the separation can be carried out by utilizing different boiling points of various chlorides.
8) The heating of the membrane distillation utilizes the residual heat of the flue gas of the furnace.
Example 2
The filtrate (raw water) of step 6) of the above example 1 was subjected to primary distillation at 100 ℃ and 272mbar, and then evaporated to obtain 1# product water (25% of the volume of the raw water), the liquid remaining after distillation was concentrated water (i.e., the concentrated solution of fig. 1, the volume of which is 75% of the volume of the raw water), the concentrated water was subjected to secondary distillation at 110 ℃ and 157mbar, the evaporated liquid was 3# product water (the volume of which is 25% of the volume of the raw water), the remaining liquid was 2# concentrated water (the volume of which is 50% of the volume of the raw water), the 3# product water was subjected to tertiary distillation at 116 ℃ and 117mbar, the evaporated liquid was 5# product water, and the remaining liquid was 4# product water, as shown in fig. 2-3.
The raw water, 1#, 2#, 3#, 4#, and 5# produced water in example 2 were analyzed to obtain a content analysis table of each substance as shown in table 2.
TABLE 2 table for analyzing contents of respective substances
As can be seen from Table 2, tin is mainly concentrated in the No. 2 produced water, and other liquids are very little, which indicates that the enrichment degree is higher, and the enrichment degree is far higher than that of other metals such as arsenic and hydrochloric acid. The concentrated water No. 2 contains most of tin for subsequent recycling, and other produced water contains little tin and can be used for leaching materials.
Comparative example 1
The filtrate (raw water) of step 6) of the above example 1 was subjected to primary distillation at 100 ℃ and 101mbar, and the evaporated liquid was 1# produced water (25% by volume of the raw water), the remaining liquid after distillation was concentrated water (75% by volume of the raw water), the concentrated water was subjected to secondary distillation at 100 ℃ and 101mbar, the evaporated liquid was 3# produced water (25% by volume of the raw water), the remaining liquid was 2# concentrated water (50% by volume of the raw water), the 3# produced water was subjected to tertiary distillation at 100 ℃ and 101mbar, the evaporated liquid was 5# produced water, and the remaining liquid was 4# produced water.
The raw water, 1#, 2#, 3#, 4#, and 5# produced water in comparative example 1 were analyzed to obtain the content analysis table of each substance as shown in table 2.
TABLE 3 table for content analysis of each substance
| Serial number | HCL(g/l) | Containing tin (g/l) |
| 0# (raw water) | 223 | 29.7 |
| 1# | 127.41 | 0.22 |
| 2# | 310.24 | 45.87 |
| 3# | 170.26 | 0.21 |
| 4# | 198.24 | 0.19 |
| 5# | 160.51 | 0.19 |
Example 3
The raw water is from Chenzhou in Hunan province, and the water quality of the raw water is residual liquid after ore is dissolved by hydrochloric acid, and the residual liquid contains hydrochloric acid with certain solubility and salt with certain concentration.
And (3) taking 500mL of raw water solution to perform a distillation concentration experiment in a three-neck flask, measuring the boiling point temperature of the solution in the distillation process, collecting distillation condensate water, and weighing to calculate the concentration ratio.
A small test membrane module is adopted to carry out a single-effect vacuum type membrane distillation test, and the single-effect flux of the material during operation is simulated and calculated by testing the saline flux, so that the feasibility of adopting a membrane distillation technology is evaluated.
Taking 500ml of raw water, heating and concentrating, measuring the boiling point, collecting condensate, wherein the volume of the raw water is 500ml, the mass is 600g in total, and the density rho =1.199g/ml. After a period of heating concentration, the volume of the solution is gradually reduced, and finally, the heating concentration is stopped after the concentrated solution has crystal salt, and the solution is weighed after being cooled.
129.6g of concentrated water, 425.1g of produced water and 554.7g of concentrated water are obtained, and due to the fact that the initial hydrochloric acid content is high, a part of hydrogen chloride gas is dissipated in the evaporation process and is not condensed, and therefore the sum of the quality of the concentrated water and the produced water is smaller than that of the raw water, as shown in the figure 4.
During evaporation, the concentration increased with decreasing volume, and the acidity decreased from 9.71mol/L to 8.04mol/L, as shown in Table 4.
TABLE 4 acidity situation
| Water sample | Total acidity mol/L |
| Raw water | 9.71 |
| Concentrated water | 8.90 |
| Produce water | 8.04 |
The acidity of produced water is about 8.04mol/L, which shows that when the re-concentration multiple is more than 4 times through the concentration of the membrane distillation technology, hydrochloric acid solution with the concentration of more than 75 percent can be simultaneously recovered, and the concentration of the recovered hydrochloric acid can reach 8.04mol/L.
As can be seen from FIG. 5, the raw water can roll on the membrane surface, no adhesion is generated, and the hydrophobic property is good. The concentrated water still has a certain hydrophobic angle on the surface of the membrane, can roll on the surface of the membrane, but has partial adhesion phenomenon, and the hydrophobic property of the concentrated water is reduced to a certain degree.
The relationship between the concentration multiple and the flux of the single-effect membrane is calculated, as shown in fig. 6, it can be seen from fig. 6 that as the concentration multiple increases, the temperature rise of the boiling point of the solution increases to reduce the flux of the single-effect membrane, and the water yield decreases in the actual evaporation process.
