PT101680B - PROCESS OF CONTROLLED LEACHING OF NATURAL MANGAN DIOXIDE THROUGH THE USE OF CHLORIDYRIC ACID - Google Patents
PROCESS OF CONTROLLED LEACHING OF NATURAL MANGAN DIOXIDE THROUGH THE USE OF CHLORIDYRIC ACID Download PDFInfo
- Publication number
- PT101680B PT101680B PT101680A PT10168095A PT101680B PT 101680 B PT101680 B PT 101680B PT 101680 A PT101680 A PT 101680A PT 10168095 A PT10168095 A PT 10168095A PT 101680 B PT101680 B PT 101680B
- Authority
- PT
- Portugal
- Prior art keywords
- leaching
- natural
- values
- chloridyric
- acid
- Prior art date
Links
- 238000002386 leaching Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title description 5
- 239000002253 acid Substances 0.000 title 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 230000000694 effects Effects 0.000 claims description 4
- 230000003993 interaction Effects 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 230000007928 solubilization Effects 0.000 description 4
- 238000005063 solubilization Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000032580 NMDA receptor encephalitis Diseases 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 manganese salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C22B47/00—Obtaining manganese
- C22B47/0018—Treating ocean floor nodules
- C22B47/0045—Treating ocean floor nodules by wet processes
- C22B47/0054—Treating ocean floor nodules by wet processes leaching processes
- C22B47/0063—Treating ocean floor nodules by wet processes leaching processes with acids or salt solutions
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ocean & Marine Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oceanography (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Paper (AREA)
Description
O presente invento diz respeito a um processo de extracção e recuperação de materiais deletérios do dióxido de manganês natural (NMD) sob a acção de uma sequência de equipamentos que controlam condições físicoquímicas previamente definidas.The present invention relates to a process of extraction and recovery of harmful materials of natural manganese dioxide (NMD) under the action of a sequence of equipment that control previously defined physicochemical conditions.
O estado da técnica indica a possibilidade de se preparar um dióxido de manganês sintético. O dióxido de manganês electrolítico (EMD) é obtido a partir da electrólise de uma solução de MnSO4, tendo como matériaprima o MnO2 ou o MnCO3. O dióxido de manganês químico (CMD) também é obtido por precipitação de MnO2 numa solução de manganês (oxidação de sais de manganês bivalentes). No entanto, na indústria não é conhecida a utilização do processo de lixiviação do MnO2 em que é mantida a estrutura do dióxido natural e são eliminados os metais pesados do NMD.The state of the art indicates the possibility of preparing a synthetic manganese dioxide. Electrolytic manganese dioxide (EMD) is obtained from the electrolysis of a MnSO 4 solution, using either MnO 2 or MnCO 3 as raw material. Chemical manganese dioxide (CMD) is also obtained by precipitation of MnO 2 in a manganese solution (oxidation of divalent manganese salts). However, in the industry it is not known to use the MnO 2 leaching process in which the structure of the natural dioxide is maintained and the heavy metals of the NMD are eliminated.
A composição do minério de manganês varia de região para região nos continentes e no fundo dos mares. Por esse motivo, para além dos tratamentos já existentes, certos países estão preocupados com os nódulos marítimos e têm vindo a desenvolver técnicas para a recuperação dos metais presentes nas matrizes de manganês (Ni, Co, Mn, entre outros), tratamentos eThe composition of manganese ore varies from region to region on the continents and the bottom of the seas. For this reason, in addition to existing treatments, certain countries are concerned with maritime nodules and have been developing techniques for the recovery of metals present in manganese matrices (Ni, Co, Mn, among others), treatments and
-2técnicas que ainda permanecem insuficientes no caso de importantes jazidas de minério.-2 techniques that still remain insufficient in the case of important ore deposits.
O objectivo do presente processo consiste em realizar o tratamento do dióxido de manganês natural (NMD) de uma maneira conveniente ainda não contemplada pelo estado da técnica.The aim of the present process is to carry out the treatment of natural manganese dioxide (NMD) in a convenient manner not yet contemplated by the state of the art.
No início foram feitos ensaios exploratórios de lixiviação do NMD através da utilização de ácido clorídrico, tendo como objectivo principal a eventual ocorrência de solubilização preferencial de materiais deletérios (Cu, Ni, Fe, Co, Mn, entre outros) em relação à matriz de MnO2. Quando se procedeu à realização desses ensaios foram tidas em consideração variáveis tais como a temperatura, a concentração de HC1, o tempo de reacção e a reutilização do licor clorídrico filtrado. Todos estes parâmetros mostraram ser importantes.At the beginning, exploratory NMD leaching tests were carried out using hydrochloric acid, with the main objective of the eventual occurrence of preferential solubilization of harmful materials (Cu, Ni, Fe, Co, Mn, among others) in relation to the MnO matrix 2 . When carrying out these tests, variables such as temperature, HCl concentration, reaction time and the reuse of the filtered hydrochloric liquor were taken into account. All of these parameters proved to be important.
A solubilização dos diversos componentes presentes na matriz de manganês foi considerada de grande importância porque a concentração de um mineral através do processo de lixiviação é realizada com a solubilização das impurezas.The solubilization of the various components present in the manganese matrix was considered of great importance because the concentration of a mineral through the leaching process is carried out with the solubilization of the impurities.
Depois de terem sido definidos os resultados estatísticos, foram então programados ensaios de optimização entre os quais se encontravam incluídos o de densidade da polpa devido à importância que esta variável tem nas instalações industriais. Nesta fase de optimização foi determinado qual o efeito que quatro variáveis independentes (concentração de HC1, temperatura, tempo de lixiviação e densidade da polpa), que variam ao mesmo tempo, exercem sobre as variáveis dependentes (regeneração do MnO2 e teores de Cu e Ni no concentrado).After the statistical results had been defined, optimization tests were then programmed, among which the pulp density was included due to the importance that this variable has in industrial installations. In this optimization phase, it was determined the effect that four independent variables (HCl concentration, temperature, leaching time and pulp density), which vary at the same time, exert on the dependent variables (MnO 2 regeneration and Cu and Ni in the concentrate).
Nesta avaliação final, em relação ao teor de Cu e Ni e à regeneração do MnO2, foram confirmados os efeitos das diversas variáveis independentes e das respectivas interacções. Principalmente foi demonstrada a importância da concentração de HC1 e da temperatura em comparação com as outras variáveis.In this final evaluation, in relation to the Cu and Ni content and the MnO 2 regeneration, the effects of the various independent variables and the respective interactions were confirmed. Mainly it was demonstrated the importance of the concentration of HCl and the temperature in comparison with the other variables.
Ensaios optimizados apresentaram os seguintes valores condicionais:Optimized tests presented the following conditional values:
- Concentração de HC1 = 9 a 25% em peso, dependendo dos valores esperados para a extracção de materiais deletérios e para a regeneração do MnO2.- HCl concentration = 9 to 25% by weight, depending on the expected values for the extraction of harmful materials and for the regeneration of MnO 2 .
- Tempo de lixiviação = 10 a 60 minutos, dependendo dos valores esperados para a extracção de materiais deletérios e para a regeneração do MnO2.- Leaching time = 10 to 60 minutes, depending on the expected values for the extraction of harmful materials and for the regeneration of MnO 2 .
- Temperatura = 80 a 95°C, em que o limite de 95°C é devido ao facto de ser bastante difícil utilizar o HC1 acima dessa temperatura devido à sua tensão de vapor e poder oxidante.- Temperature = 80 to 95 ° C, where the limit of 95 ° C is due to the fact that it is very difficult to use HCl above that temperature due to its vapor tension and oxidizing power.
- Densidade da polpa = 9 a 25% em peso, dependendo da concentração de HC1 utilizada na realização do processo.- Pulp density = 9 to 25% by weight, depending on the concentration of HCl used in the process.
-4Na tabela seguinte são apresentados alguns valores optimizados escolhidos de entre os referidos valores condicionais:-4In the following table are presented some optimized values chosen from those conditional values:
Na Figura 1 da folha 1 dos desenho anexo encontra-se representado o fluxograma do equipamento básico concebido para a extracção de materiais deletérios do dióxido de manganês natural (NMD). As suas partes estão enumeradas do seguinte modo:Figure 1 of sheet 1 of the attached drawings shows the flowchart of the basic equipment designed for the extraction of harmful materials from natural manganese dioxide (NMD). Its parts are listed as follows:
1. correia transportadora1. conveyor belt
2. silo de alimentação doseada de NMD2. NMD metered feed silo
3. reservatório de água e de ácido clorídrico3. water and hydrochloric acid reservoir
4. tubagem equipada com alimentador-doseador4. piping equipped with dosing feeder
5. correia transportadora5. conveyor belt
6. tanque de lixiviação6. leach tank
7. motor7. engine
8. misturador8. mixer
9. aquecedor9. heater
10. moto-bomba10. moto-bomb
11. conduta (tubagem ou elevador de baldes)11. pipeline (tubing or bucket elevator)
12. filtro12. filter
13. tubagem13. piping
14. canalete14. channel
15. motor15. engine
16. secador de tambor16. drum dryer
17. transportador17. conveyor
De acordo com o fluxograma, a extracção de materiais deletérios do dióxido de manganês natural (NMD) é realizada através das seguintes etapas básicas:According to the flow chart, the extraction of harmful materials from natural manganese dioxide (NMD) is carried out through the following basic steps:
Parte da solução aquosa de ácido clorídrico que se acha contida no interior do reservatório (3) é despejada para dentro do tanque (6) através da tubagem (4) equipada com alimentador-doseador. O aquecedor é posto a funcionar e, quando a temperatura atinge um valor pré-estabelecido, uma determinada quantidade de dióxido de manganês natural (NMD) triturado que se acha depositado no silo alimentador-doseador (2) vai ser despejada para dentro do tanque (6) por meio da correia (5). Depois da densidade da polpa ter sido desta maneira levada a atingir o valor desejado, o motor (7) é posto em funcionamento, o que irá fazer com que o misturador (8) vá ser posto em movimento durante o período de tempo definido como necessário para se concluir a operação de lixiviação. É então que a moto-bomba (10) é posta a trabalhar, indo desse modo conduzir o produto lixiviado para o filtro (12) através da conduta (11). Depois da polpa ter sido toda filtrada, a massa aglomerada vai cair no canalete (14), indo a seguir passar através do secador de tambor (16) que é accionado pelo motor (15); o licor clorídrico resultante da filtragem vai regressar novamente ao tanque (6) através da tubagem (13). A partir desse momento dá-se início a um novo ciclo semelhante ao que se acaba de descrever.Part of the aqueous hydrochloric acid solution that is contained inside the reservoir (3) is poured into the tank (6) through the pipe (4) equipped with a dosing feeder. The heater is started and, when the temperature reaches a pre-established value, a certain amount of crushed natural manganese dioxide (NMD) that is deposited in the feeder-dosing silo (2) will be poured into the tank ( 6) through the belt (5). After the pulp density has been brought to the desired value in this way, the motor (7) is started, which will cause the mixer (8) to be started for the period of time defined as necessary to complete the leaching operation. It is then that the motor-pump (10) is set to work, thereby driving the leachate product into the filter (12) through the duct (11). After the pulp has been completely filtered, the agglomerated mass will fall into the channel (14), and then pass through the drum dryer (16), which is driven by the motor (15); the hydrochloric liquor resulting from the filtration will return to the tank (6) again through the pipe (13). From that moment, a new cycle similar to the one just described begins.
-6A reutilização sucessiva do licor clorídrico, além de fazer aumentar centração de metais pesados - que é fundamental para a sua ulterior ção por meio de processos químicos e (ou) electroquímicos - resulta num ito da selectividade da solubilização dos referidos metais em relação ao . No entanto, sempre que tem lugar um novo ciclo, deve proceder-se à > suplementar da solução de HC1 + H2O contida no interior do reservatório fim de fazer com que a concentração do agente de lixiviação se mantenha m valor constante.-6The successive reuse of hydrochloric liquor, in addition to increasing the concentration of heavy metals - which is essential for its further use by means of chemical and (or) electrochemical processes - results in a success in the selectivity of the solubilization of said metals in relation to. However, whenever a new cycle takes place, the> HCl + H 2 O solution contained inside the tank must be supplemented in order to keep the concentration of the leaching agent constant.
A operação de purificação do dióxido de manganês natural (NMD) lescrita apresenta as seguintes vantagens em relação ao referido minério o:The purified operation of the natural manganese dioxide (NMD) mentioned above has the following advantages in relation to said ore o:
- A extracção dos metais pesados faz com que seja possível utilizar D no fabrico de pilhas electroquímicas sem mercúrio - que é a tendência al actualmente em vigor devido aos problemas ambientais.- The extraction of heavy metals makes it possible to use D in the manufacture of electrochemical batteries without mercury - which is the trend currently in force due to environmental problems.
- O aumento do teor de MnO2 faz aumentar a durabilidade das electroquímicas.- The increase in MnO 2 content increases the durability of electrochemicals.
