[go: up one dir, main page]

WO1997006785A1 - Particules de poudres a surface modifiee - Google Patents

Particules de poudres a surface modifiee Download PDF

Info

Publication number
WO1997006785A1
WO1997006785A1 PCT/IL1996/000062 IL9600062W WO9706785A1 WO 1997006785 A1 WO1997006785 A1 WO 1997006785A1 IL 9600062 W IL9600062 W IL 9600062W WO 9706785 A1 WO9706785 A1 WO 9706785A1
Authority
WO
WIPO (PCT)
Prior art keywords
water soluble
group
mineral
metal cations
water
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.)
Ceased
Application number
PCT/IL1996/000062
Other languages
English (en)
Inventor
Isaac Yaniv
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.)
Baran Advanced Materials 94 Ltd
Original Assignee
Baran Advanced Materials 94 Ltd
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 Baran Advanced Materials 94 Ltd filed Critical Baran Advanced Materials 94 Ltd
Priority to AU66291/96A priority Critical patent/AU6629196A/en
Publication of WO1997006785A1 publication Critical patent/WO1997006785A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/021—Calcium carbonates
    • C09C1/022—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/675—Oxides, hydroxides or carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/90—Other properties not specified above
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape

Definitions

  • This invention relates to surface-modified powders of natural and artificial minerals based on Ca and/or Mg such as MgO, talc (3MgO SiO2-H2O), Mg(OH)2, CaCO3, CaMg(CO3)2, MgCO3, Ca(OH)2, CaSO and mixtures thereof.
  • the invention also relates to methods for their production and their use.
  • the invention makes it possible to alter the crystallographic nature of the particles as well as their surface charges and to form powders of improved performance and compatibility with a variety of materials, such as plastics and cellulose, and lowers the cost of their production.
  • the present invention is particularly important in the production of powders for the paper industry, for the fertilizer industry, for the cosmetic industry, for the paint industry, for the ceramic industry, for the plastic and rubber industries, etc.
  • Powders are intensively used in numerous applications, e.g. fillers and flame retardants in the paper and in the plastics industries, as raw materials for ceramics and cements, as constituents in cosmetics, etc..
  • their particle size distribution should be controlled, usually reduced, and their surface properties should be compatible with those of the substrates with which these powders are to be used.
  • Another approach for obtaining fine powders involves their controlled recrystallization or precipitation by reacting suitable reactants.
  • any slurry of fine powders be stable, namely, that the fine particles will not undergo coalescence and the solids will not separate or precipitate even after long periods of time. This can be achieved, among other methods, by imparting large electric charges to the surfaces of the fine particles.
  • a typical and most important example is powdered CaCO3- Knowing the surface properties of calcite and understanding of how to modify them in order to improve its separation from other minerals and its properties as a major filler in the plastics and the paper industries, are of prime importance.
  • the known art allows to obtain, quite easily, negatively charged chalk powders by grinding/milling calcite or precipitating it by reacting e.g. Ca(OH)2 and CO2 in water to form PCC (precipitated calcium carbonate).
  • PCC precipitated calcium carbonate
  • the products obtained are negatively charged with small electric charges that do not prevent the coalescence ofthe fine particles and their precipitation out of the produced slurries.
  • the calcite powders obtained do not attract carboxylic acid salts and cellulose, which are negatively charged.
  • the surface ofthe calcite are coated with minor impurities that turn the overall surface charge to weakly positive. However, this does not improve much the relevant properties of the calcite powders.
  • this working pH range is not broad enough to produce calcite of prime properties, as specified above.
  • the electric charges on its surface are not sufficient to prevent the flocculation of the fine particles and also the tendency of the calcite particles to adsorb negatively charged species such as cellulose and fatty acid salts onto their surfaces is quite limited or non-existent.
  • Obtaining highly positively charged calcite particles that do not flocculate and also strongly attract carboxylic acid salts and cellulose is, as mentioned above, of prime industrial importance.
  • the calcite highly positively charged at the pH range above 6, especially at above 7, is also important in the beneficiation of phosphate rocks, in which the calcite can be coated, selectively, with inexpensive carboxylic acid salts and be separated from the apatite, francolite, crandalite, etc.; in the polymers and plastics industry, where the calcite is coated with fatty acids prior to its use as a filler; in the paper industry, at which the attachment of the relatively expensive cellulose to the maximum amount of the relatively inexpensive calcite may give rise to outstanding economical benefits; in the production of highly positively charged fine powders (regular and PCC) in stable and transportable slurries; in the production of highly positively charged PCC in which operation the following advantages can be achieved: a) Operating under an additional controlling parameter (temperature, pH, stirring, etc.) over the crystalline size distribution, b) Obtaining, mainly, single crystals that are already coated with the suitable reagent(s).