From the above analysis, it is known that the solution can be concentrated 4 times or more using membrane distillation techniques; the produced water with the volume of more than 75 percent of the original water can be recovered, and the concentration of the hydrochloric acid of the produced water can reach 8.04mol/L; the raw water has good hydrophobic property, and the hydrophobic property of the concentrated water is slightly reduced.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to imply that the scope of the application is limited to these examples; within the context of the present application, features from the above embodiments or from different embodiments may also be combined, steps may be implemented in any order, and there are many other variations of different aspects of one or more embodiments in the present application as described above, which are not provided in detail for the sake of brevity.
It is intended that the one or more embodiments of the present application cover all such alternatives, modifications, and variations as fall within the broad scope of the present application. Therefore, any omissions, modifications, substitutions, improvements, and the like that may be made without departing from the spirit and principles of one or more embodiments of the present application are intended to be included within the scope of the present application.
Claims (10)
1. A method for recovering tin from tin-containing materials is characterized by comprising the following steps,
1) Mixing the tin-containing material and distilled hydrochloric acid, leaching and filtering to obtain primary filtrate and primary filter residue;
2) Mixing the primary filter residue with concentrated hydrochloric acid with the mass concentration of at least 35.5%, leaching, and filtering to obtain secondary filtrate and secondary filter residue;
3) Rinsing the secondary filter residue, and filtering to obtain a rinsing liquid and rinsed filter residue;
4) Performing ammonium chloride tin precipitation on the primary filtrate, the secondary filtrate and the rinsing liquid to obtain ammonium stannate chloride, and filtering to obtain ammonium stannate chloride filter residues and filtrate;
5) Carrying out membrane distillation on the filtrate to obtain the distilled hydrochloric acid, and increasing the heating temperature and reducing the distillation pressure when distilling along with the increase of the concentration multiple during distillation, wherein the heating temperature during distillation is increased by 2-6 ℃ when the concentration multiple is increased by 1 time;
6) And dissolving the ammonium stannate filter residue, and performing replacement treatment to obtain the metallic tin.
2. The method for recovering tin from a tin-containing material as set forth in claim 1, wherein the heating temperature during distillation is increased by 3 to 5 ℃ for every 1-fold increase in the concentration.
3. A process according to claim 1 for recovering tin from a tin-containing material, wherein the primary filtrate, secondary filtrate and rinse are subjected to membrane distillation at a distillation temperature of 100 ℃ and a pressure of 272mbar; when the concentration multiple is 3 times, the heating temperature during distillation is 110 ℃, and the pressure value is 157mbar; the heating temperature during distillation was 116 deg.C and the pressure was 117mbar when the concentration factor was 5 times.
4. The method for recovering tin from a tin-containing material according to claim 1, wherein the concentration by mass of the distilled hydrochloric acid is 10 to 20%.
5. The method for recovering tin from tin-containing material as claimed in claim 1, wherein in the step 1), the liquid-solid ratio of the distilled hydrochloric acid to the tin-containing material is 4-6:1, and stirring is performed during leaching at a rotation speed of 45-100r/min.
6. The method for recovering tin from tin-containing materials as claimed in claim 1, wherein step 1) is carried out by adding an oxidant during leaching or by oxygen pressure leaching, wherein the oxidant is sodium chlorate or hydrogen peroxide.
7. The method for recovering tin from tin-containing materials according to claim 6, wherein the addition amount of sodium chlorate is 10-15 kg/ton, the addition amount of hydrogen peroxide is 15-20 kg/ton, the pressure of oxygen pressure leaching is 1.5MPa, and the oxygen partial pressure is 7.5MPa.
8. A process according to any one of claims 1 to 7, wherein in step 2) the liquid to solid ratio of concentrated hydrochloric acid to primary filter residue is from 3 to 6:1.
9. A method for recovering tin from tin-containing materials as claimed in any one of claims 1 to 7, wherein in step 2), the leaching is carried out by using a closed reaction vessel, and a liquid level covering ball for preventing volatilization is added on the liquid level during the filtration.
10. The method for recovering tin from a tin-containing material according to any one of claims 1 to 7, wherein in the step 4), the pH of the primary filtrate, the secondary filtrate and the rinsing liquid is adjusted to 0.7 to 0.8 before tin precipitation is carried out, and the amount of ammonium chloride added is 3.5 to 3.8 times the theoretical value.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211689542.5A CN115896478A (en) | 2022-12-27 | 2022-12-27 | Method for recovering tin from tin-containing material |
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| JP2008297608A (en) * | 2007-05-31 | 2008-12-11 | Mitsubishi Materials Corp | Method for separating/recovering tin |
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| CN102392130A (en) * | 2011-12-13 | 2012-03-28 | 郴州市金贵银业股份有限公司 | Method for recovering lead and tin from zinc leaching residues |
| CN112410578A (en) * | 2020-10-23 | 2021-02-26 | 刘罗平 | Comprehensive recovery method for tin precipitation of tin-containing material by oxygen pressure alkaline leaching of calcium salt |
| CN114892007A (en) * | 2022-05-18 | 2022-08-12 | 云南锡业股份有限公司铜业分公司 | Method for recovering valuable metals from selenium steaming slag of complex copper anode slime |
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| JP2008297608A (en) * | 2007-05-31 | 2008-12-11 | Mitsubishi Materials Corp | Method for separating/recovering tin |
| CN101514396A (en) * | 2009-04-03 | 2009-08-26 | 郴州市宇腾化工有限公司 | Method for separating tin and stibium from tin-lead anode slime |
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| CN112410578A (en) * | 2020-10-23 | 2021-02-26 | 刘罗平 | Comprehensive recovery method for tin precipitation of tin-containing material by oxygen pressure alkaline leaching of calcium salt |
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