WO2023178902A1 - Method for recovering soluble tungstate in tungsten-containing waste - Google Patents
Method for recovering soluble tungstate in tungsten-containing waste Download PDFInfo
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- WO2023178902A1 WO2023178902A1 PCT/CN2022/108808 CN2022108808W WO2023178902A1 WO 2023178902 A1 WO2023178902 A1 WO 2023178902A1 CN 2022108808 W CN2022108808 W CN 2022108808W WO 2023178902 A1 WO2023178902 A1 WO 2023178902A1
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- Prior art keywords
- tungsten
- containing waste
- leachate
- solution
- alkali
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- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 104
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000010937 tungsten Substances 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000002699 waste material Substances 0.000 title claims abstract description 23
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 37
- 238000002386 leaching Methods 0.000 claims abstract description 27
- 239000002244 precipitate Substances 0.000 claims abstract description 16
- 239000002893 slag Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 42
- 230000008569 process Effects 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 238000004064 recycling Methods 0.000 description 9
- 238000000605 extraction Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 239000005750 Copper hydroxide Substances 0.000 description 2
- 229910018661 Ni(OH) Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- 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
Definitions
- the invention belongs to the technical field of metal tungsten recycling, and specifically relates to a method for recycling soluble tungstate in tungsten-containing waste materials.
- Tungsten is a rare strategic metal with a series of unique properties such as high melting point, high density, and low thermal expansion coefficient. It is widely used in national defense, aerospace, energy, mining and other fields. In recent years, due to the increased intensity of tungsten resource mining, tungsten reserves have been consumed too quickly, and the sustainable development of tungsten resources is facing new challenges. Therefore, it is of great significance to vigorously develop the efficient resource utilization of tungsten and tungsten alloy waste.
- tungsten-containing scrap With the continuous innovation in the production technology and application fields of tungsten-containing products, tungsten-containing scrap has gradually become complex and diverse. More than 50% of the world's tungsten resources are used to make cemented carbide, and the tungsten content in scrap cemented carbide has Reaching 74 ⁇ 91%.
- the methods for separating and recovering metals in tungsten-containing scrap include inorganic acid leaching, chlorination, zinc fusion, oxidation-reduction, etc.
- tungsten-containing waste materials have gradually become complex and diverse.
- tungsten-containing scraps such as scrap cemented carbide through a selective acid dissolution process
- the purpose of the present invention is to efficiently recover a small amount of tungsten in the leachate obtained from acid-soluble tungsten-containing waste, thereby improving the efficient resource utilization of complex tungsten-containing waste, promoting the separation of tungsten and cobalt, and obtaining good economic benefits. and environmental benefits.
- a method for recycling soluble tungstate in tungsten-containing waste materials including the following steps:
- the reagent used to adjust the pH in step S2 is an inorganic base or an organic base. It can be understood that the reagent used to adjust the pH is an alkaline solvent that does not precipitate with tungsten, including but not limited to NaOH, KOH, Na 2 CO 3 , NH 3 ⁇ H 2 O, etc.
- the calcination temperature in step S3 is 300-900°C, more preferably, the calcination temperature is 300-700°C; it can be understood that the calcination time can be adjusted according to the amount of materials used.
- the alkali leaching process in step S3 is specifically: adding the sintered material into the alkali solution and reacting at 50-100°C; more preferably, reacting at 70-100°C.
- the alkali leaching reaction time can be set according to the actual situation.
- the alkali solution is an alkaline solution that does not precipitate with tungsten, including but not limited to NaOH, KOH or a mixture of the two, and the concentration of the alkali solution is 30-180g/L; more preferably, the alkali solution The concentration of alkali solution is 60 ⁇ 180g/L.
