WO2024138593A1 - Process method for recovering tin, iron and manganese by sulfuric acid elution of tantalum slag - Google Patents
Process method for recovering tin, iron and manganese by sulfuric acid elution of tantalum slag Download PDFInfo
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- WO2024138593A1 WO2024138593A1 PCT/CN2022/143744 CN2022143744W WO2024138593A1 WO 2024138593 A1 WO2024138593 A1 WO 2024138593A1 CN 2022143744 W CN2022143744 W CN 2022143744W WO 2024138593 A1 WO2024138593 A1 WO 2024138593A1
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- manganese
- slag
- tin
- sulfuric acid
- iron
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 74
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000011135 tin Substances 0.000 title claims abstract description 46
- 239000002893 slag Substances 0.000 title claims abstract description 44
- 229910052718 tin Inorganic materials 0.000 title claims abstract description 44
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 36
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000011572 manganese Substances 0.000 title claims abstract description 34
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 33
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 25
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000010828 elution Methods 0.000 title abstract 2
- 239000000706 filtrate Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 16
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 12
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 11
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 11
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000004064 recycling Methods 0.000 claims abstract description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 8
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 7
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 7
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 6
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 6
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 6
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 238000011085 pressure filtration Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003546 flue gas Substances 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 230000001698 pyrogenic effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000012065 filter cake Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 239000007832 Na2SO4 Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- 241001274216 Naso Species 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- -1 iron-manganese-tantalum Chemical compound 0.000 description 1
- IGSZZIUPCQHSQB-UHFFFAOYSA-N manganese tantalum Chemical compound [Mn][Ta] IGSZZIUPCQHSQB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Definitions
- the invention belongs to the field of waste recovery and environmental protection, and specifically relates to a process for eluting sulfuric acid from tantalum slag containing tin, iron and manganese, and comprehensively recovering tin, iron and manganese.
- Tantalum is an important rare metal with a high melting point and has been widely used in many fields.
- the method of smelting tantalum ore by high-temperature roasting with concentrated sulfuric acid is to make tantalum soluble, extract it with water, and then recover it from the filtrate. If the tantalum ore contains tin, iron and manganese, the remaining tantalum slag contains 15% to 20% sulfuric acid, 7% to 8% Sn, 6% to 15% Fe, 6% to 10% Mn, and the rest is water and gangue.
- the tin contained in the tantalum slag is a high-value resource. It can generally be disposed of in a fuming furnace to recover high-grade tin-containing smoke.
- the raw materials contain a large amount of sulfuric acid, the environmental load of the smelting flue gas is huge, the operation is difficult, and sometimes the fuming furnace equipment is damaged; on the other hand, because of the high manganese content, the fuming furnace slag type is not suitable for smelting, which causes difficulties, so a large amount of filter residue inventory is accumulated, resulting in the difficulty of using resources and waste, and at the same time forming serious environmental safety hazards.
- the purpose of the present invention is to provide a process for eluting tantalum slag with sulfuric acid to recover tin, iron and manganese, so as to elute tantalum slag containing tin, iron and manganese with sulfuric acid and recover tin, iron and manganese at the same time.
- step C Add hydrogen peroxide to the acidic filtrate obtained in step A to oxidize Fe 2+ in the filtrate to Fe 3+ .
- the amount of hydrogen peroxide added depends on the amount of Fe 2+ in the tantalum slag. It is sufficient to oxidize all Fe 2+ to Fe 3+ .
- the filtrate is reserved for later use.
- the method of the present invention can leach and separate the residual sulfuric acid, ferrous sulfate and manganese sulfate in the tantalum slag, thereby reducing the improper influence on the slag type during the recovery of the pyro-fuming furnace and the adverse impact of a large amount of sulfuric acid-containing flue gas on the environment; at the same time, the tin grade is improved by 200%, which greatly improves the tin recovery index and increases the economic benefits; the iron and manganese recovered incidentally also have certain resources and economic benefits. This method enables the precious resources that cannot be directly used by the fuming furnace to achieve real environmental protection and harmless utilization.
Abstract
A process method for recovering tin, iron and manganese by sulfuric acid elution of tantalum slag, comprising: adding water into tantalum slag to leach soluble sulfuric acid, ferrous sulfate and manganese sulfate in the tantalum slag, and carrying out filter pressing to separate acidic filtrate and tin-containing filter residues; and oxidizing Fe2+ in the acidic filtrate into Fe3+, carrying out precipitation separation on Fe3+, carrying out filter pressing to obtain iron slag, continuously adding sodium carbonate into the filtrate to generate manganese carbonate precipitate, and carrying out filter pressing to obtain manganese slag. According to the method, residual sulfuric acid, ferrous sulfate and manganese sulfate in the tantalum slag are leached and separated, so that the improper impact on the slag type and the adverse effect of a large amount of sulfuric acid-containing flue gas on the environment during recovery by a pyrogenic fuming furnace can be reduced; and moreover, the tin grade is improved, and the recovered iron and manganese have certain resources and economic benefits. According to the method, real environment-friendly recycling and harmless utilization of valuable resources which cannot be directly utilized by the fuming furnace are realized.
Description
本发明属于废料回收及环保领域，具体涉及从含锡铁锰的钽渣中洗脱硫酸，同时综合回收锡铁锰的工艺方法。The invention belongs to the field of waste recovery and environmental protection, and specifically relates to a process for eluting sulfuric acid from tantalum slag containing tin, iron and manganese, and comprehensively recovering tin, iron and manganese.
钽为重要的稀有高熔点金属，已被广泛应用于诸多领域。采用浓硫酸熟化高温焙烧方法冶炼钽矿，是将钽变成可溶性后用水浸提取，再从滤液中回收，若钽矿中含锡铁锰，则余下的钽渣中含硫酸15％～20％、Sn 7％～8％、Fe 6％～15％、Mn 6％～10％，其余为水和脉石。钽渣中含有的锡属高价值资源，一般可采用烟化炉将其处置，以回收高品位的含锡烟尘，但因原料中一方面含大量的硫酸，使冶炼烟气的环保负荷巨大，操作困难，有时会对烟化炉设备造成损坏；另一方面因含较高的锰，使烟化炉渣型不适合冶炼，造成困难，故使大量的滤渣库存积压，造成资源的难以利用而浪费，同时形成严重的环保安全隐患。Tantalum is an important rare metal with a high melting point and has been widely used in many fields. The method of smelting tantalum ore by high-temperature roasting with concentrated sulfuric acid is to make tantalum soluble, extract it with water, and then recover it from the filtrate. If the tantalum ore contains tin, iron and manganese, the remaining tantalum slag contains 15% to 20% sulfuric acid, 7% to 8% Sn, 6% to 15% Fe, 6% to 10% Mn, and the rest is water and gangue. The tin contained in the tantalum slag is a high-value resource. It can generally be disposed of in a fuming furnace to recover high-grade tin-containing smoke. However, because the raw materials contain a large amount of sulfuric acid, the environmental load of the smelting flue gas is huge, the operation is difficult, and sometimes the fuming furnace equipment is damaged; on the other hand, because of the high manganese content, the fuming furnace slag type is not suitable for smelting, which causes difficulties, so a large amount of filter residue inventory is accumulated, resulting in the difficulty of using resources and waste, and at the same time forming serious environmental safety hazards.
发明内容Summary of the invention
本发明的目的是，针对上述现有技术的不足，提供一种钽渣洗脱硫酸回收锡铁锰的工艺方法，以对含有锡铁锰的钽渣进行硫酸洗脱，同时回收锡铁锰。The purpose of the present invention is to provide a process for eluting tantalum slag with sulfuric acid to recover tin, iron and manganese, so as to elute tantalum slag containing tin, iron and manganese with sulfuric acid and recover tin, iron and manganese at the same time.
