ES2471317A1 - Procedure for the generation of high porosity calcium carbonate microparticles by wet process from waste from the natural stone transformation industry (Machine-translation by Google Translate, not legally binding) - Google Patents

Procedure for the generation of high porosity calcium carbonate microparticles by wet process from waste from the natural stone transformation industry (Machine-translation by Google Translate, not legally binding) Download PDF

Info

Publication number
ES2471317A1
ES2471317A1 ES201232009A ES201232009A ES2471317A1 ES 2471317 A1 ES2471317 A1 ES 2471317A1 ES 201232009 A ES201232009 A ES 201232009A ES 201232009 A ES201232009 A ES 201232009A ES 2471317 A1 ES2471317 A1 ES 2471317A1
Authority
ES
Spain
Prior art keywords
calcium carbonate
polymer
caco3
particles
synthesis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
ES201232009A
Other languages
Spanish (es)
Other versions
ES2471317B1 (en
Inventor
Jos� Manuel �NDUJAR PERAL
Francisco Javier MART�NEZ FERN�NDEZ
Ignacio MART�NEZ SOLER
Alfonso Cortes Izurdiaga
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fundacion Centro Tecnologico Andaluz de La Piedra
Original Assignee
Fundacion Centro Tecnologico Andaluz de La Piedra
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fundacion Centro Tecnologico Andaluz de La Piedra filed Critical Fundacion Centro Tecnologico Andaluz de La Piedra
Priority to ES201232009A priority Critical patent/ES2471317B1/en
Publication of ES2471317A1 publication Critical patent/ES2471317A1/en
Application granted granted Critical
Publication of ES2471317B1 publication Critical patent/ES2471317B1/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
    • C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F1/00—Methods of preparing compounds of the metals beryllium, magnesium, aluminium, calcium, strontium, barium, radium, thorium, or the rare earths, in general

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

Procedure for the generation of high porosity calcium carbonate microparticles from the waste of the natural stone transformation industry. The object of the present invention is related to a process for the generation of high porosity microparticles of calcium carbonate by the wet route from residues of the natural stone industry in aqueous solution. The process is characterized in that the calcium carbonate formation reaction takes place in the presence of a surface charge stabilizing agent and a copolymer and can be carried out in coexistence with other substances, so that there is no need to pretreat the starting solutions. A final calcination step is necessary to remove the calcium carbonate copolymer and the porous structure is generated. The process is susceptible to be industrialized and the product obtained through it, the high porosity microparticles of calcium carbonate, can be used as a raw material in many different sectors, such as construction, food, cosmetics, etc. (Machine-translation by Google Translate, not legally binding)

Description

Procedimiento para la generación de micro partículas de carbonato cálcico de alta porosidad por vía húmeda a partir de residuos de la industria de transformación de la piedra natural Procedure for the generation of micro particles of high-porosity calcium carbonate by means of waste from the natural stone processing industry waste

CAMPO TÉCNICO TECHNICAL FIELD

El objeto de la presente invención, tal y como se expresa en el enunciado de esta memoria descriptiva, est� relacionado con un procedimiento para la generación de micropart�culas de alta porosidad de carbonato cálcico por la vía húmeda. El procedimiento es susceptible de ser industrializable y el producto obtenido a través de él, las micropart�culas de alta porosidad de carbonato cálcico, pueden ser utilizadas como materia prima en multitud de sectores distintos, tales como construcción, alimentación, cosm�tica, etc. The object of the present invention, as expressed in the statement of this specification, is related to a process for the generation of high porosity microparticles of calcium carbonate by the wet route. The process is capable of being industrializable and the product obtained through it, the high porosity microparticles of calcium carbonate, can be used as raw material in many different sectors, such as construction, food, cosmetics, etc. .

ANTECEDENTES DE LA INVENCIÓN BACKGROUND OF THE INVENTION

Los materiales altamente porosos con huecos conectados tridimensionalmente presentan actualmente un gran interés industrial debido a sus posibles aplicaciones como trampas fotónicas, materiales diel�ctricos, soportes catalíticos y rellenos en materiales estructurales para reducir su densidad. Por su carácter relativamente blando y su tendencia a colapsar a altas temperaturas, el carbonato cálcico es una materia prima adecuada para generar estructuras de poros huecos. Se han usado diferentes tecnologías a escala de laboratorio para conseguir este fin usando matrices de diferentes tipos y condiciones, pero los micro poros de las partículas resultantes se distribuyen fundamentalmente en la superficie de las partículas generadas. Es más interesante, sin embargo, generar redes de poros interconectados tridimensionalmente en todo el volumen de la partícula. En el caso de la invención que se propone se ha conseguido realizar esta red tridimensional mediante la tecnología que se describe en esta memoria. Highly porous materials with three-dimensionally connected holes present a great industrial interest due to their possible applications such as photonic traps, dielectric materials, catalytic supports and fillers in structural materials to reduce their density. Because of its relatively soft nature and its tendency to collapse at high temperatures, calcium carbonate is a suitable raw material to generate hollow pore structures. Different technologies have been used on a laboratory scale to achieve this purpose using matrices of different types and conditions, but the micro pores of the resulting particles are distributed mainly on the surface of the generated particles. It is more interesting, however, to generate three-dimensionally interconnected pore networks across the entire volume of the particle. In the case of the proposed invention, this three-dimensional network has been achieved by means of the technology described herein.