  • Dolomite (CaMg(CO3)2) and partially calcined dolomite at ⁇ 900°C that gives rise to
  • MgO CaCO3 are ideal candidates for treatment according to the present invention, as they can be subjected to fast grinding/milling by using suitable surface modification methods.
  • the brightness of the MgO improves the overall properties of the final fine powder.
  • the desire to turn powder minerals, that are regularly weakly charged with negative charges, into highly positively charged materials is a general phenomenon.
  • the surface charges of other minerals such as CaMg(CO3)2, MgCO3, Ca(OH)2 and CaSO4 can be turned highly positive by applying the present invention.
  • the resulting surface-modified minerals strongly absorb carboxylic acid salts, which are negatively charged. This leads to substantial advantages in a large variety of applications. For instance, grinding/milling calcite or precipitating calcium carbonate by reacting Ca(OH)2 and CO2 produce products that are usually charged by weak negative electric charges, as described above.
  • carboxylic acid salts results in a very inefficient adsorption of the carboxylates onto the surface of the fine particles. However, this is changed dramatically when the adsorption of the carboxylates is done in the presence water-soluble salts of bi- and tri-valent cations, as described in the examples to follow. A similar behavior is manifested by brucite.
  • surface-modified minerals are Mg(OH)2, MgO, 3MgO SiO2-H2O, CaCO3, CaMg(CO3)2, MgCO3, Ca(OH)2, CaSO4 and mixtures thereof.
  • the concentrations of the water soluble salts should, preferably, be as low as possible, in order to avoid the intensive and expensive washing ofthe final products (the fine powders), which is one ofthe drawbacks ofthe present art, in which processes the minerals are produced in brines.
  • the optimal concentration ofthe salts may vary from case to another, but the tendency is to minimize it as much as possible.
  • the water-soluble salts are selected from halides, sulfates, sulfites, nitrates, nitrites, organic sulfates and organic sulfonates of bivalent and trivalent cations.
  • the halides and sulfates of Mg 4-1" and Al +++ and the halides of Ca "1-1" are the preferable salts.
  • the chloride and sulfate of Mg "1-1" are the most preferable salts.
  • the water-soluble salts can be prepared, in situ, by reacting basic minerals with the required amounts of suitable acids and thereafter controlling the pH by using an appropriate base.
  • the pH can be controlled by using common and inexpensive industrial bases, such as NaOH, MgO, Mg(OH)2, CaO, Ca(OH)2, ammonia, amines, etc..
  • the preferred base is the relatively inexpensive Ca(OH)2-
  • the surface-modification of the minerals is carried out in situ during the grinding/milling of the corresponding minerals with amounts of water of at least 0.5 wt%.
  • the surface-modified minerals are prepared in situ during the wet grinding/milling of the corresponding minerals.
  • Naturally the surface-modified minerals can be further treated with carboxylic (polycarboxylic) acids and/or carboxylic (polycarboxylic) acid salts and/or carboxylic (polycarboxylic) acid anhydrides.
  • the carboxylic and polycarboxylic acid salts are selected from, Na + , Mg* 4" , Al " "1- * " and Ca -1" salts.
  • the carboxylic acids and/or their anhydrides and/or salts are added to the inorganic materials as such or together with other substances.
  • the optimum pH range for applying these carboxylic acids is above the pKa values ofthe respective acids.
  • the carboxylic acids and/or carboxylic acid salts and or carboxylic acid anhydrides may or may not have polymerized, in situ, during the production ofthe powders, or may have partially polymerized, in situ, during the production of the powders, and when it has polymerized it is dimerized and/or oligomerized and/or polymerized in the presence or the absence of any added polymerization initiators.
  • the polymerization initiators, if added, are selected from among organic azo compounds and organic peroxide compounds, such as percarboxy lates; inorganic peroxides, such as. hydrogen peroxide, persulfates, percarbonates and perborates.
  • additives that are commonly used in the art are chosen from among long chain fatty acid esters, paraffins, polymer greases, waxes and silicone rubbers. Of course, other conventional additives can also be added. In a prefe ⁇ ed mode of operation, these additives may be pre-mixed with suitable carboxylic acids.
  • the production of the surface-modified minerals and the beneficiation of the various minerals can be carried out in sti ⁇ ed reactors and/or in flotation reactors, or in any other suitable equipment, as will be easily recognized by the skilled person.
  • Tests # 10, 10a and 10b are reference experiments.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