- Existe uma forte procura industrial e comercial para os outros tos extraídos nas etapas de purificação. Por conseguinte, a partir do MnCO3 ibter-se o MnCl3, além de aditivos para combustíveis. O Ni, o Cu e o Co etais de elevado valor devido ao facto de serem utilizados em indústrias alizadas.- There is a strong industrial and commercial demand for the other items extracted in the purification stages. Therefore, from MnCO 3 ibter if it MnCl 3, and fuel additives. High value Ni, Cu and Co etals due to the fact that they are used in specialized industries.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BR9401472A BR9401472A (en) | 1994-04-07 | 1994-04-07 | Controlled leaching process for natural manganese dioxide using hydrochloric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PT101680A PT101680A (en) | 1995-11-30 |
| PT101680B true PT101680B (en) | 1997-04-30 |
Family
ID=4058746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PT101680A PT101680B (en) | 1994-04-07 | 1995-03-29 | PROCESS OF CONTROLLED LEACHING OF NATURAL MANGAN DIOXIDE THROUGH THE USE OF CHLORIDYRIC ACID |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPH07277737A (en) |
| AU (1) | AU685174B2 (en) |
| BE (1) | BE1008675A3 (en) |
| BR (1) | BR9401472A (en) |
| CA (1) | CA2144925C (en) |
| ES (1) | ES2103233B1 (en) |
| FR (1) | FR2718429B1 (en) |
| NL (1) | NL1000073C1 (en) |
| OA (1) | OA10219A (en) |
| PT (1) | PT101680B (en) |
| ZA (1) | ZA95664B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2607873C1 (en) * | 2015-09-28 | 2017-01-20 | федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский горный университет" | Method of processing of ferromanganese concretions |
| CN113387391B (en) * | 2021-07-30 | 2022-05-24 | 广西埃索凯新材料科技有限公司 | Manganese sulfate production system based on manganese oxide ore |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2240586A1 (en) * | 1972-08-18 | 1974-02-28 | Krupp Gmbh | Leaching sea bed manganese nodules with hydrochloric acid - to recover copper, nickel, cobalt, manganese and iron |
| US4002717A (en) * | 1975-01-09 | 1977-01-11 | Deepsea Ventures, Inc. | Refining of manganese oxide ores |
| CA1061568A (en) * | 1975-01-17 | 1979-09-04 | Antoine Van Peteghem | Process for extracting metal values from manganiferous ocean floor nodule ore |
| DE2623837A1 (en) * | 1976-03-30 | 1977-10-13 | Eleusis Bauxite Mines Inc | METHOD FOR PRODUCING ACTIVE MANGANE DIOXIDE |
| US4150091A (en) * | 1977-11-21 | 1979-04-17 | Sun Ocean Ventures, Inc. | Manganese ore leaching process |
| DE4329086A1 (en) * | 1993-08-30 | 1995-03-02 | Gewerk Keramchemie | Process for the hydrometallurgical reprocessing of used batteries for recovering the raw materials |
-
1994
- 1994-04-07 BR BR9401472A patent/BR9401472A/en not_active IP Right Cessation
- 1994-12-01 AU AU79140/94A patent/AU685174B2/en not_active Expired
-
1995
- 1995-01-09 OA OA60601A patent/OA10219A/en unknown
- 1995-01-27 ZA ZA95664A patent/ZA95664B/en unknown
- 1995-02-07 JP JP7019003A patent/JPH07277737A/en active Pending
- 1995-02-15 ES ES09500301A patent/ES2103233B1/en not_active Expired - Fee Related
- 1995-03-17 CA CA002144925A patent/CA2144925C/en not_active Expired - Fee Related
- 1995-03-29 PT PT101680A patent/PT101680B/en not_active IP Right Cessation
- 1995-04-04 BE BE9500307A patent/BE1008675A3/en active
- 1995-04-06 NL NL1000073A patent/NL1000073C1/en not_active IP Right Cessation
- 1995-04-07 FR FR9504185A patent/FR2718429B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| ES2103233A1 (en) | 1997-09-01 |
| AU7914094A (en) | 1995-10-19 |
| BR9401472A (en) | 1995-11-07 |
| ZA95664B (en) | 1995-09-28 |
| OA10219A (en) | 1997-09-19 |
| BE1008675A3 (en) | 1996-07-02 |
| PT101680A (en) | 1995-11-30 |
| NL1000073C1 (en) | 1995-10-09 |
| CA2144925C (en) | 2006-09-19 |
| AU685174B2 (en) | 1998-01-15 |
| JPH07277737A (en) | 1995-10-24 |
| FR2718429A1 (en) | 1995-10-13 |
| FR2718429B1 (en) | 1997-01-24 |
| CA2144925A1 (en) | 1995-10-08 |
| ES2103233B1 (en) | 1998-07-01 |
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