DESCRIPCI�N DE LA INVENCIÓN DESCRIPTION OF THE INVENTION

En el caso de la invención que se propone se ha conseguido obtener partículas de carbonato cálcico con una red porosa tridimensional. In the case of the proposed invention, it has been possible to obtain particles of calcium carbonate with a three-dimensional porous network.

En términos generales, la presente invención se refiere a un procedimiento que permite obtener partículas de carbonato cálcico micro y meso porosas a partir de residuos de transformación de la piedra natural por vía húmeda mediante la introducción de agentes estabilizadores de carga superficial y copol�meros en las partículas durante el proceso de generación de las mismas. Los residuos de transformación de la piedra natural son disoluciones acuosas que contienen restos de material p�treo y, por tanto, una concentración determinada de carbonato cálcico. Estos residuos, además, proceden de los procesos de aserrado, apomazado, pulido y, en general, de cualquier proceso asociado a la transformación de cualquier piedra natural, principalmente mármoles y calizas, que requiera una refrigeración externa por agua. Alternativamente, puede ser válida para la aplicación del método descrito en la presente patente cualquier disolución acuosa que contenga carbonato cálcico, sin perjuicio de que aparezcan otras sustancias en disolución. In general terms, the present invention relates to a process that allows to obtain micro and meso porous calcium carbonate particles from wet stone transformation residues by introducing surface loading stabilizing agents and copolymers in the particles during the process of generating them. The transformation residues of natural stone are aqueous solutions that contain remains of stone material and, therefore, a certain concentration of calcium carbonate. This waste also comes from the processes of sawing, tapping, polishing and, in general, from any process associated with the transformation of any natural stone, mainly marble and limestone, that requires external water cooling. Alternatively, any aqueous solution containing calcium carbonate may be valid for the application of the method described in the present patent, without prejudice to the appearance of other substances in solution.

Inicialmente, la disolución acuosa de carbonato cálcico se trata con una disolución de ácido clorhídrico, gener�ndose en la reacción una disolución acuosa de cloruro de calcio y liber�ndose di�xido de carbono: Initially, the aqueous calcium carbonate solution is treated with a solution of hydrochloric acid, an aqueous solution of calcium chloride being generated in the reaction and carbon dioxide being released:

CaCO3 + 2 HCl = CaCl2 + CO2 + H2O CaCO3 + 2 HCl = CaCl2 + CO2 + H2O

Posteriormente, la disolución de cloruro cálcico previamente preparada se introduce en un reactor tipo tanque agitado junto con estabilizadores de carga y un copol�mero, y se hace reaccionar con una corriente gaseosa de di�xido de carbono ajustando pH, caudal de di�xido de carbono, temperatura y nivel de agitaci�n. Los estabilizadores de carga son tensioactivos de tipo ani�nico, cati�nico o neutro hidrosolubles. Los copol�meros son del tipo poliestireno, ácido poliacr�lico o polivinil pirrolidina. En este reactor se generan las partículas de carbonato cálcico, siendo la reacción química la inversa de la que se expuso anteriormente: Subsequently, the previously prepared calcium chloride solution is introduced into a stirred tank reactor together with charge stabilizers and a copolymer, and reacted with a gaseous stream of carbon dioxide by adjusting pH, dioxide flow rate. of carbon, temperature and agitation level. The charge stabilizers are water-soluble, anionic, cationic or neutral surfactants. The copolymers are of the polystyrene, polyacrylic acid or polyvinyl pyrrolidine type. In this reactor the calcium carbonate particles are generated, the chemical reaction being the inverse of the one set forth above:

CaCl2 + CO2 + H2O + Estabilizadores de carga + Copol�mero = CaCO3+ 2 HCl CaCl2 + CO2 + H2O + Load stabilizers + Copolymer = CaCO3 + 2 HCl

Puede aprovecharse el CO2 generado en la primera reacción como reactivo en esta segunda, siempre y cuando se acondicione adecuadamente. The CO2 generated in the first reaction can be used as a reagent in this second one, as long as it is properly conditioned.

Las partículas de carbonato cálcico pueden aislarse mediante filtración de la disolución. Posteriormente se secan con aire caliente. Finalmente, se someten a calentamiento en horno a una temperatura comprendida entre 150 y 250�C, dependiendo del co-pol�mero empleado. El co-pol�mero, que se encuentra embebido en la masa de la micro-partícula, se destruye y genera la red tridimensional de poros que se interconectan en todo el volumen de las partículas generadas. The calcium carbonate particles can be isolated by filtration of the solution. They are subsequently dried with hot air. Finally, they are subjected to oven heating at a temperature between 150 and 250 ° C, depending on the co-polymer used. The co-polymer, which is embedded in the mass of the micro-particle, is destroyed and generates the three-dimensional network of pores that interconnect throughout the volume of the generated particles.

Este proceso permite una fácil réplica a escala industrial y la obtención de las micropart�culas deseadas con las propiedades adecuadas. This process allows easy replication on an industrial scale and obtaining the desired microparticles with the appropriate properties.