L'invention concerne un procédé relatif à l'élaboration de minéraux ayant une surface modifiée et constitué essentiellement de poudres minérales naturelles et/ou artificielles insolubles dans l'eau ou modérément solubles dans l'eau, à base de Ca et/ou Mg. Les particules de poudre sont revêtues de sels hydrosolubles de cations métalliques bivalents et/ou trivalents (dont la concentration est supérieure à 100 ppm pour CaCo3 et supérieure à 500 ppm pour les autres minéraux, sur la base de la solution aqueuse), pour un pH contrôlé dans une fourchette comprise entre 5,5 et 12,5 ou, si le potentiel zéro naturel des minéraux spécifiques est inférieur à 5, à un pH compris entre ce potentiel et 12,5.
PCT/IL1996/000062 1995-08-07 1996-07-24 Particules de poudres a surface modifiee Ceased WO1997006785A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU66291/96A AU6629196A (en) 1995-08-07 1996-07-24 Surface-modified powders

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IL11485395A IL114853A0 (en) 1995-08-07 1995-08-07 Surface-modified powders
IL114853 1995-08-07

Publications (1)

Publication Number Publication Date
WO1997006785A1 true WO1997006785A1 (fr) 1997-02-27

Family

ID=11067842

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IL1996/000062 Ceased WO1997006785A1 (fr) 1995-08-07 1996-07-24 Particules de poudres a surface modifiee

Country Status (3)

Country Link
AU (1) AU6629196A (fr)
IL (1) IL114853A0 (fr)
WO (1) WO1997006785A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7323201B2 (en) 2004-06-08 2008-01-29 Tate & Lyle Ingredients Americas, Inc. Highly soluble form of tricalcium citrate, and methods of its making and use

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113484217B (zh) * 2021-07-06 2024-06-18 西南石油大学 一种去白云石化过程的模拟实验方法
CN113522931B (zh) * 2021-07-09 2023-03-24 浙江工业大学 基于硫化矿物表面原位快速成膜的矿物氧化产酸抑制方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5444113A (en) * 1988-08-08 1995-08-22 Ecopol, Llc End use applications of biodegradable polymers

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5444113A (en) * 1988-08-08 1995-08-22 Ecopol, Llc End use applications of biodegradable polymers

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7323201B2 (en) 2004-06-08 2008-01-29 Tate & Lyle Ingredients Americas, Inc. Highly soluble form of tricalcium citrate, and methods of its making and use
US7781003B2 (en) 2004-06-08 2010-08-24 Tate & Lyle Ingredients Americas, Inc. Highly soluble form of tricalcium citrate, and methods of its making and use

Also Published As

Publication number Publication date
AU6629196A (en) 1997-03-12
IL114853A0 (en) 1995-12-08

Similar Documents

Publication Publication Date Title
JP6802168B2 (ja) 天然炭酸カルシウムを沈降炭酸カルシウムへ変換する方法プロセス
US6235107B1 (en) Method for separating mixture of finely divided minerals and product thereof
US5938833A (en) Chemical process for fractionating mineral particles based on particle size
AU2011240183B2 (en) Process to prepare surface-modified mineral material, resulting products and uses thereof
GB2317167A (en) Preparing calcium carbonate particles of uniform size
US3798046A (en) Modified, precipitated alumino silicate pigments and an improved method for preparing same
EP0556311A1 (fr) Pigments mineraux composite agreges
CN1498925A (zh) 一种复组合填料及其制备方法
WO2005075353A1 (fr) Carbonate particulaire naturel
USRE30568E (en) Modified, precipitated alumino silicate pigments
WO1997006785A1 (fr) Particules de poudres a surface modifiee
US3915734A (en) Modified precipitated alumino silicate pigments and method for preparing same
US5584394A (en) Colored titaniferous coating pigment obtained as a flocculated by-product in a kaolin purification process
EP1255791B1 (fr) Pigments composites contenant des cristaux de carbonate metallique precipites in-situ
US3909286A (en) Modified, precipitated alumino silicate pigments
US6074473A (en) Low viscosity, high solids content slurry
WO1997013815A2 (fr) Poudres enrobees d'un polymere
US12275853B2 (en) Process for preparing surface-reacted calcium carbonate
CA2230892C (fr) Poudres enrobees d'un polymere
WO1996031446A1 (fr) Nouveaux procedes d'elaboration des poudres fines
Ahmed et al. Improvement of Egyptian talc quality for industrial uses by flotation process and leaching

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE HU IL IS JP KE KG KP KR KZ LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG US UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM

121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase