WO2010125205A1 - Method for producing ferrous sulphate from pyrite ash - Google Patents

Method for producing ferrous sulphate from pyrite ash Download PDF

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Publication number
WO2010125205A1
WO2010125205A1 PCT/ES2009/070120 ES2009070120W WO2010125205A1 WO 2010125205 A1 WO2010125205 A1 WO 2010125205A1 ES 2009070120 W ES2009070120 W ES 2009070120W WO 2010125205 A1 WO2010125205 A1 WO 2010125205A1
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Prior art keywords
ferrous sulfate
pyrite
ashes
iron
stage
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PCT/ES2009/070120
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Spanish (es)
French (fr)
Inventor
Stephen Michael Jones
Antonio Daigo San Andres
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Tioxide Europe, S.L.
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Priority to PCT/ES2009/070120 priority Critical patent/WO2010125205A1/en
Publication of WO2010125205A1 publication Critical patent/WO2010125205A1/en

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    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/14—Sulfates
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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 object of the present invention relates to the production of ferrous sulfate having as raw material the ashes obtained in the production of sulfuric acid by roasting pyrites.
  • a solution of ferrous sulfate in acidic aqueous medium is first obtained.
  • the dissolution of iron sulfates is reduced to pass all the ions to the ferrous form, using iron scrap.
  • the solid products obtained, heptahydrate or monohydrate have applications in the field of agriculture, contribution of iron to crops; in cement, as a Cr6 + reducer; in water treatment, as primary flocculant; in iron oxide pigment manufacturing or in animal feed, among others.
  • the most widely used ferrous salt is SO 4 Fe • 7H 2 O sulfate, which is commercially known as green or coated vitriol. It is obtained in the form of monoclinic crystals, green in color, by evaporation of an iron solution in dilute sulfuric acid and in Depending on the evaporation conditions, pressure, temperature, ion concentrations, etc., the heptahydrate form or the monohydrate form SO 4 Fe • H 2 O can be precipitated, more difficult to achieve but with an iron content noticeably older
  • the source of the acid solution of ferrous sulfate is the metallurgical industry, in the pickling of ferrous metals by means of sulfuric acid and the titanium dioxide industry, where ilmenite is attacked with sulfuric acid producing a solution of iron sulfates and titanium, from which ferrous sulfate is separated by vacuum crystallization.
  • the Sierra de Huelva (Spain) is historically known as an area rich in metal sulphides and the development of the area has been based on the extraction and use of this mineral to recover the components of these sulphides.
  • the method object of the invention consists in attacking the ashes of pyrite (ferric oxide) with sulfuric acid, to produce an iron sulfate liquor, which once reduced serves as raw material for the manufacture of ferrous sulfate in two forms of hydrate. tion, heptahydrate and monohydrate.
  • the process begins by recovering the pyrite ashes from the old tanks and transporting the mineral to the treatment plant where, first, the ore is dried and ground by ball mills until a smaller particle size is achieved. to 45 microns.
  • the sulfuric acid used can be fresh, with a concentration of 98.5%, or recycled from other stages of the process or from other processes that generate sulfuric acid as a coproduct.
  • the concentration can range from 10% to 98.5%.
  • Different parameters such as times, reagent temperatures, liquid addition sequences, stirring and mixing periods are controlled in order to achieve the highest possible reaction efficiency, around 95%.
  • the reaction product, pasty liquid is dissolved in weak acids or in clean water, obtaining the digestion liquor.
  • the weight ratio of acid / mineral weight can be between 1 and 5 and the reaction temperature is maintained between 5O 0 C and 15O 0 C by means of steam supplying the reaction mass.
  • the digestion liquor is formed by the sulfuric acid that was put in excess to achieve the highest attack efficiency and the soluble sulfates of the metals present in the pyrite ash, mainly ferric sulfate, which must be reduced to obtain the ferrous sulfate.
  • the reduction is carried out using iron scrap, by passing the digestion liquor through the scrap we managed to transform the ferric ion into ferrous while increasing the concentration of iron in the solution called reduced liquor.
  • the reduction of the content of ferric ions is made up to values below 10 grams per liter.
  • the next stage aims to purify that reduced liquor by eliminating the solids present in the solution and which are a consequence of the fact that the efficiency of the attack phase is not 100%.
  • the solids are removed by passing the solution through decanters, where a flocculant is added that agglomerates insoluble particles that are separated from the liquid phase, allowing to obtain a liquor free of insoluble materials.
  • the decanters purges pass through rotary filters in which the solids are destined for other applications outside this process and the liquid obtained is joined with the clean liquor.
  • the clean liquor is pumped into vacuum crystallizers, where by means of steam ejectors a strong vacuum is produced that allows the boiling of the liquor and the consequent evaporation of part of the water of the solution, considerably reducing the temperature and reaching the solubility product of ferrous sulfate heptahydrate according to the phase diagram of the solutions of ferrous sulfate in acidic medium.
  • the temperature of the input solution of sulfates in aqueous acidic medium to crystallization may be between 30 and 70 0 C and the output from 40 to 10 0 C.
  • the crystalline suspension formed here can be sent to a second crystallizer, connected to a heat exchanger that allows its cooling by means of a refrigerating group, and which facilitates the formation of ferrous sulfate heptahydrate crystals.
  • the output current of this second crystallizer is sent to a thickener where, due to gravity, a purge rich in crystals is achieved at the bottom of the thickener, while a clean liquid of solids overflows from the top.
  • the purge of this thickener is fed to centrifuges that separate the crystals from the liquid phase by sieves. This liquid phase joins with the thickener overflow and is part of the diluted acids used in the attack or dissolution phase of pyrite ashes.
  • the process consists in bringing the purified liquor in the decanters to special tanks, with an anti-acid coating and a very slow stirring, where a quantity is added on the liquor determined from concentrated sulfuric acid, in proportions that vary between 1 part of acid and 4 parts of liquor and 3 parts of acid and 4 parts of liquor, and hot precipitation of ferrous sulfate monohydrate occurs.
  • a quantity is added on the liquor determined from concentrated sulfuric acid, in proportions that vary between 1 part of acid and 4 parts of liquor and 3 parts of acid and 4 parts of liquor, and hot precipitation of ferrous sulfate monohydrate occurs.
  • With slow agitation maturation and growth of the monohydrate crystals that separate into spark plug filters occur, in which the solid separated in the filters is dried by means of an air stream inside the filters themselves. spark plugs, obtaining acid filtrates that are used in the attack phase of the mineral and a solid formed mostly by ferrous sulfate monohydrate.
  • ferrous sulfate monohydrate which consists in eliminating the stage of purification of the reduced liquor, so that the process would be to feed the reduced tanks with reduced liquor, where the corresponding amount of Sulfuric acid to produce the precipitation of ferrous sulfate monohydrate and after the growth and maturation of the crystals, the spark plug filters would be fed, separating the liquid phase that would return to the attack of the mineral and the solid phase that would be the ferrous sulfate monohydrate.
  • This monohydrate can be marketed directly or the free acidity that accompanies it can be neutralized, with limestones, dolomites or any other material that reacts with sulfuric acid and that gives us reaction products that either bring some benefit to the product final or contribute inert. Once the product has been neutralized, it can be granulated, palletized or compacted in order to obtain an easier and more stable handling product.
  • the acid will be added in specially coated and thermally insulated tanks, with constant and slow stirring, to favor the formation and growth of ferrous sulfate monohydrate crystals.
  • the product obtained by the above methods and which in its composition contains an amount of iron, in ferrous form, between 15% and 32% of the total weight of the product finally obtained is also object of the present invention.
  • a flocculant is added to the reduced liquor to agglutinate the micro particles of the undigested digestion residues, which are separated by decantation or filtration, leaving us a clear and clean liquor that will enter the crystallization stage.
  • reaction mass After 16 minutes mixture is heated and the reaction is initiated and maintained at 9O 0 C for 180 minutes, after which it stops heating and added 1900 ml of water to dissolve the reaction mass.
  • This digestion liquor is reacted with 91 g of iron scrap, obtaining 3000 ml of reduced liquor, which contains 111 g / 1 of total iron, without the presence of ferric iron.
  • This digestion liquor is reacted with 123 g of iron scrap, obtaining 3100 ml of reduced liquor, which contains 129 g / 1 of total iron, with 3 g / 1 of ferric iron.
  • Water treatment Directly as primary flocculant for wastewater or after its transformation into ferric sulfate for treatment and purification of drinking and wastewater.
  • Manufacturing of pigments As raw material for the manufacture of pigment based on iron oxides, for printer toner.
  • Animal feed As raw material for obtaining products based on iron sulfate suitable for manufacturing compound feed for animal feed
  • Animal feed As a raw material for obtaining products based on iron sulfate from high purity, suitable for manufacturing compound feed for animal feed
  • Granulate is used for:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
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  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The subject matter of the present invention relates to the production of a solution of ferrous sulphate, in aqueous acid medium the raw material being the ash obtained in the production of sulphuric acid by means of roasting of pyrites. The iron sulphate solution is reduced to convert all the ions to the ferrous form, using scrap iron. The ferrous sulphate solution provides solid heptahydrate by vacuum crystallization or likewise solid monohydrate, by addition of concentrated sulphuric acid. The resulting solid products (heptahydrate or monohydrate) can be used in the field of agriculture, as a source of iron for crops, in cement, as a Cr6+ reducer, in water treatment, as primary flocculant, in the production of iron oxide pigment, in animal nutrition, etc.

Description

MÉTODO DE FABRICACIÓN DE SULFATO FERROSO A PARTIR DE METHOD OF MANUFACTURE OF FERROUS SULPHATE FROM
CENIZAS DE PIRITAPIRITA ASHES
DESCRIPCIÓN OBJETO DE LA INVENCIÓNDESCRIPTION OBJECT OF THE INVENTION
El objeto de la presente invención se refiere a la obtención de sulfato ferroso teniendo como materia prima las cenizas obtenidas en la producción de ácido sulfúrico por tostación de piritas. Se obtiene primeramente una disolución de sulfato ferroso en medio acuoso ácido. La disolución de sulfatos de hierro se reduce para pasar todos los iones a la forma ferrosa, utilizando chatarra de hierro.The object of the present invention relates to the production of ferrous sulfate having as raw material the ashes obtained in the production of sulfuric acid by roasting pyrites. A solution of ferrous sulfate in acidic aqueous medium is first obtained. The dissolution of iron sulfates is reduced to pass all the ions to the ferrous form, using iron scrap.
De la disolución de sulfato ferroso se obtiene heptahidrato, sólido, por cristalización a vacio o mo- nohidrato, también sólido, por adición de ácido sulfúrico concentrado.From the solution of ferrous sulfate, solid heptahydrate is obtained by crystallization under vacuum or monohydrate, also solid, by the addition of concentrated sulfuric acid.
Los productos sólidos obtenidos, heptahidrato o monohidrato, tienen aplicaciones en el campo de la agricultura, aporte de hierro a los cultivos; en el cemento, como reductor del Cr6+; en tratamiento de aguas, como floculante primario; en fabricación de pigmento de óxido de hierro o en alimentación animal, entre otros.The solid products obtained, heptahydrate or monohydrate, have applications in the field of agriculture, contribution of iron to crops; in cement, as a Cr6 + reducer; in water treatment, as primary flocculant; in iron oxide pigment manufacturing or in animal feed, among others.
ANTECEDENTES DE LA INVENCIÓNBACKGROUND OF THE INVENTION
La sal ferrosa más ampliamente usada es el sulfato SO4Fe • 7H2O, que se conoce comercialmente como vitriolo verde o caparrosa. Se obtiene en forma de cristales monoclinicos, de color verde, por evaporación de una disolución de hierro en ácido sulfúrico diluido y en función de las condiciones de evaporación, presión, temperatura, concentraciones de iones, etc., se puede precipitar bien la forma heptahidratada o bien la forma mo- nohidratada SO4Fe • H2O, más difícil de conseguir pero con un contenido en hierro sensiblemente mayor.The most widely used ferrous salt is SO 4 Fe • 7H 2 O sulfate, which is commercially known as green or coated vitriol. It is obtained in the form of monoclinic crystals, green in color, by evaporation of an iron solution in dilute sulfuric acid and in Depending on the evaporation conditions, pressure, temperature, ion concentrations, etc., the heptahydrate form or the monohydrate form SO 4 Fe • H 2 O can be precipitated, more difficult to achieve but with an iron content noticeably older
Industrialmente la fuente de la disolución acida del sulfato ferroso es la industria metalúrgica, en el decapado de metales férreos por medio de ácido sulfúrico y la industria del bióxido de titanio, donde se ataca la ilmenita con ácido sulfúrico produciendo una disolución de sulfatos de hierro y titanio, de donde se separa el sulfato ferroso por cristalización a vacío.Industrially the source of the acid solution of ferrous sulfate is the metallurgical industry, in the pickling of ferrous metals by means of sulfuric acid and the titanium dioxide industry, where ilmenite is attacked with sulfuric acid producing a solution of iron sulfates and titanium, from which ferrous sulfate is separated by vacuum crystallization.
En la búsqueda de nuevas materias primas y procesos se estudió los productos derivados de la minería de la pirita, por ser este un mineral con alto contenido en hierro y en consecuencia susceptible de proporcionarnos una materia prima apta para la formación del sulfato ferroso.In the search for new raw materials and processes, the products derived from the mining of pyrite were studied, as this is a mineral with a high iron content and consequently capable of providing us with a raw material suitable for the formation of ferrous sulfate.
La sierra de Huelva (España) se conoce históricamente por ser una zona rica en sulfuros metálicos y el desarrollo de la zona se ha basado en la extracción y aprovechamiento de este mineral para recuperar los componentes de estos sulfuros.The Sierra de Huelva (Spain) is historically known as an area rich in metal sulphides and the development of the area has been based on the extraction and use of this mineral to recover the components of these sulphides.
Una de las formas de aprovechamiento ha sido la tostación de las piritas para producir ácido sulfúrico, elemento esencial de la industria química. La pirita, sulfuro de hierro, al ser tostada en una atmósfera rica en oxígeno producía anhídrido sulfuroso, en forma gaseosa, a partir del cual se fabricaba el ácido sulfúrico, y dejaba un residuo sólido, las cenizas de pirita que no han tenido ninguna aplicación y que se han ido almace- nando en lugares próximos a las plantas de producción del ácido.One of the forms of exploitation has been the roasting of pyrites to produce sulfuric acid, an essential element of the chemical industry. Pyrite, iron sulfide, when roasted in an oxygen-rich atmosphere produced sulfur dioxide, in gaseous form, from which sulfuric acid was manufactured, and left a solid residue, pyrite ashes that have had no application and they have gone stored- swimming in places close to acid production plants.
El método objeto de la invención consiste en atacar las cenizas de pirita (óxido férrico) con ácido sulfúrico, para producir un licor de sulfato de hierro, que una vez reducido sirve como materia prima para la fabricación de sulfato ferroso en dos formas de hidrata- ción, heptahidrato y monohidrato.The method object of the invention consists in attacking the ashes of pyrite (ferric oxide) with sulfuric acid, to produce an iron sulfate liquor, which once reduced serves as raw material for the manufacture of ferrous sulfate in two forms of hydrate. tion, heptahydrate and monohydrate.
DESCRIPCIÓN DE LA INVENCIÓNDESCRIPTION OF THE INVENTION
El proceso se inicia recuperando las cenizas de piritas de los antiguos depósitos y transportando el mi- neral a la planta de tratamiento donde, en primer lugar, se procede al secado del mineral y a su molienda mediante molinos de bolas hasta conseguir un tamaño de partícula inferior a 45 mieras.The process begins by recovering the pyrite ashes from the old tanks and transporting the mineral to the treatment plant where, first, the ore is dried and ground by ball mills until a smaller particle size is achieved. to 45 microns.
Una vez molido el mineral se hace reaccionar con ácido sulfúrico en digestores cerrados y conectados a un sistema de lavado de gases para depurar los productos gaseosos generados durante la reacción antes de ser vertidos a la atmósfera. El ácido sulfúrico utilizado puede ser fresco, del 98,5% de concentración, o bien reciclado de otras etapas del proceso o de otros procesos que generan ácido sulfúrico como coproducto. La concentración puede ir desde un 10% hasta un 98,5%. Se controlan diferentes parámetros como tiempos, temperaturas de reacti- vos, secuencias de adición de líquidos, agitación y periodos de mezcla con el objetivo de conseguir una eficiencia de reacción lo más alta posible, en torno al 95%. El producto de la reacción, liquido pastoso, se disuelve en ácidos débiles o en agua limpia, obteniéndose el licor de digestión. En la etapa de ataque la relación peso de ácido/ peso de mineral puede estar comprendida entre 1 y 5 y la temperatura de la reacción se mantiene entre 5O0C y 15O0C mediante el aporte de vapor a la masa de la reacción .Once the ore has been ground, it is reacted with sulfuric acid in closed digesters and connected to a gas washing system to purify the gaseous products generated during the reaction before being poured into the atmosphere. The sulfuric acid used can be fresh, with a concentration of 98.5%, or recycled from other stages of the process or from other processes that generate sulfuric acid as a coproduct. The concentration can range from 10% to 98.5%. Different parameters such as times, reagent temperatures, liquid addition sequences, stirring and mixing periods are controlled in order to achieve the highest possible reaction efficiency, around 95%. The reaction product, pasty liquid, is dissolved in weak acids or in clean water, obtaining the digestion liquor. In the attack stage, the weight ratio of acid / mineral weight can be between 1 and 5 and the reaction temperature is maintained between 5O 0 C and 15O 0 C by means of steam supplying the reaction mass.
El licor de digestión está formado por el ácido sulfúrico que se puso en exceso para conseguir la mayor eficiencia en ataque y los sulfatos solubles de los metales presentes en la ceniza de pirita, principalmente sulfato férrico, que deben ser reducidos para obtener el sulfato ferroso. La reducción se lleva acabo utilizando chatarra de hierro, al hacer pasar el licor de digestión a través de la chatarra conseguimos transformar el ion férrico en ferroso a la vez que aumentamos la concentración de hierro en la disolución llamada licor reducido. La reducción del contenido de iones férricos se realiza hasta valores por debajo de 10 gramos por litro.The digestion liquor is formed by the sulfuric acid that was put in excess to achieve the highest attack efficiency and the soluble sulfates of the metals present in the pyrite ash, mainly ferric sulfate, which must be reduced to obtain the ferrous sulfate. The reduction is carried out using iron scrap, by passing the digestion liquor through the scrap we managed to transform the ferric ion into ferrous while increasing the concentration of iron in the solution called reduced liquor. The reduction of the content of ferric ions is made up to values below 10 grams per liter.
La siguiente etapa tiene como objetivo la purificación de ese licor reducido por eliminación de los sólidos presentes en la disolución y que son consecuencia de que la eficiencia de la fase de ataque no es del 100%. Los sólidos se eliminan haciendo pasar la disolución a través de unos decantadores, donde se le añade un floculante que aglomera las partículas insolubles que son separadas de la fase liquida, permitiendo la obtención de un licor exento de materiales insolubles. Las purgas de los decantadores pasan por unos filtros rotativos en los que los sólidos son destinados a otras aplicaciones fuera de este proceso y el líquido obtenido se une con el licor limpio.The next stage aims to purify that reduced liquor by eliminating the solids present in the solution and which are a consequence of the fact that the efficiency of the attack phase is not 100%. The solids are removed by passing the solution through decanters, where a flocculant is added that agglomerates insoluble particles that are separated from the liquid phase, allowing to obtain a liquor free of insoluble materials. The decanters purges pass through rotary filters in which the solids are destined for other applications outside this process and the liquid obtained is joined with the clean liquor.
A partir de este punto el proceso tiene dos ca- minos diferentes en función del producto que queramos obtener: heptahidrato o monohidrato.From this point the process has two ca- different mines depending on the product we want to obtain: heptahydrate or monohydrate.
Para obtener sulfato ferroso heptahidratado el licor limpio se bombea a unos cristalizadores a vacio, donde por medio de unos eyectores de vapor se produce un fuerte vacio que permite la ebullición del licor y la consiguiente evaporación de parte del agua de la disolución disminuyendo considerablemente la temperatura y llegándose a alcanzar el producto de solubilidad del sulfato ferroso heptahidrato de acuerdo con el diagrama de fases de las disoluciones de sulfato ferroso en medio ácido. La temperatura de la disolución de entrada de los sulfatos en medio acuoso ácido a cristalización puede estar entre 30 y 70 0C y la de salida desde 40 a 10 0C.In order to obtain ferrous sulfate heptahydrate, the clean liquor is pumped into vacuum crystallizers, where by means of steam ejectors a strong vacuum is produced that allows the boiling of the liquor and the consequent evaporation of part of the water of the solution, considerably reducing the temperature and reaching the solubility product of ferrous sulfate heptahydrate according to the phase diagram of the solutions of ferrous sulfate in acidic medium. The temperature of the input solution of sulfates in aqueous acidic medium to crystallization may be between 30 and 70 0 C and the output from 40 to 10 0 C.
La suspensión de cristales aqui formada puede enviarse a un segundo cristalizador, conectado a un cambiador de calor que permite su enfriamiento mediante un grupo frigorífico, y que facilita la formación de los cristales de sulfato ferroso heptahidratado. La corriente de salida de éste segundo cristalizador se envia a un espesador donde por acción de la gravedad se consigue una purga rica en cristales por la parte inferior del espesador, mientras que por la parte alta rebosa un liquido limpio de sólidos. La purga de este espesador se alimenta a unas centrifugas que separan los cristales de la fase liquida mediante tamices. Esta fase liquida se une con el rebose del espesador y forma parte de los ácidos diluidos que se utilizan en la fase de ataque o disolución de las cenizas de piritas. Los cristales separados en la centrifugas son el sulfato ferroso heptahidratado . Es también objeto de la presente invención el producto obtenido mediante el anterior método y que en su composición contiene una cantidad de hierro, en forma ferrosa, entre un 12 y un 20% del peso total del produc- to finalmente obtenido.The crystalline suspension formed here can be sent to a second crystallizer, connected to a heat exchanger that allows its cooling by means of a refrigerating group, and which facilitates the formation of ferrous sulfate heptahydrate crystals. The output current of this second crystallizer is sent to a thickener where, due to gravity, a purge rich in crystals is achieved at the bottom of the thickener, while a clean liquid of solids overflows from the top. The purge of this thickener is fed to centrifuges that separate the crystals from the liquid phase by sieves. This liquid phase joins with the thickener overflow and is part of the diluted acids used in the attack or dissolution phase of pyrite ashes. The crystals separated in the centrifuges are ferrous sulfate heptahydrate. Also object of the present invention is the product obtained by the above method and which in its composition contains an amount of iron, in ferrous form, between 12 and 20% of the total weight of the product finally obtained.