Las concentraciones de los agentes tensioactivos necesarias para la generación de las partículas porosas es baja e inferior a 5 mM/l. La secuencia de pasos que tiene lugar en este proceso de generación es la que se expone a continuación. En primer lugar, se produce una micela compleja por unión del tensioactivo y el coloide base de cloruro de calcio que actúa como núcleo de condensación para la precipitación de las micropart�culas. En segundo lugar, el carbónico de adsorbe sobre los núcleos ya formados y a continuación el calcio de la disolución reacciona con el carbónico adsorbido embebiendo en su seno al copol�mero de forma aleatoria. En tercer lugar, se produce el crecimiento de las partículas hasta el tamaño máximo congruente con la concentración de tensioactivo. Si de ese punto se recogen las partículas obtenidas para llevarlas a un secadero de aire caliente a 130 �C en contra corriente y finalmente se calcinan en horno a una temperatura comprendida entre 150 y 250 �C (dependiendo del copol�mero empleado), pueden obtenerse las partículas micro y meso porosas por eliminación del copol�mero de la estructura interna de las partículas. Una vez secas y calcinadas, las partículas deben retirarse para su almacenamiento en condiciones de sequedad. The concentrations of the surfactants necessary for the generation of the porous particles is low and less than 5 mM / l. The sequence of steps that takes place in this generation process is as set out below. First, a complex micelle is produced by binding the surfactant and the calcium chloride base colloid that acts as a condensation core for the precipitation of the microparticles. Secondly, the adsorbe carbonic on the already formed nuclei and then the calcium in the solution reacts with the adsorbed carbonic by embedding the copolymer randomly therein. Thirdly, particle growth occurs up to the maximum size consistent with the concentration of surfactant. If from that point the particles obtained are collected to take them to a hot air dryer at 130 ° C against the current and finally they are calcined in the oven at a temperature between 150 and 250 ° C (depending on the copolymer used), they can the porous micro and meso particles are obtained by removing the copolymer from the internal structure of the particles. Once dried and calcined, the particles should be removed for storage under dry conditions.

Las ventajas de este procedimiento descrito son las siguientes: The advantages of this procedure described are the following:

--
El proceso permite la generación de partículas micro y meso porosas con una red tridimensional de poros distribuida en todo el volumen de la partícula.  The process allows the generation of porous micro and meso particles with a three-dimensional network of pores distributed throughout the volume of the particle.

--
El proceso permite la generación de micro-partículas con poros en red tridimensional a gran escala reduciendo as� los costes de producción.  The process allows the generation of micro-particles with pores in a large-scale three-dimensional network thus reducing production costs.

--
El proceso permite la reutilización de un residuo.  The process allows the reuse of a waste.

--
El proceso es fácilmente controlable dadas las variables implicadas en el mismo.  The process is easily controllable given the variables involved in it.

DESCRIPCI�N DE LOS DIBUJOS DESCRIPTION OF THE DRAWINGS

La figura 1 muestra un diagrama de flujo de un ejemplo de caso práctico de aplicación industrial del procedimiento objeto de la presente patente. Figure 1 shows a flow chart of a case study example of industrial application of the process object of the present patent.

El proceso ejemplo consta de las siguientes etapas: The example process consists of the following stages:

5 - Generación de cloruro cálcico por reacción de lodos de mármol con ácido clorhídrico (1). 5 - Generation of calcium chloride by reaction of marble sludge with hydrochloric acid (1).

--
Deshidrataci�n y neutralización del gas carbónico resultante por adsorción en columna (2).  Dehydration and neutralization of the resulting carbonic gas by column adsorption (2).

--
Almacenamiento del carbónico a presión (3). Storage of carbon dioxide under pressure (3).

10 - Neutralización de la disolución de cloruro cálcico por absorción en columna (4). 10 - Neutralization of the calcium chloride solution by column absorption (4).

--
Generación de partículas de carbonato cálcico por reacción entre el carbónico y la disolución en tanque agitado en presencia de los agentes de superficie y el copol�mero (5).  Generation of calcium carbonate particles by reaction between the carbonic and the stirred tank solution in the presence of surface agents and the copolymer (5).

Los agentes de superficie a usar se seleccionan en función de las aplicaciones 15 posteriores que se les vaya a dar a las partículas obtenidas. En función de estos agentes de superficie se seleccionan las condiciones operativas de producción. The surface agents to be used are selected according to the subsequent applications that will be given to the particles obtained. Depending on these surface agents, the operating conditions of production are selected.

La disolución obtenida del tanque (5), se puede decantar y filtrar posteriormente para obtener una pasta. Si esa pasta se seca con aire caliente y posteriormente se calcina a una temperatura comprendida entre 150 y 250�C, pueden obtenerse las The solution obtained from the tank (5), can be decanted and filtered later to obtain a paste. If that paste is dried with hot air and then calcined at a temperature between 150 and 250�C, the

20 partículas porosas. De ahí deben trasladarse a almacenamiento hermético en condiciones de humedad inferior al 1%. 20 porous particles From there they must be transferred to airtight storage under conditions of humidity below 1%.

Claims (2)