- tungsten-containing waste usually also contains impurity elements such as Fe, Ni, Cu, and Al, which will enter the leachate during the acid leaching process; the present invention utilizes this feature to precipitate the above metal ions to form corresponding Fe(OH) 3 , Ni(OH) 2, etc. precipitate, through the flocculation of this type of precipitation, the tungsten (existing in the form of tungstate, tungsten-containing heteropolyacid, etc.) in the leachate is captured and adsorbed, and the tungsten in the leachate is of tungsten is fixed in the precipitate.
- impurity elements such as Fe, Ni, Cu, and Al
- the filter residue obtained from alkali leaching can be added to the leachate as a flocculant for recycling.
- the recycling method of the present invention has low cost, good recycling effect and is green and environmentally friendly, and provides technical guidance for the industrial recycling of complex tungsten-containing waste materials.
- the invention provides a method for recycling soluble tungstate in tungsten-containing waste materials. The specific steps are:
- the process is specifically as follows: take 500g of scrap cemented carbide and place it in a 2L beaker, add 1L of sulfuric acid, acetic acid, nitric acid or their mixed acid (5M) to perform acid leaching of cobalt under stirring conditions. After reacting for 12 hours, filter to obtain the dissolved cobalt liquid (i.e. leachate). Since scrap cemented carbide contains a variety of metal elements, the leachate obtained by the present invention also contains Fe, Ni, Cu, Al and other metal elements in addition to Co and W.
- the obtained filter residue can be re-added to the leachate in step (1) as a flocculant for recycling. Moreover, tests have proven that within the same pH adjustment range, the removal rate of W in the leachate is significantly increased, indicating that the impurity phase contained in the leachate can be recycled as a flocculant to realize the resource utilization of soluble tungstate.
- the tungsten extraction effects are 50%, 82%, 88%, 98%, 98.2% and 98.5% respectively (the difference between the original cobalt content in the leachate and the tungsten content in the filter residue obtained from alkali leaching/the original cobalt content in the leachate, when adsorbed by default All the tungsten in the leachate has been flocculated). It shows that as the alkali content increases, the tungsten extraction effect of the flocculant gradually increases. When the alkalinity rises to 120g/L, the tungsten extraction effect changes little.
- the tungsten extraction rates are respectively: 55%, 64%, 80%, 98.6, 99% and 99.1% (the calculation method is the same as in Example 2). It shows that increasing the alkali boiling temperature is beneficial to the leaching of tungsten, and the optimal alkali boiling temperature is 70 to 100°C.
- the tungsten extraction rates are 80%, 90%, 85% and 60% respectively (the calculation method is the same as in Example 2), indicating that after the tungsten-containing slag is sintered at 300-700°C, the flocculant structure is destroyed and the adsorbed tungsten-containing slag is released. Heteropolyacid, and then extract tungsten through alkali leaching, and the sintering temperature of 900°C is too high, forming complex compounds between some tungsten and metal elements (such as iron, copper, etc.), thus reducing the subsequent tungsten extraction effect by alkali boiling.
- the adsorption of soluble tungsten through the flocculation precipitation generated in the leachate can effectively reduce the tungsten in the leachate; then through sintering and alkali leaching, the tungsten is separated from the precipitation to achieve efficient recovery of tungsten resources.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Disclosed is a method for recovering soluble tungstate in tungsten-containing waste, comprising the specific steps of: leaching the tungsten-containing waste by using an acid solution to obtain a tungsten-containing leachate, adjusting the pH value of the leachate to 2-14 so that a precipitate that adsorbs tungsten is produced in the leachate, filtering to obtain a tungsten-containing slag, calcinating the tungsten-containing slag, and then performing alkali leaching on a sintered material. According to the method, a small amount of tungsten in an acid leachate can be efficiently recovered, thereby improving the efficient resource utilization of complex tungsten-containing waste.
Description
本发明属于金属钨回收技术领域，具体涉及一种回收含钨废料中可溶性钨酸盐的方法。The invention belongs to the technical field of metal tungsten recycling, and specifically relates to a method for recycling soluble tungstate in tungsten-containing waste materials.