Si lo que se quiere obtener es el sulfato ferroso monohidratado, el proceso consiste en llevar el licor purificado en los decantadores a unos tanques especia- les, con un revestimiento anti ácido y una agitación muy lenta, donde se añade sobre el licor, una cantidad determinada de ácido sulfúrico concentrado, en unas proporciones que varían entre 1 parte de ácido y 4 partes de licor y 3 partes de ácido y 4 partes de licor, y en caliente se produce la precipitación del sulfato ferroso monohidratado. Con la agitación lenta se produce la maduración y el crecimiento de los cristales de monohidra- to que se separan en unos filtros de bujías, en la que el sólido separado en los filtros se seca mediante co- rriente de aire dentro de los propios filtros de bujías, obteniéndose unos filtrados ácidos que son utilizados en la fase de ataque del mineral y un sólido formado en su mayor parte por sulfato ferroso monohidratado.If what is to be obtained is ferrous sulfate monohydrate, the process consists in bringing the purified liquor in the decanters to special tanks, with an anti-acid coating and a very slow stirring, where a quantity is added on the liquor determined from concentrated sulfuric acid, in proportions that vary between 1 part of acid and 4 parts of liquor and 3 parts of acid and 4 parts of liquor, and hot precipitation of ferrous sulfate monohydrate occurs. With slow agitation, maturation and growth of the monohydrate crystals that separate into spark plug filters occur, in which the solid separated in the filters is dried by means of an air stream inside the filters themselves. spark plugs, obtaining acid filtrates that are used in the attack phase of the mineral and a solid formed mostly by ferrous sulfate monohydrate.
Hay una variante al proceso de obtención del sulfato ferroso monohidratado que consiste en eliminar la etapa de la purificación del licor reducido, con lo que el proceso sería alimentar con licor reducido a los tanques de precipitación, donde se le añadiría la canti- dad correspondiente de ácido sulfúrico para producir la precipitación del sulfato ferroso monohidratado y tras el crecimiento y maduración de los cristales se alimentaría a los filtros de bujías, separando la fase liquida que volvería al ataque del mineral y la fase sólida que sería el sulfato ferroso monohidratado. Este monohidrato se puede comercializar directamente o bien se puede neutralizar la acidez libre que le acompaña, con calizas, dolomitas o cualquier otro mate- rial que reaccione con el ácido sulfúrico y que nos dé unos productos de reacción que o bien aporten algún beneficio al producto final o bien aporten inertes. Una vez neutralizado el producto se puede granular, paleti- zar o compactar con el fin de obtener un producto de ma- nejo más fácil y más estable.There is a variant to the process of obtaining ferrous sulfate monohydrate which consists in eliminating the stage of purification of the reduced liquor, so that the process would be to feed the reduced tanks with reduced liquor, where the corresponding amount of Sulfuric acid to produce the precipitation of ferrous sulfate monohydrate and after the growth and maturation of the crystals, the spark plug filters would be fed, separating the liquid phase that would return to the attack of the mineral and the solid phase that would be the ferrous sulfate monohydrate. This monohydrate can be marketed directly or the free acidity that accompanies it can be neutralized, with limestones, dolomites or any other material that reacts with sulfuric acid and that gives us reaction products that either bring some benefit to the product final or contribute inert. Once the product has been neutralized, it can be granulated, palletized or compacted in order to obtain an easier and more stable handling product.
La adición del acido se hará en tanques especialmente revestidos y aislados térmicamente, con una agitación constante y lenta, para favorecer la formación y el crecimiento de los cristales de sulfato ferroso monohidrato .The acid will be added in specially coated and thermally insulated tanks, with constant and slow stirring, to favor the formation and growth of ferrous sulfate monohydrate crystals.
Es también objeto de la presente invención el producto obtenido mediante los anteriores métodos y que en su composición contiene una cantidad de hierro, en forma ferrosa, entre un 15% y un 32% del peso total del producto finalmente obtenido.The product obtained by the above methods and which in its composition contains an amount of iron, in ferrous form, between 15% and 32% of the total weight of the product finally obtained is also object of the present invention.
REALIZACIÓN PREFERENTE DE LA INVENCIÓNPREFERRED EMBODIMENT OF THE INVENTION
Primer ejemplo de realización.First example of realization.
Ataque de la ceniza de pirita con ácido sulfúrico fresco y posterior cristalización del licor obtenido .Attack of the pyrite ash with fresh sulfuric acid and subsequent crystallization of the liquor obtained.
400 g de cenizas de pirita, con un contenido en hierro total de 59%, se hacen reaccionar con 1000 g de ácido sulfúrico del 98.5% de riqueza y con 2200 mi de agua. Tras 16 minutos de mezcla se calienta y se inicia la reacción, manteniéndose a 90 0C durante 300 minutos, al cabo de los cuales se deja de calentar y se añaden 1900 mi de agua para disolver la masa de la reacción .400 g of pyrite ashes, with a total iron content of 59%, are reacted with 1000 g of sulfuric acid of 98.5% of wealth and with 2200 ml of water. After 16 minutes mixture is heated and the reaction is initiated and maintained at 90 0 C for 300 minutes, after which stops heating and added 1900 ml of water to dissolve the reaction mass.
Se obtiene de esta forma 3150 mi de licor de digestión, con una densidad de 1288 g/1 y un contenido en hierro total (suma de ferroso más férrico) de 75 g/1In this way, 3150 ml of digestion liquor is obtained, with a density of 1288 g / 1 and a total iron content (sum of ferrous plus ferrous) of 75 g / 1
Este licor de digestión se le hace reaccionar con 145 g de chatarra de hierro, obteniéndose 3150 mi de licor reducido, que contiene 158 g/1 de hierro total, de los que 2 g/1 son de hierro férrico.This digestion liquor is reacted with 145 g of iron scrap, obtaining 3150 ml of reduced liquor, which contains 158 g / 1 of total iron, of which 2 g / 1 are ferric iron.
Al licor reducido se la añade un floculante que permita aglutinar las micro partículas de los residuos inatacados de digestión, que se separan por decantación o filtración, dejándonos un licor claro y limpio que entrará a la etapa de cristalización.A flocculant is added to the reduced liquor to agglutinate the micro particles of the undigested digestion residues, which are separated by decantation or filtration, leaving us a clear and clean liquor that will enter the crystallization stage.
900 mi del licor reducido y clarificado se le hace pasar por cristalizadores a vacío, donde hierve y se concentra, disminuyendo su temperatura hasta 16 0C y precipitando 397 g de sulfato ferroso heptahidratado, con un contenido en hiero ferroso del 18.5% y acidez libre del 1.3%.900 ml of the reduced and clarified liquor is passed through vacuum crystallizers, where it boils and concentrates, decreasing its temperature to 16 0 C and precipitating 397 g of ferrous sulfate heptahydrate, with a ferrous iron content of 18.5% and free acidity of 1.3%.
Segudo ejemplo de realización.I follow an example of realization.
Ataque de la ceniza de pirita con ácido sulfúrico fresco y reciclado procedente de cristalizaciones anteriores y cristalización del licor obtenido . 300 g de cenizas de pirita, con un contenido en hierro total del 59%, se hacen reaccionar con 540 g de ácido sulfúrico del 98.5% de riqueza, 2000 g de efluente procedente de cristalizaciones anteriores y que contiene 11% de ácido sulfúrico, y con 1000 g de agua.Attack of the pyrite ash with fresh and recycled sulfuric acid from previous crystallizations and crystallization of the liquor obtained. 300 g of pyrite ash, with a total iron content of 59%, are reacted with 540 g of sulfuric acid of 98.5% richness, 2000 g of effluent from previous crystallizations and containing 11% of sulfuric acid, and with 1000 g of water.
Tras 16 minutos de mezcla se calienta y se inicia la reacción, manteniéndose a 9O0C durante 180 minutos, al cabo se los cuales se deja de calentar y se añaden 1900 mi de agua para disolver la masa de la reacción .After 16 minutes mixture is heated and the reaction is initiated and maintained at 9O 0 C for 180 minutes, after which it stops heating and added 1900 ml of water to dissolve the reaction mass.
Se obtiene de esta forma 2900 mi de licor de digestión, con una densidad de 1299 g/1 y un contenido en hierro total (suma de ferroso más férrico) de 84 g/1.In this way, 2900 ml of digestion liquor is obtained, with a density of 1299 g / 1 and a total iron content (sum of ferrous plus ferric) of 84 g / 1.
Este licor de digestión se le hace reaccionar con 91 g de chatarra de hierro, obteniéndose 3000 mi de licor reducido, que contiene 111 g/1 de hierro total, sin presencia de hierro férrico.This digestion liquor is reacted with 91 g of iron scrap, obtaining 3000 ml of reduced liquor, which contains 111 g / 1 of total iron, without the presence of ferric iron.
Al licor reducido se la añade un floculante que permita aglutinar las micro partículas de los residuos inatacados de digestión, que se separan por decantación o filtración, dejándonos un licor claro y limpio que entrará a la etapa de cristalización.A flocculant is added to the reduced liquor to agglutinate the micro particles of the undigested digestion residues, which are separated by decantation or filtration, leaving us a clear and clean liquor that will enter the crystallization stage.
1500 mi del licor reducido y clarificado se le hace pasar por cristalizadores a vacío, donde hierve y se concentra, disminuyendo su temperatura hasta 16 0C y precipitando 504 g de sulfato ferroso heptahidratado, con un contenido en hiero ferroso del 18.5 % y acidez libre del 1.5 %. Tercer ejemplo de realización.1500 ml of the reduced and clarified liquor is passed through vacuum crystallizers, where it boils and concentrates, decreasing its temperature to 16 0 C and precipitating 504 g of ferrous sulfate heptahydrate, with a ferrous iron content of 18.5% and free acidity 1.5% Third embodiment example.
Ataque de la ceniza de pirita con ácido sulfúrico reciclado procedente de obtención de sulfato ferroso monohidratado de ensayos anteriores y precipitación de monohidrato en el licor obtenido.Attack of pyrite ash with recycled sulfuric acid from obtaining ferrous sulfate monohydrate from previous tests and precipitation of monohydrate in the liquor obtained.
300 g de cenizas de pirita, con un contenido en hierro total del 59%, se hacen reaccionar con 2160 g de efluente procedente de precipitaciones anteriores y que contiene 22% de ácido sulfúrico.300 g of pyrite ashes, with a total iron content of 59%, are reacted with 2160 g of effluent from previous precipitations and containing 22% sulfuric acid.
Tras un corto periodo de mezcla se calienta y se inicia la reacción, manteniéndose a 9O0C durante 240 minutos, al cabo se los cuales se deja de calentar y se añaden 425 g del mismo efluente anteriormente utilizado y 2000 mi de agua para disolver la masa de la reacción.After a short period of mixture is heated and the reaction is initiated and maintained at 9O 0 C for 240 minutes, after is which stops heating and 425 g of the same effluent was added previously used and 2000 ml of water to dissolve the reaction mass
Se obtiene de esta forma 3100 mi de licor de digestión, con una densidad de 1328 g/1 y un contenido en hierro total (suma de ferroso más férrico) de 82 g/1.In this way, 3100 ml of digestion liquor is obtained, with a density of 1328 g / 1 and a total iron content (sum of ferrous plus ferric) of 82 g / 1.