REIVINDICACIONES 1�.- Un procedimiento para la generación de partículas de carbonato cálcico micro y meso porosas por vía húmeda a partir de los lodos producidos en el corte, aserrado, apomazado y pulido de rocas marmóreas y calizas, caracterizado porque incluye las siguientes etapas: 1�.- A procedure for the generation of particles of micro calcium and meso porous calcium carbonate by wet route from the sludge produced in the sawing, sawing, tapping and polishing of marble and limestone rocks, characterized by the following stages:
--
Reacci�n química entre la suspensión acuosa de lodos de corte con ácido clorhídrico, con generación de di�xido de carbono gaseoso y una suspensión de cloruro de calcio. Chemical reaction between the aqueous sludge slurry suspension with hydrochloric acid, generating gaseous carbon dioxide and a calcium chloride suspension.
--
Reacci�n química entre la suspensión de cloruro de calcio as� obtenida con di�xido de carbono, en presencia de un agente estabilizador de carga (tensioactivo hidrosoluble de naturaleza cati�nica, ani�nica o neutra) y un copol�mero (poliestireno, ácido poliacr�lico o polivinil pirrolidina), con generación de ácido clorhídrico y de carbonato cálcico en forma de partículas con el copol�mero embebido en su estructura. Chemical reaction between the calcium chloride suspension thus obtained with carbon dioxide, in the presence of a charge stabilizing agent (water-soluble surfactant of a catholic, anionic or neutral nature) and a copolymer ( polystyrene, polyacrylic acid or polyvinyl pyrrolidine), with generation of hydrochloric acid and calcium carbonate in particulate form with the copolymer embedded in its structure.
--
Secado de la suspensión obtenida y calcinación final de las partículas a una temperatura entre 150 y 250�C, con lo que el copol�mero del interior de las partículas se destruye generando una estructura porosa tridimensional. Drying of the suspension obtained and final calcination of the particles at a temperature between 150 and 250 ° C, whereby the copolymer inside the particles is destroyed generating a three-dimensional porous structure.
2�.- Procedimiento según reivindicación 1 realizado a partir de cualquier tipo de residuo de la industria de transformación y extracción de piedra natural carbonatada, que previamente se ha acondicionado como disolución acuosa. 2�.- Procedure according to claim 1 made from any type of residue from the processing and extraction industry of carbonated natural stone, which has previously been conditioned as an aqueous solution. 3�.- Un procedimiento según reivindicación 1 caracterizado porque se realiza a partir de una disolución acuosa cualquiera que contiene carbonato cálcico en disolución, independientemente de la presencia de cualquier otro tipo de compuestos químicos o mineral�gicos que influyan en la pureza del material. 3.- A process according to claim 1 characterized in that it is carried out from any aqueous solution containing calcium carbonate in solution, regardless of the presence of any other type of chemical or mineral compounds that influence the purity of the material. Figura 1 Figure 1 OFICINA ESPAÑOLA DE PATENTES Y MARCAS SPANISH OFFICE OF THE PATENTS AND BRAND N.� solicitud: 201232009 Application No.: 201232009 ESPA�A SPAIN Fecha de presentación de la solicitud: 21.12.2012 Date of submission of the application: 21.12.2012 Fecha de prioridad: Priority Date: INFORME SOBRE EL ESTADO DE LA TECNICA REPORT ON THE STATE OF THE TECHNIQUE 51 Int. Cl. : C01F11/18 (2006.01) C01F1/00 (2006.01) 51 Int. Cl.: C01F11 / 18 (2006.01) C01F1 / 00 (2006.01) DOCUMENTOS RELEVANTES RELEVANT DOCUMENTS
Categor�a Category
56 Documentos citados Reivindicaciones afectadas 56 Documents cited Claims Affected
A TO
LINA ZHAO et al. Biomimetic synthesis of hollow microspheres of calcium carbonate crystals in the presence of polymer and surfactant. Colloids and surfaces. A: Physicochemical and engineering aspects. 11.11.2011. Vol: 393, páginas: 139-143. . Introduction, 2. Experiment, 4. Conclusions. 1-3 LINA ZHAO et al. Biomimetic synthesis of hollow microspheres of calcium carbonate crystals in the presence of polymer and surfactant. Colloids and surfaces. A: Physicochemical and engineering aspects. 11.11.2011. Vol: 393, pages: 139-143. . Introduction, 2. Experiment, 4. Conclusions. 1-3
A TO
SHEN et al. Morphological control of calcium carbonate crystals by polyvinylpyrrolidone and sodium dodecyl benzene sulfonate. Colloids and surfaces, A: Physicochemical and engineering aspects. 10.12.2004, Vol. 251, N� 1-3, páginas: 87-91. 1. Introduction, 2. Experiment, 4. Conclusions. 1-3 SHEN et al. Morphological control of calcium carbonate crystals by polyvinylpyrrolidone and sodium dodecyl benzene sulfonate. Colloids and surfaces, A: Physicochemical and engineering aspects. 10.12.2004, Vol. 251, No. 1-3, pages: 87-91. 1. Introduction, 2. Experiment, 4. Conclusions. 1-3
A TO
PAN et al. Controlled synthesis of hollow calcite microspheres modulated by polyacrylic acid and sodium dodecyl sulfonate. Materials letters, 21.04.2007, Vol. 61, N� 13, páginas: 2810-2813. Resumen, 1. Introduction, 4. Conclusions. 1-3 PAN et al. Controlled synthesis of hollow calcite microspheres modulated by polyacrylic acid and sodium dodecyl sulfonate. Materials letters, 04/21/2007, Vol. 61, No. 13, pages: 2810-2813. Summary, 1. Introduction, 4. Conclusions. 1-3