钨是一种稀有的战略金属，具有高熔点、高密度、低热膨胀系数等一系列独特的性能，广泛应用于国防、航天、能源、矿山等领域。近年来，由于钨资源开采强度加大，导致钨储量消耗过快，钨资源的可持续发展正面临新的挑战，故大力发展钨及钨合金废料的高效资源化利用具有重大意义。Tungsten is a rare strategic metal with a series of unique properties such as high melting point, high density, and low thermal expansion coefficient. It is widely used in national defense, aerospace, energy, mining and other fields. In recent years, due to the increased intensity of tungsten resource mining, tungsten reserves have been consumed too quickly, and the sustainable development of tungsten resources is facing new challenges. Therefore, it is of great significance to vigorously develop the efficient resource utilization of tungsten and tungsten alloy waste.
随着含钨制品生产技术和应用领域的不断创新，含钨废料也逐渐呈现复杂多样性，其中全球超过50％的钨资源用于制造硬质合金，而废旧硬质合金中的钨含量就已经达到74～91％。目前，分离回收含钨废料中金属的方法有无机酸浸出法、氯化法、锌熔法、氧化还原法等。With the continuous innovation in the production technology and application fields of tungsten-containing products, tungsten-containing scrap has gradually become complex and diverse. More than 50% of the world's tungsten resources are used to make cemented carbide, and the tungsten content in scrap cemented carbide has Reaching 74~91%. At present, the methods for separating and recovering metals in tungsten-containing scrap include inorganic acid leaching, chlorination, zinc fusion, oxidation-reduction, etc.
然而，随着含钨制品生产技术和应用领域的不断创新，含钨废料也逐渐呈现复杂多样性。如在通过选择性酸溶工艺从废旧硬质合金等含钨废料中回收钴的过程中，发现钨会以可溶性杂多酸的形式溶解于酸性浸出液中，从而造成部分钨资源的分散流失，且不利于后续钨、钴的分离，增加处理成本。However, with the continuous innovation in the production technology and application fields of tungsten-containing products, tungsten-containing waste materials have gradually become complex and diverse. For example, in the process of recovering cobalt from tungsten-containing scraps such as scrap cemented carbide through a selective acid dissolution process, it was found that tungsten will be dissolved in the acid leachate in the form of soluble heteropoly acid, resulting in the dispersion and loss of some tungsten resources, and It is not conducive to the subsequent separation of tungsten and cobalt and increases processing costs.
发明内容Contents of the invention
针对上述问题，本发明的目的在于对酸溶含钨废料所得的浸出液中的少量钨进行高效回收，进而提高复杂含钨废料的高效资源化利用，促进钨、钴的分离，获取良好的经济效益和环境效益。In response to the above problems, the purpose of the present invention is to efficiently recover a small amount of tungsten in the leachate obtained from acid-soluble tungsten-containing waste, thereby improving the efficient resource utilization of complex tungsten-containing waste, promoting the separation of tungsten and cobalt, and obtaining good economic benefits. and environmental benefits.
为了实现上述目的，本发明的技术方案具体如下：In order to achieve the above objects, the technical solutions of the present invention are as follows:
一种回收含钨废料中可溶性钨酸盐的方法，包括以下步骤：A method for recycling soluble tungstate in tungsten-containing waste materials, including the following steps:
S1、采用酸液浸取含钨废料得到含钨的浸出液；S1. Use acid solution to leach tungsten-containing waste to obtain tungsten-containing leachate;
S2、调节浸出液的pH值至3～12使浸出液产生沉淀，所述沉淀可以吸附可溶性钨酸盐，过滤得到含钨渣；S2. Adjust the pH value of the leach solution to 3 to 12 to cause the leach solution to precipitate. The precipitate can adsorb soluble tungstate and filter to obtain tungsten-containing slag;
S3、对含钨渣进行煅烧，然后再对烧结料进行碱浸，反应结束得到滤液和滤渣。S3. Calculate the tungsten-containing slag, and then perform alkali leaching on the sintered material. After the reaction is completed, the filtrate and filter residue are obtained.
优选地，步骤S2中调节pH所用的试剂无机碱或有机碱。可以理解的是，调节pH所用的试剂为与钨不发生沉淀的碱性溶剂，包括但不限于NaOH、KOH、Na
2CO
3、NH
3·H
2O等。
Preferably, the reagent used to adjust the pH in step S2 is an inorganic base or an organic base. It can be understood that the reagent used to adjust the pH is an alkaline solvent that does not precipitate with tungsten, including but not limited to NaOH, KOH, Na 2 CO 3 , NH 3 ·H 2 O, etc.
优选地，步骤S3中煅烧的温度为300～900℃，更加优选地，煅烧的温度为300～700℃；可以理解的是，煅烧时间可根据用料的多少进行加碱。Preferably, the calcination temperature in step S3 is 300-900°C, more preferably, the calcination temperature is 300-700°C; it can be understood that the calcination time can be adjusted according to the amount of materials used.
优选地，步骤S3中碱浸的过程具体为：将烧结料加入碱液中，于50～100℃反应；更加优选地，于70～100℃反应。碱浸反应时间可根据实际情况设置。Preferably, the alkali leaching process in step S3 is specifically: adding the sintered material into the alkali solution and reacting at 50-100°C; more preferably, reacting at 70-100°C. The alkali leaching reaction time can be set according to the actual situation.
优选地，所述碱液为与钨不发生沉淀的碱性溶液，包括但不限于NaOH、KOH或二者混合等，所述碱液的浓度为30～180g/L；更加优选地，所述碱液的浓度为60～180g/L。Preferably, the alkali solution is an alkaline solution that does not precipitate with tungsten, including but not limited to NaOH, KOH or a mixture of the two, and the concentration of the alkali solution is 30-180g/L; more preferably, the alkali solution The concentration of alkali solution is 60~180g/L.
本发明的有益效果为：The beneficial effects of the present invention are:
由于含钨废料中除了W和Co外，通常还含有Fe、Ni、Cu、Al等杂质元素且在酸浸过程中会进入浸出液；本发明利用该特点，通过调节pH使上述金属离子沉淀生成对应的Fe(OH)
3、Ni(OH)
2等沉淀，通过该类沉淀的絮凝作用，对浸出液中的钨(以钨酸盐、含钨杂多酸等形式存在)进行捕获吸附，将浸出液中的钨固定于沉淀中。再通过对含钨沉淀的烧结，破坏上述絮凝剂的结构与形貌，使钨脱附，进而通过碱浸回收钨。另外，碱浸所得滤渣可被投加至浸出液中作为絮凝剂，进行循环使用。
In addition to W and Co, tungsten-containing waste usually also contains impurity elements such as Fe, Ni, Cu, and Al, which will enter the leachate during the acid leaching process; the present invention utilizes this feature to precipitate the above metal ions to form corresponding Fe(OH) 3 , Ni(OH) 2, etc. precipitate, through the flocculation of this type of precipitation, the tungsten (existing in the form of tungstate, tungsten-containing heteropolyacid, etc.) in the leachate is captured and adsorbed, and the tungsten in the leachate is of tungsten is fixed in the precipitate. Then, by sintering the tungsten-containing precipitate, the structure and morphology of the above-mentioned flocculant are destroyed, so that the tungsten is desorbed, and then the tungsten is recovered through alkali leaching. In addition, the filter residue obtained from alkali leaching can be added to the leachate as a flocculant for recycling.
本发明的回收方法成本低、回收效果好且绿色环保，为复杂含钨废料的工业化回收利用提供了技术指导。The recycling method of the present invention has low cost, good recycling effect and is green and environmentally friendly, and provides technical guidance for the industrial recycling of complex tungsten-containing waste materials.
为了使本发明的技术方案更加清晰，下面将结合实施方式对本发明作进一步详细描述，但本发明的实施方式不仅仅局限于下述实施例。In order to make the technical solution of the present invention clearer, the present invention will be described in further detail below in conjunction with the embodiments, but the embodiments of the present invention are not limited to the following examples.
本发明提供了一种回收含钨废料中可溶性钨酸盐的方法，其具体步骤为：The invention provides a method for recycling soluble tungstate in tungsten-containing waste materials. The specific steps are:
(1)采用酸液浸取含钨废料得到含钨的浸出液。在本发明的实施例中，该过程具体为：取废旧硬质合金500g置于2L烧杯中，加入1L硫酸、醋酸、硝酸或其混合酸(5M)在搅拌条件下进行酸浸溶钴，经反应12h后过滤获取溶钴液(即浸出液)。由于废旧硬质合金中含有多种金属元素，故本发明所得的浸出液中除了Co、W外，还含有Fe、Ni、Cu、Al等金属元素。(1) Use acid solution to leach tungsten-containing waste to obtain tungsten-containing leachate. In the embodiment of the present invention, the process is specifically as follows: take 500g of scrap cemented carbide and place it in a 2L beaker, add 1L of sulfuric acid, acetic acid, nitric acid or their mixed acid (5M) to perform acid leaching of cobalt under stirring conditions. After reacting for 12 hours, filter to obtain the dissolved cobalt liquid (i.e. leachate). Since scrap cemented carbide contains a variety of metal elements, the leachate obtained by the present invention also contains Fe, Ni, Cu, Al and other metal elements in addition to Co and W.
(2)调节浸出液的pH值至3～12使浸出液中的Fe、Co、Ni等金属离子形成Fe(OH)
3、Co(OH)
2、Ni(OH)
2等沉淀进而吸附钨，待过滤后获得含钨渣。可以理解的是，若是浸出液中不含有Fe、Ni、Al、Cu等元素或其含量极低，可以根据需要，酌量添加对应的金属离子溶液。另外，由于浸出液中Co为大量元素，也可以调节pH以避免Co生成沉淀，当然即使钴沉淀后在烧结碱浸过程中，也成实现钨、钴分离。
(2) Adjust the pH value of the leach solution to 3 to 12 so that metal ions such as Fe, Co, and Ni in the leach solution form Fe(OH) 3 , Co(OH) 2 , Ni(OH) 2 and other precipitates to adsorb tungsten, which will be filtered Finally, tungsten-containing slag is obtained. It can be understood that if the leachate does not contain Fe, Ni, Al, Cu and other elements or the content is extremely low, the corresponding metal ion solution can be added as needed. In addition, since Co is a large element in the leach solution, the pH can also be adjusted to prevent Co from precipitating. Of course, even after cobalt precipitates, tungsten and cobalt can be separated during the sintering alkali leaching process.
(3)对含钨渣进行煅烧，破坏沉淀的结构和形貌，释放钨。然后再对烧结料进行碱浸，反应结束得到滤液和滤渣。(3) Calculate the tungsten-containing slag to destroy the structure and morphology of the precipitation and release tungsten. Then the sintered material is subjected to alkali leaching, and the filtrate and filter residue are obtained after the reaction is completed.
所得滤渣可以重新投加至步骤(1)的浸出液中作为絮凝剂，进行循环使用。而且经试验证明：在相同pH调节范围内，浸出液中W的去除率明显增高，说明浸出液中所含杂质相能很好作为絮凝剂循环使用，实现可溶性钨酸盐的资源化利用。The obtained filter residue can be re-added to the leachate in step (1) as a flocculant for recycling. Moreover, tests have proven that within the same pH adjustment range, the removal rate of W in the leachate is significantly increased, indicating that the impurity phase contained in the leachate can be recycled as a flocculant to realize the resource utilization of soluble tungstate.