为达上述目的，本发明所采用的技术方案是：一种钽渣洗脱硫酸回收锡铁锰的工艺方法，该方法步骤如下，结合参见图1：To achieve the above purpose, the technical solution adopted by the present invention is: a process for recovering tin, iron and manganese by eluting sulfuric acid from tantalum slag, the steps of which are as follows, with reference to FIG1:
A.一次水洗。按固液比(重量)1：(1.2-1.6)，将钽渣加水打浆，搅拌浸出钽渣中可溶性的硫酸、硫酸亚铁和硫酸锰，压滤，分离出酸性滤液及含锡滤渣；含锡滤渣进入步骤B，酸性滤液备用。A. One-time water washing. According to the solid-liquid ratio (weight) of 1:(1.2-1.6), add water to the tantalum slag to make a pulp, stir to leach out the soluble sulfuric acid, ferrous sulfate and manganese sulfate in the tantalum slag, filter by pressure to separate the acidic filtrate and the tin-containing filter residue; the tin-containing filter residue enters step B, and the acidic filtrate is reserved.
上述所提钽渣中含硫酸15％～20％、Sn 7％～8％、Fe 6％～15％、Mn 6％～10％，其余为水和脉石。其中，Fe以硫酸亚铁形式存在，Mn以硫酸锰形式存在。The tantalum slag mentioned above contains 15% to 20% sulfuric acid, 7% to 8% Sn, 6% to 15% Fe, 6% to 10% Mn, and the rest is water and gangue. Among them, Fe exists in the form of ferrous sulfate and Mn exists in the form of manganese sulfate.
B.二次水洗。按固液比(重量)1：(1.2-1.6)，将含锡滤渣加水打浆，搅匀，压滤，所得滤渣即为含锡钽渣产品，产品中含Sn 13％-18％、Mn≤0.6％，含锡钽渣中锡品位提升、锰含量降低，有利于烟化炉产出高锡烟尘，便于后续火法冶炼；滤液返回步骤A循环利用。B. Secondary water washing. According to the solid-liquid ratio (weight) of 1:(1.2-1.6), add water to the tin-containing filter residue to make a pulp, stir evenly, and filter press. The obtained filter residue is the tin-containing tantalum slag product, which contains Sn 13%-18% and Mn ≤ 0.6%. The tin grade of the tin-containing tantalum slag is improved and the manganese content is reduced, which is conducive to the production of high-tin smoke dust in the fuming furnace and is convenient for subsequent pyrometallurgy; the filtrate is returned to step A for recycling.
C.于步骤A所得的酸性滤液中加入双氧水，以氧化滤液中的Fe
2+为Fe
3+，双氧水的加入量视钽渣中Fe
2+的量而定，只要将Fe
2+全部氧化为Fe
3+即可，然后加氢氧化钠调pH值为3.6-3.8使Fe
3+沉淀分离，压滤，所得滤渣即为铁渣，含Fe量为45％-55％，滤液备用。
C. Add hydrogen peroxide to the acidic filtrate obtained in step A to oxidize Fe 2+ in the filtrate to Fe 3+ . The amount of hydrogen peroxide added depends on the amount of Fe 2+ in the tantalum slag. It is sufficient to oxidize all Fe 2+ to Fe 3+ . Then add sodium hydroxide to adjust the pH value to 3.6-3.8 to precipitate and separate Fe 3+ . Press filter to obtain the filter residue, which is iron slag with an Fe content of 45%-55%. The filtrate is reserved for later use.
D.于步骤C所得滤液中加入碳酸钠至溶液终pH值为10-10.5，同时碳酸钠会与滤液中的硫酸锰反应生成碳酸锰沉淀，反应式为：Na
2CO
3+MnSO
4→MnCO
3↓+Na
2SO
4，压滤，所得滤渣即为锰渣，含Mn量为25-35％，滤液备用。
D. Add sodium carbonate to the filtrate obtained in step C until the final pH value of the solution is 10-10.5. At the same time , sodium carbonate will react with manganese sulfate in the filtrate to form manganese carbonate precipitate. The reaction formula is: Na2CO3 + MnSO4 → MnCO3 ↓+ Na2SO4 . Press filter to obtain the manganese residue, which contains 25-35% Mn. The filtrate is reserved.