Este licor de digestión se le hace reaccionar con 123 g de chatarra de hierro, obteniéndose 3100 mi de licor reducido, que contiene 129 g/1 de hierro total, con 3 g/1 de hierro férrico.This digestion liquor is reacted with 123 g of iron scrap, obtaining 3100 ml of reduced liquor, which contains 129 g / 1 of total iron, with 3 g / 1 of ferric iron.
A 1000 mi de este licor reducido se le añaden 250 mi de ácido sulfúrico del 98.5% de riqueza, obteniéndose un precipitado de sulfato ferroso monohidrato, que una vez separado pesa 399g y que tiene un contenido en hiero ferroso del 24.0% y acidez libre del 10.3%. APLICACIÓN INDUSTRIALTo 1000 ml of this reduced liquor is added 250 ml of 98.5% rich sulfuric acid, obtaining a precipitate of ferrous sulfate monohydrate, which once separated weighs 399g and has a ferrous iron content of 24.0% and free acidity of the 10.3% INDUSTRIAL APPLICATION
Sulfato ferroso heptahidratadoFerrous Sulfate Heptahydrate
Agricultura: Aporte de hierro para evitar la clorosis férrica de los cítricos, principalmente. Agente anti limacos, para prevención de plagas.Agriculture: Iron supply to prevent iron chlorosis of citrus fruits, mainly. Anti-limacos agent, for pest prevention.
Tratamiento de aguas: Directamente como floculante primario para aguas residuales o bien tras su transformación en sulfato férrico para tratamiento y depuración de aguas potables y residuales.Water treatment: Directly as primary flocculant for wastewater or after its transformation into ferric sulfate for treatment and purification of drinking and wastewater.
Minería: En proceso de flotación y como agente reductor en varios procesos de mineríaMining: In the process of flotation and as a reducing agent in several mining processes
Fabricación de pigmentos: Como materia prima para la fabricación de pigmento en base a óxidos de hierro, para toner de impresoras.Manufacturing of pigments: As raw material for the manufacture of pigment based on iron oxides, for printer toner.
Alimentación animal: Como materia prima para la obtención de productos en base a sulfato de hierro aptos para fabricación de piensos compuestos para alimentación animalAnimal feed: As raw material for obtaining products based on iron sulfate suitable for manufacturing compound feed for animal feed
Industria del cemento: Como agente reductor de cromo hexavalente en la aplicación del cemento Pórtland.Cement industry: As a hexavalent chromium reducing agent in the application of Portland cement.
Sulfato ferroso monohidratadoFerrous Sulfate Monohydrate
Se puede utilizar directamente o bien tras un proceso de granulación. Directamente se utiliza para:It can be used directly or after a granulation process. It is directly used to:
Alimentación animal: Como materia prima para la obtención de productos en base a sulfato de hierro de alta pureza, aptos para fabricación de piensos compuestos para alimentación animalAnimal feed: As a raw material for obtaining products based on iron sulfate from high purity, suitable for manufacturing compound feed for animal feed
Industria del cemento: Como agente reductor de cromo hexavalente, añadido en la etapa final del proceso de fabricación, en la aplicación del cemento Pórtland.Cement industry: As a hexavalent chromium reducing agent, added in the final stage of the manufacturing process, in the application of Portland cement.
Granulado se utiliza para:Granulate is used for:
Agricultura: Aporte de hierro para evitar la clorosis férrica de los cítricos, principalmente. Como agente de relleno en la fabricación de fertilizantes por blending.Agriculture: Iron supply to prevent iron chlorosis of citrus fruits, mainly. As a filling agent in blending fertilizer manufacturing.
Industria del cemento: Como agente reductor de cromo hexavalente en la aplicación del cemento Pórtland, añadiéndolo en la etapa de molienda del clinquer. Cement industry: As a hexavalent chromium reducing agent in the application of Portland cement, adding it in the grinding stage of the clinquer.

Claims

REIVINDICACIONES
1.- Método de fabricación de sulfato ferroso a partir de cenizas de pirita, caracterizado porque comprende una primera etapa de ataque de las cenizas de pirita con ácido sulfúrico de una concentración entre un 10% a un 98,5% de riqueza y posterior disolución de los sulfatos resultantes en medio acuoso ácido y una segunda etapa de reducción química en la que se realiza la recirculación de la disolución de los sulfatos en medio acuoso ácido sobre chatarra de hierro para la reducción del contenido en iones férricos (Fe3+) hasta valores por debajo de 10 gramos por litro.1.- Method of manufacturing ferrous sulfate from pyrite ashes, characterized in that it comprises a first stage of attack of pyrite ashes with sulfuric acid of a concentration between 10% to 98.5% of wealth and subsequent dissolution of the resulting sulfates in acidic aqueous medium and a second stage of chemical reduction in which the recirculation of the sulfate solution in acidic aqueous medium is carried out on iron scrap for the reduction of the ferric ion content (Fe 3+ ) until values below 10 grams per liter.
2.- Método de fabricación de sulfato ferroso a partir de cenizas de pirita, según la reivindicación 1, caracterizado porque en la etapa de ataque la relación peso de ácido/peso de mineral puede estar comprendida entre 1 a 5.2. Method of manufacturing ferrous sulfate from pyrite ashes, according to claim 1, characterized in that in the attack stage the weight ratio of acid / mineral weight can be comprised between 1 and 5.