实施例1浸出液pH对钨回收率的影响Example 1 Effect of pH of leach solution on tungsten recovery rate
按上述步骤(1)取500mL浸出液，使用KOH溶液调节浸出液的pH分别 至3、6、9、12，搅拌12h后，过滤分离沉淀与浸出液，浸出液中W去除率分别为：85％、87％、95％和96％。Take 500mL of leachate according to the above steps (1), use KOH solution to adjust the pH of the leachate to 3, 6, 9, and 12 respectively. After stirring for 12 hours, filter and separate the precipitate and leachate. The removal rates of W in the leachate are: 85% and 87% respectively. , 95% and 96%.
由此可见，pH的升高有助于可溶性钨酸盐的富集。其原因为：pH变化范围在3～6时，主要形成的是氢氧化铁和氢氧化铜沉淀；pH在6～9时，除生成氢氧化铁和氢氧化铜沉淀外，还生成氢氧化镍沉淀；pH在9～12时，除上述沉淀均生成外，还生成氢氧化钴沉淀。因此随着pH的升高，沉淀产生量越大，吸附的可溶性钨酸盐越多。It can be seen that the increase in pH contributes to the enrichment of soluble tungstate. The reason is: when the pH range is 3 to 6, iron hydroxide and copper hydroxide precipitates are mainly formed; when the pH range is 6 to 9, in addition to iron hydroxide and copper hydroxide precipitates, nickel hydroxide is also formed. Precipitation; when the pH is between 9 and 12, in addition to the above-mentioned precipitates, cobalt hydroxide precipitates are also formed. Therefore, as the pH increases, the amount of precipitation increases, and more soluble tungstate is adsorbed.
实施例2碱浸工艺中碱用量对钨回收率的影响Example 2 Effect of alkali dosage on tungsten recovery rate in alkali leaching process
取500mL浸出液，使用KOH溶液调节浸出液的pH至12，搅拌12h后过滤得到含钨渣，并将其于500℃烧结2h。考察了碱浸工艺中NaOH浓度分为30、60、90、120、150和180g/L时，于80℃反应2h时对钨回收率的影响。Take 500 mL of leach solution, use KOH solution to adjust the pH of the leach solution to 12, stir for 12 hours, filter to obtain tungsten-containing slag, and sinter it at 500°C for 2 hours. The effect on the tungsten recovery rate when the NaOH concentration in the alkali leaching process was divided into 30, 60, 90, 120, 150 and 180g/L at 80°C for 2 hours was investigated.
提钨效果分别为50％、82％、88％、98％、98.2％和98.5％(浸出液中原始钴含量与碱浸所得滤渣中的含钨量之差/浸出液中原始钴含量，默认吸附时已将浸出液中的钨全部絮凝下来)。说明随着碱含量的升高，对絮凝剂提钨效果逐渐增强，当碱度升至120g/L后提钨效果变化不大。The tungsten extraction effects are 50%, 82%, 88%, 98%, 98.2% and 98.5% respectively (the difference between the original cobalt content in the leachate and the tungsten content in the filter residue obtained from alkali leaching/the original cobalt content in the leachate, when adsorbed by default All the tungsten in the leachate has been flocculated). It shows that as the alkali content increases, the tungsten extraction effect of the flocculant gradually increases. When the alkalinity rises to 120g/L, the tungsten extraction effect changes little.
实施例3碱浸时间对钨回收率的影响Example 3 Effect of alkali leaching time on tungsten recovery rate
取500mL浸出液，使用KOH溶液调节浸出液的pH至12，搅拌12h后过滤得到含钨渣，并将其于500℃烧结2h。对烧结料在120g/L的NaOH溶液中于80℃进行碱浸，碱浸时间分别为1、2、3、4、5h。提钨率分别为60％、82％、92％、98.6％和98.8％(计算方式同实施例2)，说明延长碱煮时间有利于钨的浸出。Take 500 mL of leach solution, use KOH solution to adjust the pH of the leach solution to 12, stir for 12 hours, filter to obtain tungsten-containing slag, and sinter it at 500°C for 2 hours. The sintered materials were alkaline leached in 120g/L NaOH solution at 80°C. The alkali leaching times were 1, 2, 3, 4, and 5 hours respectively. The tungsten extraction rates were 60%, 82%, 92%, 98.6% and 98.8% respectively (the calculation method is the same as Example 2), indicating that extending the alkali boiling time is beneficial to the leaching of tungsten.