E.将步骤D所得滤液送入MVR蒸发器蒸发，过饱和析出硫酸钠晶体，将晶体离心分离、烘干，即得硫酸钠产品；蒸发所得冷凝水返回步骤B循环利用；离心所得母液返回至MVR蒸发器中循环利用。E. The filtrate obtained in step D is sent to an MVR evaporator for evaporation, sodium sulfate crystals are precipitated by supersaturation, and the crystals are centrifuged and dried to obtain the sodium sulfate product; the condensed water obtained by evaporation is returned to step B for recycling; the mother liquor obtained by centrifugation is returned to the MVR evaporator for recycling.
本发明方法处理含锡铁锰的钽渣后，能浸出分离钽渣中残余的硫酸、硫酸亚铁和硫酸锰，从而减少火法烟化炉回收时对渣型的不当影响和大量含硫酸烟气对环境的不利影响；同时锡品位提升，提高幅度达200％，大幅提高锡的回收指标，增加经济效益；附带回收的铁和锰也有一定的资源和经济效益。本方法使得烟化炉无法直接利用的贵重资源实现真正的环保资源化、无害化利用。After treating tantalum slag containing tin, iron and manganese, the method of the present invention can leach and separate the residual sulfuric acid, ferrous sulfate and manganese sulfate in the tantalum slag, thereby reducing the improper influence on the slag type during the recovery of the pyro-fuming furnace and the adverse impact of a large amount of sulfuric acid-containing flue gas on the environment; at the same time, the tin grade is improved by 200%, which greatly improves the tin recovery index and increases the economic benefits; the iron and manganese recovered incidentally also have certain resources and economic benefits. This method enables the precious resources that cannot be directly used by the fuming furnace to achieve real environmental protection and harmless utilization.
图1为本发明的工艺流程图。Fig. 1 is a process flow chart of the present invention.
本文中各物质的含量均为质量含量。The contents of each substance in this article are all by mass.
实施例1Example 1
在试验室条件下，于500mL水中加入330g含锡铁锰钽渣(含锡铁锰钽渣含Sn 7％、Fe 12％、Mn 6.5％、硫酸16％)，常温搅拌浸出约30分钟，用真空抽滤机抽滤得到一次滤饼和过滤液(一次洗水)。于该一次滤饼中加入1.5倍重量的水，打浆，搅匀，进行二次水洗浸后真空抽滤，得到二次滤饼和滤液，将二次滤饼烘干后化验得到含Sn约18％、Mn约0.8％、Fe约1.0％的二次洗后的高锡脱铁锰钽渣，有利于用烟化炉挥发回收其中的锡。将上述二次水洗的过滤水返回到前液循环利用。将前述得到的一次洗水，因为采用二次逆流水浸洗，得到含量较高的含硫酸、硫酸铁和硫酸锰溶液，加入约45mL的质量浓度为24％的双氧水，搅拌约15分钟使溶液中二价铁转化成三价铁，加入质量浓度约30％的NaOH液，使溶液的pH值调节到3.6～3.8时，真空抽滤此浆液得到含三价铁的滤饼和含硫酸锰的过滤清液，将含铁滤饼烘干化验Fe约45％。将上述含硫酸锰的清液加入适量含量约20％Na
2CO
3溶液发生下述化学反应：MnSO
4+Na
2CO
3＝MnCO
3↓+Na
2SO
4，当溶液pH控制在10.5时真空抽滤此浆液得到MnCO
3滤饼和含Na
2SO
4清液，烘干滤饼化验，含Mn 36％，是很好的锰原材料。
Under laboratory conditions, 330g of tin-containing iron-manganese-tantalum slag (containing 7% Sn, 12% Fe, 6.5% Mn, and 16% sulfuric acid) was added to 500mL of water, stirred and leached at room temperature for about 30 minutes, and filtered with a vacuum filter to obtain a primary filter cake and a filtrate (primary washing water). 1.5 times the weight of water was added to the primary filter cake, beaten, stirred, and washed twice with water and then vacuum filtered to obtain a secondary filter cake and a filtrate. The secondary filter cake was dried and then tested to obtain a secondary washed high-tin iron-removed manganese-tantalum slag containing about 18% Sn, about 0.8% Mn, and about 1.0% Fe, which was beneficial to volatilize and recover the tin therein with a fuming furnace. The filtered water of the above-mentioned secondary washing was returned to the front liquid for recycling. The primary washing water obtained above is washed with secondary countercurrent water to obtain a solution containing high content of sulfuric acid, iron sulfate and manganese sulfate. About 45 mL of hydrogen peroxide with a mass concentration of 24% is