3.- Método de fabricación de sulfato ferroso a partir de cenizas de pirita, según cualquiera de las reivindicaciones anteriores, caracterizado porque la temperatura de la reacción se mantiene entre 5O0C y 15O0C mediante el aporte de vapor a la masa de la reacción .3. Method of manufacturing ferrous sulfate from pyrite ashes, according to any one of the preceding claims, characterized in that the reaction temperature is maintained between 5O 0 C and 15O 0 C by providing steam to the mass of the reaction .
4.- Método de fabricación de sulfato ferroso a partir de cenizas de pirita, según cualquiera de las reivindicaciones anteriores, caracterizado porque comprende una posterior etapa de depuración de la disolución reducida de sulfato ferroso que comprende la eliminación de los sólidos inatacados de las cenizas de pirita por medio de floculación y decantación. 4. Method of manufacturing ferrous sulfate from pyrite ashes, according to any of the preceding claims, characterized in that it comprises a subsequent stage of purification of the reduced solution of ferrous sulfate comprising the removal of the unbound solids from the ashes of pyrite by means of flocculation and decantation.
5.- Método de fabricación de sulfato ferroso a partir de cenizas de pirita, según cualquiera de las reivindicaciones anteriores, caracterizado porque comprende una posterior etapa de cristalización mediante la utilización de cristalizadores a vacio que permiten la ebullición de la disolución de los sulfatos en medio acuoso ácido con el consiguiente enfriamiento y concentración en sulfato ferroso, hasta conseguir la formación de cristales de sulfato ferroso heptahidratado .5. Method of manufacturing ferrous sulfate from pyrite ashes, according to any of the preceding claims, characterized in that it comprises a subsequent crystallization stage by using vacuum crystallizers that allow the boiling of the sulfate solution in medium. aqueous acid with the consequent cooling and concentration in ferrous sulfate, until the formation of ferrous sulfate crystals heptahydrate.
6.- Método de fabricación de sulfato ferroso a partir de cenizas de pirita, según la reivindicación 5, caracterizado porque la temperatura de la disolución de entrada de los sulfatos en medio acuoso ácido a cristalización puede estar entre 30 y 70 0C y la de salida desde 40 a 10 0C.6. Method of manufacture of ferrous sulfate from pyrite ash, according to claim 5, wherein the temperature of the input solution of sulfates in aqueous acidic medium to crystallization may be between 30 and 70 0 C and the output from 40 to 10 0 C.
7.- Método de fabricación de sulfato ferroso a partir de cenizas de pirita, según las reivindicaciones 5 ó 6, caracterizado porque comprende una posterior etapa de concentración en cristales mediante la utilización de unos espesadores, donde por acción de la gravedad se consigue una purga rica en cristales por la parte inferior del espesador, mientras que por la parte alta rebosa un liquido limpio de sólidos.7. Method of manufacturing ferrous sulfate from pyrite ashes, according to claims 5 or 6, characterized in that it comprises a later stage of concentration in crystals through the use of thickeners, where a purge is achieved by gravity rich in crystals at the bottom of the thickener, while at the top it overflows a clean liquid of solids.
8.- Método de fabricación de sulfato ferroso a partir de cenizas de pirita, según la reivindicación 7, caracterizado porque comprende una posterior etapa de separación de los cristales mediante el uso de equipos centrifugadores para la separación con el uso de los tamices de los cristales formados. 8. Method of manufacturing ferrous sulfate from pyrite ashes, according to claim 7, characterized in that it comprises a subsequent stage of separation of the crystals by using centrifugal equipment for separation with the use of the sieves of the crystals formed.
9.- Producto obtenido según las reivindicaciones 1 a 8 y que en su composición contiene una cantidad de hierro, en forma ferrosa, entre un 12% y un 20% del peso total del producto finalmente obtenido.9. Product obtained according to claims 1 to 8 and which in its composition contains an amount of iron, in ferrous form, between 12% and 20% of the total weight of the product finally obtained.
10.- Método de fabricación de sulfato ferroso a partir de cenizas de pirita, según cualquiera de las reivindicaciones 1 a 4, caracterizado porque comprende una etapa posterior de precipitación de sulfato ferroso monohidratado (SO4Fe • H2O) por adición de ácido sulfúrico en una proporción entre 1 parte de ácido y 4 partes de disolución de los sulfatos resultantes en medio acuoso ácido y 3 partes de ácido y 4 partes de disolución de los sulfatos resultantes en medio acuoso ácido.10. Method of manufacturing ferrous sulfate from pyrite ashes, according to any one of claims 1 to 4, characterized in that it comprises a subsequent step of precipitation of ferrous sulfate monohydrate (SO 4 Fe • H 2 O) by the addition of acid sulfuric acid in a proportion between 1 part of acid and 4 parts of dissolution of the resulting sulfates in acidic aqueous medium and 3 parts of acid and 4 parts of dissolution of the resulting sulfates in acidic aqueous medium.
11.- Método de fabricación de sulfato ferroso a partir de cenizas de pirita, según la reivindicación 10, caracterizado porque comprende una etapa posterior de separación de monohidrato mediante la utilización de filtros de bujías en la que el sólido separado en los filtros se seca mediante corriente de aire dentro de los propios filtros de bujías.11. Method of manufacturing ferrous sulfate from pyrite ashes, according to claim 10, characterized in that it comprises a subsequent stage of monohydrate separation by using spark plug filters in which the solid separated in the filters is dried by air flow inside the spark plug filters themselves.
12.- Producto obtenido según cualquiera de las reivindicaciones 1 a 8 ó 10 y 11 y que en su composición contiene una cantidad de hierro, en forma ferrosa, entre un 15% y un 32% de peso total del producto finalmente obtenido . 12. Product obtained according to any of claims 1 to 8 or 10 and 11 and which in its composition contains an amount of iron, in ferrous form, between 15% and 32% of the total weight of the product finally obtained.
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