实施例4碱浸温度对钨回收率的影响Example 4 Effect of alkali leaching temperature on tungsten recovery rate
取500mL浸出液，使用KOH溶液调节浸出液的pH至12，搅拌12h后过滤得到含钨渣，并将其于500℃烧结2h。对烧结料在120g/L的NaOH溶液中分别于50、60、70、80、90和100℃碱浸4h。Take 500 mL of leach solution, use KOH solution to adjust the pH of the leach solution to 12, stir for 12 hours, filter to obtain tungsten-containing slag, and sinter it at 500°C for 2 hours. The sintered materials were alkaline immersed in 120g/L NaOH solution at 50, 60, 70, 80, 90 and 100°C for 4 hours respectively.
提钨率分别为：55％、64％、80％、98.6、99％和99.1％(计算方式同实施例2)。说明提高碱煮温度有利于钨的浸出，其中较优的碱煮温度为70～100℃。The tungsten extraction rates are respectively: 55%, 64%, 80%, 98.6, 99% and 99.1% (the calculation method is the same as in Example 2). It shows that increasing the alkali boiling temperature is beneficial to the leaching of tungsten, and the optimal alkali boiling temperature is 70 to 100°C.
实施例5煅烧温度对钨回收率的影响Example 5 Effect of calcination temperature on tungsten recovery rate
取500mL浸出液，使用KOH溶液调节浸出液的pH至3～6，搅拌12h后过滤得到含钨渣，并将其分别于300、500、700、900℃烧结2h，再对烧结料在同一条件下碱浸得滤渣和滤液。Take 500 mL of leach solution, use KOH solution to adjust the pH of the leach solution to 3 to 6, stir for 12 hours, filter to obtain tungsten-containing slag, and sinter it at 300, 500, 700, and 900°C for 2 hours respectively, and then alkali sinter the sintered material under the same conditions. Leaching the filter residue and filtrate.
提钨率分别为80％、90％、85％和60％(计算方式同实施例2)，说明含钨渣经300～700℃烧结后，絮凝剂结构发生了破坏，释放了吸附的含钨杂多酸，进而通过碱浸提钨，而900℃烧结温度过高，形成了部分钨与金属元素(如铁、铜等)复杂的化合物，从而降低了后续碱煮提钨效果。The tungsten extraction rates are 80%, 90%, 85% and 60% respectively (the calculation method is the same as in Example 2), indicating that after the tungsten-containing slag is sintered at 300-700°C, the flocculant structure is destroyed and the adsorbed tungsten-containing slag is released. Heteropolyacid, and then extract tungsten through alkali leaching, and the sintering temperature of 900°C is too high, forming complex compounds between some tungsten and metal elements (such as iron, copper, etc.), thus reducing the subsequent tungsten extraction effect by alkali boiling.
实施例6煅烧时间对钨回收率的影响Example 6 Effect of calcination time on tungsten recovery rate
取500mL浸出液，使用KOH溶液调节浸出液的pH至3～6，搅拌12h后过滤得到含钨渣，并将其于500℃分别烧结1、2、3、4和5h，再对烧结料在同一条件下碱浸得滤渣和滤液。提钨率分别为45、90、90.2、90.4和85％。Take 500 mL of leach solution, use KOH solution to adjust the pH of the leach solution to 3-6, stir for 12 hours, filter to obtain tungsten-containing slag, and sinter it at 500°C for 1, 2, 3, 4 and 5 hours respectively, and then sinter the sintered material under the same conditions. The filter residue and filtrate are obtained by leaching with alkali. The tungsten extraction rates are 45, 90, 90.2, 90.4 and 85% respectively.