A TO
JI et al. The synthesis of hollow CaCO3 microspheres in mixed solutions of surfactant and polymer. Material letters, 19.12.2007, Vol. 62, N�: 4-5, páginas: 751-754. Resumen, 1. Introduction, 2. Experiment, 4. Conclusions. 1-3 JI et al. The synthesis of hollow CaCO3 microspheres in mixed solutions of surfactant and polymer. Material letters, 19.12.2007, Vol. 62, N�: 4-5, pages: 751-754. Summary, 1. Introduction, 2. Experiment, 4. Conclusions. 1-3
A TO
C�LFEN H et al. A systematic examination of the morphogenesis of calcium carbonate in the presence of a double-hydrophilic block copolymer. Chemistry-A European Journal, 2001, Vol. 7, N� 1, páginas: 106-116. Crystallization of CaCO3. 1-3 C�LFEN H et al. A systematic examination of the morphogenesis of calcium carbonate in the presence of a double-hydrophilic block copolymer. Chemistry-A European Journal, 2001, Vol. 7, No. 1, pages: 106-116. Crystallization of CaCO3. 1-3
A TO
NEIRA-CARRILLO A et al. Synthesis and characterization of sulfonated polymethylsiloxane polymer as template for crystal growth of CaCO3. Colloid and Polymer Science, 04.12.2008, Vol. 287, N� 4, páginas: 385-393. Introduction, Cristallization method. 1-3 NEIRA-CARRILLO A et al. Synthesis and characterization of sulfonated polymethylsiloxane polymer as template for crystal growth of CaCO3. Colloid and Polymer Science, 04.12.2008, Vol. 287, No. 4, pages: 385-393. Introduction, Cristallization method. 1-3
A TO
LI W et al. Submicronic calcite particles with controlled morphology tailored by polymer skeletons via carbonation route with compressed or supercritical CO2. Green Chemistry, 2009, Vol. 11, N� 10, páginas: 1541-1549. Resumen. 1-3 LI W et al. Submicronic calcite particles with controlled morphology tailored by polymer skeletons via carbonation route with compressed or supercritical CO2. Green Chemistry, 2009, Vol. 11, No. 10, pages: 1541-1549. Summary. 1-3
A TO
TW 200823156 A (CHIN MIN INST OF TECHNOLOGY) 01.06.2008, resumen [en línea] recuperado de EPODOC/EPO y WPI/DERWENT. 1-3 TW 200823156 A (CHIN MIN INST OF TECHNOLOGY) 01.06.2008, summary [online] retrieved from EPODOC / EPO and WPI / DERWENT. 1-3
Categor�a de los documentos citados X: de particular relevancia Y: de particular relevancia combinado con otro/s de la misma categoría A: refleja el estado de la técnica O: referido a divulgación no escrita P: publicado entre la fecha de prioridad y la de presentación de la solicitud E: documento anterior, pero publicado después de la fecha de presentación de la solicitud Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the submission of the application E: previous document, but published after the date of submission of the application
El presente informe ha sido realizado • para todas las reivindicaciones • para las reivindicaciones n�: This report has been prepared • for all claims • for claims no:
Fecha de realización del informe 28.03.2014 Date of realization of the report 28.03.2014
Examinador M. González Rodríguez Página 1/5 Examiner M. González Rodríguez Page 1/5
INFORME DEL ESTADO DE LA TÉCNICA REPORT OF THE STATE OF THE TECHNIQUE Documentaci�n mínima buscada (sistema de clasificación seguido de los símbolos de clasificación) C01F Bases de datos electrónicas consultadas durante la búsqueda (nombre de la base de datos y, si es posible, términos de Minimum documentation sought (classification system followed by classification symbols) C01F Electronic databases consulted during the search (name of the database and, if possible, terms of b�squeda utilizados) INVENES, EPODOC, WPI, XPESP, COMPENDEX, INSPEC, MEDLINE, NPL, HCAPLUS. search used) INVENES, EPODOC, WPI, XPESP, COMPENDEX, INSPEC, MEDLINE, NPL, HCAPLUS. OPINI�N ESCRITA  WRITTEN OPINION Fecha de Realización de la Opinión Escrita: 28.03.2014 Date of Written Opinion: 28.03.2014 Declaraci�n Statement
Novedad (Art. 6.1 LP 11/1986) Novelty (Art. 6.1 LP 11/1986)
Reivindicaciones Reivindicaciones 1-3 SI NO Claims Claims 1-3 IF NOT
Actividad inventiva (Art. 8.1 LP11/1986) Inventive activity (Art. 8.1 LP11 / 1986)
Reivindicaciones Reivindicaciones 1-3 SI NO Claims Claims 1-3 IF NOT
Se considera que la solicitud cumple con el requisito de aplicación industrial. Este requisito fue evaluado durante la fase de examen formal y técnico de la solicitud (Artículo 31.2 Ley 11/1986). The application is considered to comply with the industrial application requirement. This requirement was evaluated during the formal and technical examination phase of the application (Article 31.2 Law 11/1986). Base de la Opinión.-  Opinion Base.- La presente opinión se ha realizado sobre la base de la solicitud de patente tal y como se publica. This opinion has been made on the basis of the patent application as published. OPINI�N ESCRITA  WRITTEN OPINION 1. Documentos considerados.-1. Documents considered.- A continuación se relacionan los documentos pertenecientes al estado de la técnica tomados en consideración para la realización de esta opinión. The documents belonging to the state of the art taken into consideration for the realization of this opinion are listed below.
Documento Document
Número Publicación o Identificación Fecha Publicación Publication or Identification Number publication date
D01 D01
LINA ZHAO et al. Biomimetic synthesis of hollow microspheres of calcium carbonate crystals in the presence of polymer and surfactant. 11.11.2011 LINA ZHAO et al. Biomimetic synthesis of hollow microspheres of calcium carbonate crystals in the presence of polymer and surfactant. 11.11.2011
D02 D02
SHEN et al. Morphological control of calcium carbonate crystals by polyvinylpyrrolidone and sodium dodecyl benzene sulfonate. 20.12.2004 SHEN et al. Morphological control of calcium carbonate crystals by polyvinylpyrrolidone and sodium dodecyl benzene sulfonate. 20.12.2004
D03 D03
PAN et al. Controlled synthesis of hollow calcite microspheres modulated by polyacrylic acid and sodium dodecyl sulfonate. 21.04.2007 PAN et al. Controlled synthesis of hollow calcite microspheres modulated by polyacrylic acid and sodium dodecyl sulfonate. 04/21/2007
D04 D04
JI et al. The synthesis of hollow CaCO3 microspheres in mixed solutions of surfactant and polymer. 19.12.2007 JI et al. The synthesis of hollow CaCO3 microspheres in mixed solutions of surfactant and polymer. 19.12.2007
D05 D05
C�LFEN H et al. A systematic examination of the morphogenesis of calcium carbonate in the presence of a double-hydrophilic block copolymer. 05.01.2001 C�LFEN H et al. A systematic examination of the morphogenesis of calcium carbonate in the presence of a double-hydrophilic block copolymer. 05.01.2001
D06 D06
NEIRA-CARRILLO A et al. Synthesis and characterization of sulfonated polymethylsiloxane polymer as template for crystal growth of CaCO3. 04.12.2008 NEIRA-CARRILLO A et al. Synthesis and characterization of sulfonated polymethylsiloxane polymer as template for crystal growth of CaCO3. 04.12.2008
D07 D07
LI W et al. Submicronic calcite particles with controlled morphology tailored by polymer skeletons via carbonation route with compressed or supercritical CO2. 2009 LI W et al. Submicronic calcite particles with controlled morphology tailored by polymer skeletons via carbonation route with compressed or supercritical CO2. 2009
D08 D08
TW 200823156 A (CHIN MIN INST OF TECHNOLOGY) 01.06.2008 TW 200823156 A (CHIN MIN INST OF TECHNOLOGY) 01.06.2008
2. Declaración motivada según los artículos 29.6 y 29.7 del Reglamento de ejecución de la Ley 11/1986, de 20 de marzo, de Patentes sobre la novedad y la actividad inventiva; citas y explicaciones en apoyo de esta declaración 2. Statement motivated according to articles 29.6 and 29.7 of the Regulations for the execution of Law 11/1986, of March 20, on Patents on novelty and inventive activity; quotes and explanations in support of this statement El objeto de la invención es un procedimiento para la generación de partículas de carbonato cálcico (CaCO3) micro y meso porosas por vía húmeda que comprende tres etapas: 1. reacción química de una suspensión acuosa de lodos de rocas marmóreas y calizas con ácido clorhídrico (HCl) para formar cloruro cálcico (CaCl2); 2. reacción de la suspensión de cloruro cálcico formado (CaCl2) con di�xido de carbono (CO2) en presencia de un agente estabilizador de carga y un pol�mero; 3. Secado y calcinación de las partículas. The object of the invention is a process for the generation of micro-meso and meso porous calcium carbonate (CaCO3) particles comprising three stages: 1. chemical reaction of an aqueous sludge suspension of marble and limestone rocks with hydrochloric acid ( HCl) to form calcium chloride (CaCl2); 2. Reaction of the suspension of calcium chloride formed (CaCl2) with carbon dioxide (CO2) in the presence of a charge stabilizing agent and a polymer; 3. Drying and calcination of the particles. El documento D01 divulga un procedimiento de síntesis de microesferas de carbonato cálcico (CaCO3) mediante una reacción de precipitación a partir de cloruro de calcio (CaCl2) y carbonato de sodio (Na2CO3) en presencia de un agente tensioactivo (SDS � dodecilsulfato sádico) y un pol�mero (PVP � polivinilpirrolidona). (Ver 1. Introduction, 2. Experiment, 4. Conclusions). Document D01 discloses a method of synthesis of calcium carbonate microspheres (CaCO3) by a precipitation reaction from calcium chloride (CaCl2) and sodium carbonate (Na2CO3) in the presence of a surfactant (SDS � sadic dodecyl sulfate) and a polymer (PVP and polyvinylpyrrolidone). (See 1. Introduction, 2. Experiment, 4. Conclusions). El documento D02 divulga un procedimiento de obtención de partículas de carbonato de calcio (CaCO3) mediante la reacción de cloruro de calcio (CaCl2) con carbonato de sodio (Na2CO3) en presencia de un agente tensioactivo ani�nico (SDBS � dodecilbencenosulfonato de sodio) y un pol�mero (PVP � polivinilpirrolidona). (Ver 1. Introduction, 2. Experiment, 4. Conclusions). Document D02 discloses a process for obtaining calcium carbonate particles (CaCO3) by reacting calcium chloride (CaCl2) with sodium carbonate (Na2CO3) in the presence of an anionic surfactant (SDBS sodium dodecylbenzenesulfonate) and a polymer (PVP pol polyvinylpyrrolidone). (See 1. Introduction, 2. Experiment, 4. Conclusions). Los documentos D03 y D04 divulgan procedimientos de síntesis de microesferas de carbonato cálcico (CaCO3) utilizando como aditivos un surfactante (SDS � dodecilsulfato sádico) y un pol�mero (PAA � ácido poliacr�lico en D03 y PEG � polietietilenglicol en D04), pero en ambos casos los reactivos utilizados son cloruro cálcico (CaCl2) y carbonato de sodio (Na2CO3) -no se utiliza di�xido de carbono (CO2)-. (Ver D03: resumen, 1. Introduction, 4. Conclusions; D04: resumen, 1. Introduction, 2. Experiment, 4. Conclusions). Lo mismo ocurre con el procedimiento divulgado en D05, pero en esta caso el aditivo utilizado es un copol�mero (Ver Crystallization of CaCO3). Documents D03 and D04 disclose procedures for the synthesis of calcium carbonate microspheres (CaCO3) using as additives a surfactant (SDS � sadic dodecyl sulfate) and a polymer (PAA � polyacrylic acid in D03 and PEG � polyethylene glycol in D04), but in both cases the reagents used are calcium chloride (CaCl2) and sodium carbonate (Na2CO3) - no carbon dioxide (CO2) is used. (See D03: summary, 1. Introduction, 4. Conclusions; D04: summary, 1. Introduction, 2. Experiment, 4. Conclusions). The same applies to the procedure disclosed in D05, but in this case the additive used is a copolymer (See Crystallization of CaCO3). El documento D06 divulga un procedimiento de síntesis de partículas de carbonato cálcico (CaCO3) a partir de una suspensión de cloruro cálcico (CaCl2) por la que se hace burbujear di�xido de carbono (CO2) en presencia de un pol�mero (S-PMS � polimetilsiloxano sulfonatado), pero no se hace referencia al uso de surfactantes. (Introduction, Cristallization method). Document D06 discloses a method of synthesis of calcium carbonate particles (CaCO3) from a suspension of calcium chloride (CaCl2) by which carbon dioxide (CO2) is bubbled in the presence of a polymer (S -PMS � sulfonated polymethylsiloxane), but no reference is made to the use of surfactants. (Introduction, Cristallization method). OPINI�N ESCRITA  WRITTEN OPINION El documento D07 divulga un procedimiento de obtención de carbonato cálcico (CaCO3) en el que los reactivos utilizados son hidróxido de calcio (Ca(OH)2) y di�xido de carbono (CO2) y donde se añaden además sales de celulosa (Ver resumen). Document D07 discloses a process for obtaining calcium carbonate (CaCO3) in which the reagents used are calcium hydroxide (Ca (OH) 2) and carbon dioxide (CO2) and where cellulose salts are also added (See summary). Por último, documento D08 divulga un procedimiento de preparación de partículas de carbonato cálcico (CaCO3) a partir de residuos de la industria marmórea, donde en primer lugar se hace reaccionar la corriente de lodos marmóreos con ácido clorhídrico (HCl) para obtener cloruro cálcico (CaCl2), se ajusta el pH y a continuación se inyecta di�xido de carbono en la disolución para obtener carbonato cálcico, que se filtra y se seca. No se utilizan surfactantes � pol�meros como aditivo (Ver resumen WPI). Finally, document D08 discloses a process for preparing particles of calcium carbonate (CaCO3) from residues of the marble industry, where the stream of marble sludge is first reacted with hydrochloric acid (HCl) to obtain calcium chloride ( CaCl2), the pH is adjusted and then carbon dioxide is injected into the solution to obtain calcium carbonate, which is filtered and dried. No polymer surfactants are used as an additive (See WPI summary). Ninguno de los documentos anteriores ni ninguna combinación relevante de los mismos recoge un procedimiento de generación de partículas de carbonato cálcico micro y mesoporosas (CaCO3) con una primera etapa de reacción química de una suspensión acuosa de lodos de rocas marmóreas y calizas con ácido clorhídrico (HCl) en la que se obtiene cloruro cálcico (CaCl2), una segunda etapa donde el cloruro cálcico formado (CaCl2) reacciona con di�xido de carbono (CO2) en presencia de un agente estabilizador de carga y un pol�mero y una tercera etapa de secado y calcinación de las partículas obtenidas donde se destruye el pol�mero, tal y como se recoge en la reivindicación 1 de la solicitud. None of the above documents or any relevant combination thereof collects a method of generating micro and mesoporous calcium carbonate particles (CaCO3) with a first chemical reaction stage of an aqueous sludge suspension of marble and limestone rocks with hydrochloric acid ( HCl) in which calcium chloride (CaCl2) is obtained, a second stage where the calcium chloride formed (CaCl2) reacts with carbon dioxide (CO2) in the presence of a charge stabilizing agent and a polymer and a third drying and calcining step of the particles obtained where the polymer is destroyed, as set out in claim 1 of the application. En consecuencia, la invención tal y como se recoge en las reivindicaciones 1-3 de la solicitud, es nueva e implica actividad inventiva. Accordingly, the invention, as set forth in claims 1-3 of the application, is new and involves inventive activity.
ES201232009A 2012-12-21 2012-12-21 Procedure for the generation of micro particles of high-porosity calcium carbonate by means of waste from the natural stone processing industry waste Expired - Fee Related ES2471317B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
ES201232009A ES2471317B1 (en) 2012-12-21 2012-12-21 Procedure for the generation of micro particles of high-porosity calcium carbonate by means of waste from the natural stone processing industry waste

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
ES201232009A ES2471317B1 (en) 2012-12-21 2012-12-21 Procedure for the generation of micro particles of high-porosity calcium carbonate by means of waste from the natural stone processing industry waste

Publications (2)

Publication Number Publication Date
ES2471317A1 true ES2471317A1 (en) 2014-06-25
ES2471317B1 ES2471317B1 (en) 2015-03-10

Family

ID=50972824

Family Applications (1)

Application Number Title Priority Date Filing Date
ES201232009A Expired - Fee Related ES2471317B1 (en) 2012-12-21 2012-12-21 Procedure for the generation of micro particles of high-porosity calcium carbonate by means of waste from the natural stone processing industry waste

Country Status (1)

Country Link
ES (1) ES2471317B1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105197976A (en) * 2015-10-19 2015-12-30 高大元 Preparation method of nano calcium carbonate powder
CN107475769A (en) * 2017-08-10 2017-12-15 青阳县永诚钙业有限责任公司 A kind of preparation method for extracting calcium carbonate crystal whisker

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200823156A (en) * 2006-11-17 2008-06-01 Chin Min Inst Of Technology A method for manufacturing high purity calcium carbonate powder from marble sludge

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200823156A (en) * 2006-11-17 2008-06-01 Chin Min Inst Of Technology A method for manufacturing high purity calcium carbonate powder from marble sludge

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
CÖLFEN H et al. A systematic examination of the morphogenesis of calcium carbonate in the presence of a double-hydrophilic block copolymer. Chemistry-A European Journal, 2001, Vol. 7, Nº 1, páginas: 106-116. Crystallization of CaCO3. *
JI et al. The synthesis of hollow CaCO3 microspheres in mixed solutions of surfactant and polymer. Material letters, 19/12/2007, Vol. 62, Nº: 4-5, páginas: 751 - 754. Resumen, 1. Introduction, 2. Experiment, 4. Conclusions. *
LI W et al. Submicronic calcite particles with controlled morphology tailored by polymer skeletons via carbonation route with compressed or supercritical CO2. Green Chemistry, 2009, Vol. 11, Nº 10, páginas: 1541-1549. Resumen. *
LINA ZHAO et al. Biomimetic synthesis of hollow microspheres of calcium carbonate crystals in the presence of polymer and surfactant. Colloids and surfaces. A: Physicochemical and engineering aspects. 11/11/2011. Vol: 393, páginas: 139 - 143. . Introduction, 2. Experiment, 4. Conclusions. *
NEIRA-CARRILLO A et al. Synthesis and characterization of sulfonated polymethylsiloxane polymer as template for crystal growth of CaCO3. Colloid and Polymer Science, 04/12/2008, Vol. 287, Nº 4, páginas: 385 - 393. Introduction, Cristallization method. *
PAN et al. Controlled synthesis of hollow calcite microspheres modulated by polyacrylic acid and sodium dodecyl sulfonate. Materials letters, 21/04/2007, Vol. 61, Nº 13, páginas: 2810 - 2813. Resumen, 1. Introduction, 4. Conclusions. *
SHEN et al. Morphological control of calcium carbonate crystals by polyvinylpyrrolidone and sodium dodecyl benzene sulfonate. Colloids and surfaces, A: Physicochemical and engineering aspects. 10/12/2004, Vol. 251, Nº 1-3, páginas: 87 - 91. 1. Introduction, 2. Experiment, 4. Conclusions. *

Also Published As

Publication number Publication date
ES2471317B1 (en) 2015-03-10

Similar Documents

Publication Publication Date Title
Guo et al. Hollow carbonated hydroxyapatite microspheres with mesoporous structure: hydrothermal fabrication and drug delivery property
Guo et al. Synthesis of vaterite CaCO3 micro-spheres by carbide slag and a novel CO2-storage material
TW201516017A (en) Aerated composite materials, methods of production and uses thereof
Lombardi et al. Processing of a natural hydroxyapatite powder: from powder optimization to porous bodies development
JP2003306325A (en) Basic magnesium carbonate, its production method, and composition or structure including the basic magnesium carbonate
ES2471317A1 (en) Procedure for the generation of high porosity calcium carbonate microparticles by wet process from waste from the natural stone transformation industry (Machine-translation by Google Translate, not legally binding)
EA039534B1 (en) Catalytically active foam formation powder
Sreethawong et al. Sol–gel synthesis of mesoporous assembly of Nd2O3 nanocrystals with the aid of structure-directing surfactant
Rahmat et al. Sodium silicate as source of silica for synthesis of mesoporous SBA-15
Cheng et al. Fast fabrication of hollow silica spheres with thermally stable nanoporous shells
CN106564873A (en) Novel macro- and micro-porous thin film carbon material and preparation method of same
WO2013092650A1 (en) Process for preparing sodium bicarbonate particles
Moreira et al. A description of the formation and growth processes of CaTiO 3 mesocrystals: a joint experimental and theoretical approach
Yang et al. Preparation of high surface area CaCO3 by bubbling CO2 in aqueous suspensions of Ca (OH) 2: Effects of (NaPO3) 6, Na5P3O10, and Na3PO4 additives
JP2023541834A (en) Scalable synthesis of enveloped mineral carbon
CN101928032A (en) Organic solvent hydrothermal method for preparing cubic, flower-like or porous calcium carbonate
JP5273551B2 (en) Method for producing fibrous porous silica particles
ES2471567A1 (en) Procedure for the generation of nanoparticles of calcium carbonate by wet process from residues of the natural stone transformation industry (Machine-translation by Google Translate, not legally binding)
Peng et al. Hierarchically porous CaCO3 monoliths prepared from leaf template
CN104817094B (en) Hydration and anhydrous multistage porous calcium borate microsphere low-temperature hydrothermal-thermal conversion synthetic method
Bi et al. Synthesis and characterization of nickel-based monolithic aerogel via sol-gel method
JP5321937B2 (en) Process for producing macaroni-like calcium carbonate
JP2004359543A (en) Foamed silica gel and method for manufacturing it
Sarıcı-Özdemir Examination of the adsorption for methylene blue using different adsorbents.
RU2503619C1 (en) Method of obtaining granular sorbent

Legal Events

Date Code Title Description
FG2A Definitive protection

Ref document number: 2471317

Country of ref document: ES

Kind code of ref document: B1

Effective date: 20150310

FD2A Announcement of lapse in spain

Effective date: 20210915