added, and stirred for about 15 minutes to convert the divalent iron in the solution into trivalent iron. When the pH value of the solution is adjusted to 3.6-3.8 by adding NaOH solution with a mass concentration of about 30%, the slurry is vacuum filtered to obtain a filter cake containing trivalent iron and a filtered clear liquid containing manganese sulfate. The iron-containing filter cake is dried and tested to have Fe of about 45%. The clear liquid containing manganese sulfate is added with an appropriate amount of Na2CO3 solution with a content of about 20% to produce the following chemical reaction: MnSO4 + Na2CO3 ＝ MnCO3 ↓+ Na2SO4 . When the pH of the solution is controlled at 10.5, the slurry is vacuum filtered to obtain a MnCO3 filter cake and a clear liquid containing Na2SO4 . The filter cake is dried and tested to have Mn 36%, which is a good manganese raw material.
将上述所得含NaSO
4溶液累积后于烧杯中在电炉上蒸发浓缩生成过饱和Na
2SO
4结晶，使工艺过程符合环保处理要求。得到的NaSO
4产品可进一步增值。
The NaSO 4 solution obtained above is accumulated in a beaker and evaporated and concentrated on an electric furnace to generate supersaturated Na 2 SO 4 crystals, so that the process meets environmental protection requirements. The obtained NaSO 4 product can be further increased in value.
Claims (9)
- 一种钽渣洗脱硫酸回收锡铁锰的工艺方法，其特征在于，该方法步骤如下：A process for recovering tin, iron and manganese by eluting sulfuric acid from tantalum slag, characterized in that the method comprises the following steps:A.将钽渣加水打浆，搅拌浸出钽渣中可溶性的硫酸、硫酸亚铁和硫酸锰，压滤，分离出酸性滤液及含锡滤渣；含锡滤渣进入步骤B，酸性滤液备用；其中，钽渣含硫酸15％～20％、Sn 7％～8％、Fe 6％～15％、Mn 6％～10％，Fe以硫酸亚铁形式存在，Mn以硫酸锰形式存在；A. Add water to tantalum slag and make pulp, stir to leach soluble sulfuric acid, ferrous sulfate and manganese sulfate in the tantalum slag, filter press to separate acidic filtrate and tin-containing filter residue; the tin-containing filter residue enters step B, and the acidic filtrate is reserved; wherein, the tantalum slag contains 15% to 20% sulfuric acid, 7% to 8% Sn, 6% to 15%, and 6% to 10% Mn, Fe exists in the form of ferrous sulfate, and Mn exists in the form of manganese sulfate;B.将含锡滤渣加水打浆，搅匀，压滤，所得滤渣即为含锡钽渣产品；B. Add water to the tin-containing filter residue, mix well, and filter press. The obtained filter residue is the tin-containing tantalum slag product;C.于步骤A所得的酸性滤液中加入双氧水直至滤液中的Fe 2+氧化为Fe 3+，然后加氢氧化钠调pH值为3.6-3.8使Fe 3+沉淀分离，压滤，所得滤渣即为铁渣，滤液进入步骤D； C. Add hydrogen peroxide to the acidic filtrate obtained in step A until the Fe 2+ in the filtrate is oxidized to Fe 3+ , then add sodium hydroxide to adjust the pH value to 3.6-3.8 to precipitate and separate Fe 3+ , filter by pressure, and the obtained filter residue is the iron slag, and the filtrate enters step D;D.于滤液中加入碳酸钠至溶液终pH值为10-10.5，同时碳酸钠与滤液中的硫酸锰反应生成碳酸锰沉淀，压滤，所得滤渣即为锰渣，滤液进入步骤E；D. adding sodium carbonate to the filtrate until the final pH value of the solution is 10-10.5, and at the same time, sodium carbonate reacts with manganese sulfate in the filtrate to form manganese carbonate precipitate, and filter presses to obtain the filter residue, which is manganese residue. The filtrate enters step E;E.将滤液送入MVR蒸发器蒸发，过饱和析出硫酸钠晶体，将晶体离心分离、烘干，即得硫酸钠产品。E. The filtrate is sent to the MVR evaporator for evaporation, and sodium sulfate crystals are precipitated after supersaturation. The crystals are centrifuged and dried to obtain the sodium sulfate product.