综上所述，通过浸出液中产生的絮凝沉淀吸附可溶性钨，能有效降低浸出液中的钨；再通过烧结和碱浸，将钨从沉淀中分离，实现钨资源的高效回收。In summary, the adsorption of soluble tungsten through the flocculation precipitation generated in the leachate can effectively reduce the tungsten in the leachate; then through sintering and alkali leaching, the tungsten is separated from the precipitation to achieve efficient recovery of tungsten resources.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。The above are only preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person familiar with the technical field can easily think of changes or modifications within the technical scope disclosed in the present invention. All substitutions are within the scope of the present invention.
Claims (7)
- 一种回收含钨废料中可溶性钨酸盐的方法，其特征在于，包括以下步骤：A method for recovering soluble tungstate in tungsten-containing waste materials, which is characterized by including the following steps:S1、采用酸液浸取含钨废料得到含钨的浸出液；S1. Use acid solution to leach tungsten-containing waste to obtain tungsten-containing leachate;S2、调节浸出液的pH值至2～14使浸出液产生吸附钨的沉淀，过滤得到含钨渣，调节pH所用的试剂为与钨不发生沉淀的碱性溶剂；S2. Adjust the pH value of the leach solution to 2 to 14 to cause the leach solution to precipitate that adsorbs tungsten, and filter to obtain tungsten-containing slag. The reagent used to adjust the pH is an alkaline solvent that does not precipitate with tungsten;S3、对含钨渣进行煅烧，然后再对烧结料进行碱浸，反应结束得到滤渣和含钨滤液。S3. Calculate the tungsten-containing slag, and then perform alkali leaching on the sintered material. After the reaction is completed, the filter residue and the tungsten-containing filtrate are obtained.
- 根据权利要求1所述回收含钨废料中可溶性钨酸盐的方法，其特征在于，所述煅烧的温度为300～900℃。The method for recovering soluble tungstate in tungsten-containing waste according to claim 1, characterized in that the calcination temperature is 300 to 900°C.
- 根据权利要求2所述回收含钨废料中可溶性钨酸盐的方法，其特征在于，所述煅烧的温度为300～700℃。The method for recovering soluble tungstate in tungsten-containing waste according to claim 2, characterized in that the calcination temperature is 300 to 700°C.
- 根据权利要求1所述回收含钨废料中可溶性钨酸盐的方法，其特征在于，所述碱浸的过程为：将烧结料加入碱液中，于50～100℃下反应。The method for recovering soluble tungstate in tungsten-containing waste according to claim 1, characterized in that the alkali leaching process is: adding the sintered material into the alkali solution and reacting at 50 to 100°C.
- 根据权利要求4所述回收含钨废料中可溶性钨酸盐的方法，其特征在于，所述碱浸的过程为：将烧结料加入碱液中，于70～100℃下反应。The method for recovering soluble tungstate in tungsten-containing waste according to claim 4, characterized in that the alkali leaching process is: adding the sintered material into the alkali solution and reacting at 70 to 100°C.
- 根据权利要求4所述回收含钨废料中可溶性钨酸盐的方法，其特征在于，所述碱液为与钨不发生沉淀的碱性溶液，所述碱液的浓度为30～180g/L。The method for recovering soluble tungstate in tungsten-containing waste according to claim 4, wherein the alkali solution is an alkaline solution that does not precipitate with tungsten, and the concentration of the alkali solution is 30 to 180 g/L.
- 根据权利要求6所述回收含钨废料中可溶性钨酸盐的方法，其特征在于，所述碱液的浓度为60～180g/L。The method for recovering soluble tungstate in tungsten-containing waste according to claim 6, characterized in that the concentration of the alkali solution is 60-180g/L.
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