- 如权利要求1所述的钽渣洗脱硫酸回收锡铁锰的工艺方法，其特征在于，所述步骤A中加入的水的重量为钽渣的1.2-1.6倍。The process for eluting sulfuric acid from tantalum slag to recover tin, iron and manganese as described in claim 1, characterized in that the weight of water added in step A is 1.2-1.6 times that of the tantalum slag.
- 如权利要求1所述的钽渣洗脱硫酸回收锡铁锰的工艺方法，其特征在于，所述步骤B中加入的水的重量为含锡滤渣的1.2-1.6倍。The process for eluting sulfuric acid from tantalum slag to recover tin, iron and manganese as described in claim 1, characterized in that the weight of the water added in step B is 1.2-1.6 times the weight of the tin-containing filter residue.
- 如权利要求1所述的钽渣洗脱硫酸回收锡铁锰的工艺方法，其特征在于，所述步骤B中含锡钽渣产品含Sn 13％-18％、Mn≤0.6％。The process for recovering tin, iron and manganese by eluting tantalum slag with sulfuric acid as described in claim 1 is characterized in that the tin-containing tantalum slag product in step B contains Sn 13%-18% and Mn ≤ 0.6%.
- 如权利要求1所述的钽渣洗脱硫酸回收锡铁锰的工艺方法，其特征在于， 所述步骤B中压滤所得滤液返回步骤A循环利用。The process for eluting tantalum slag with sulfuric acid to recover tin, iron and manganese as described in claim 1 is characterized in that the filtrate obtained by pressure filtration in step B is returned to step A for recycling.
- 如权利要求1所述的钽渣洗脱硫酸回收锡铁锰的工艺方法，其特征在于，所述步骤C中滤渣含Fe量为45％-55％。The process for recovering tin, iron and manganese by eluting sulfuric acid from tantalum slag as claimed in claim 1, characterized in that the Fe content of the filter residue in step C is 45%-55%.
- 如权利要求1所述的钽渣洗脱硫酸回收锡铁锰的工艺方法，其特征在于，所述步骤D中锰渣含Mn量为25-35％。The process for recovering tin, iron and manganese by eluting sulfuric acid from tantalum slag as claimed in claim 1, characterized in that the manganese slag in step D contains 25-35% Mn.
- 如权利要求1所述的钽渣洗脱硫酸回收锡铁锰的工艺方法，其特征在于，所述步骤E中蒸发所得冷凝水返回步骤B循环利用。The process for recovering tin, iron and manganese by eluting sulfuric acid from tantalum slag as described in claim 1 is characterized in that the condensed water obtained by evaporation in step E is returned to step B for recycling.
- 如权利要求1所述的钽渣洗脱硫酸回收锡铁锰的工艺方法，其特征在于，所述步骤E中离心所得母液返回至MVR蒸发器中循环利用。The process for recovering tin, iron and manganese by eluting sulfuric acid from tantalum slag as claimed in claim 1, characterized in that the mother liquor obtained by centrifugation in step E is returned to the MVR evaporator for recycling.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024138593A1 true WO2024138593A1 (en) | 2024-07-04 |
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