WO1999024361A1 - Method for making calcium carbonate - Google Patents
Method for making calcium carbonate Download PDFInfo
- Publication number
- WO1999024361A1 WO1999024361A1 PCT/BE1998/000171 BE9800171W WO9924361A1 WO 1999024361 A1 WO1999024361 A1 WO 1999024361A1 BE 9800171 W BE9800171 W BE 9800171W WO 9924361 A1 WO9924361 A1 WO 9924361A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aqueous medium
- ppm
- treatment
- additive
- less
- Prior art date
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
-
- 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
- C01F5/00—Compounds of magnesium
- C01F5/24—Magnesium carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—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
- 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
- C01P2006/80—Compositional purity
Definitions
- the subject of the present invention is a process for the manufacture of calcium carbonate and / or calcium and magnesium carbonate particles, in which an aqueous medium of basic pH and containing Ca (OH) 2 and / or Ca is treated. (OH) 2 -Mg (OH) 2 by injecting CO 2 gas therein to form calcium carbonate and / or calcium and magnesium carbonate, and in which the carbonate particles formed are recovered.
- Document FR 2405903 also discloses a process in which the calcium is dissolved in an aqueous medium using ethanolammonium nitrate to transform the calcium into soluble calcium nitrate, and the calcium-rich filtrate is recovered by carbonation by means of CO 2 .
- the particles thus obtained are of high purity and have a whiteness index of approximately 99.5 and a zero yellow index.
- the process according to this document requires two stages of filtration which makes it expensive.
- CN 85103821 describes a process for carbonating lime milk by adding sodium hydrogen carbonate, in the presence of ethanolamine and hydrazine or Na dithionite. This process has the drawback of using a carbonation mode which involves the production of NaOH which is then removed by washing. The degree of whiteness to be obtained by this process is moreover insufficient for many applications.
- the present invention relates to a simple process which makes it possible, by the use of particular additive (s), to reduce the harmful influence of the impurities on the whiteness of the carbonate particles, while avoiding excessively excessive whiteness.
- the aqueous medium is treated in the presence of at least one additive chosen from the group consisting of hydrazine, hydroxylamine, soluble salts of hydroxylamine, and their mixtures.
- This group has the advantage of introducing into the reaction medium a powerful reducing agent which will reduce in basic medium, inter alia Mn 4+ to Mn 2+ and Fe 3+ to Fe 2+ , without requiring any other additive .
- said aqueous medium contains an amount of said additive corresponding to 0.035 to 5% by weight of Ca (OH) 2 and / or Ca (OH) 2 -Mg (OH) 2 .
- the Mn content of the Ca (OH) 2 and / or of the Ca (OH) 2 -Mg (OH) 2 is determined and the aqueous medium is treated in the presence of an aforementioned additive so that said aqueous medium contains from 1 to 8 moles, preferably from 2 to 6 moles, of additives per mole of Mn.
- said treatment is carried out at atmospheric pressure, advantageously under a pressure higher than atmospheric pressure, preferably under an actual pressure between 1, 2.10 5 Pa and 10J0 5 Pa, this treatment being carried out at a temperature between 10 and 100 ° C, advantageously between 20 and 95 ° C, preferably between 30 and 60 ⁇ C, for example around 40 ° C.
- the carbonate particles formed or a suspension containing these particles are subjected to a treatment to decompose the additive.
- a suspension of carbonate particles formed is recovered and then subjected to a treatment to decompose the additive still present in the particles.
- Such treatments are, for example, a treatment with hypochlorite (for example sodium) and / or with water having a temperature above 20 ° C., for example a temperature between 20 and 100 ° C., in particular a temperature of 70 ° C or more and / or with steam.
- the carbonate particles formed are separated from the medium, and the medium is at least partially reused to form an aqueous medium containing Ca (OH) 2 and / or Ca (OH) 2 -Mg (OH) 2 and at least one of said additives.
- the aqueous medium containing Ca (OH) 2 and / or Ca (OH) 2 -Mg (OH) 2 is formed by quenching CaO and / or CaO-MgO by aqueous medium, the additive being added to said aqueous medium before, during and / or after extinction.
- the subject of the invention is also particles of calcium carbonate having an Mn content expressed in MnO of between 80 ppm and 500 ppm, in particular between 90 and 250 ppm, and more precisely between 100 and 200 ppm, a content as Fe expressed as Fe 2 0 3 between 500 and 2000 ppm, in particular less than 1000 ppm, an average diameter by weight less than 5 ⁇ m, a whiteness index measured at 457 nm greater than or equal to 95, but less than 99 , and a yellow index less than or equal to 1.5, but greater than 0.5.
- Such particles have sufficient whiteness, but not excessive whiteness.
- a subject of the invention is also particles of calcium and magnesium carbonate having an Mn content expressed in MnO of between 50 ppm and 500 ppm, in particular between 90 and 250 ppm, and more precisely between 100 and 200 ppm, a Fe content expressed as Fe 2 O 3 less than 2000 ppm, in particular less than 1000 ppm, an average diameter by weight less than 5 ⁇ m, a whiteness index measured at 457 nm greater than or equal to 95, but less than 99, and .a yellow index less than or equal to 1.5, but greater than 0.5.
- an aqueous medium is prepared in 1 containing, for example, from 0.05 to 2.5% of additive.
- CaO particles are added to the aqueous medium so as to form a suspension or milk of Ca (OH) 2 .
- C0 2 is injected into the suspension, for example at a flow rate of 10 to 200 g of COj / hour / liter.
- the temperature of the suspension is adjusted in 3, for example between 20 and 60 ⁇ C, preferably around 40 ⁇ C.
- the injection of CO 2 is advantageously carried out in a tank maintained at an actual pressure of 1.2.10 5 to 10. 10 5 Pa, preferably 1.5 to 3.10 S Pa.
- calcium carbonate particles are recovered by filtration. The filtrate or liquid phase is then reused for the preparation in 1 of the aqueous medium intended for the extinction of CaO.
- FIG. 2 The process represented in FIG. 2 is similar to that represented in FIG. 1, except that hydrazine is used as an additive and that a suspension of particles of calcium carbonate to treatment with an aqueous solution containing sodium hypochlorite, so as to remove all traces of hydrazine. By drying in 6, dry particles are then obtained.
- the process according to FIG. 3 is similar to that of FIG.
- a soluble salt of hydroxylamine for example a salt of strong acid
- this additive being added in 2 during, but preferably after the quicklime has died out, and in 5 the suspension of carbonate particles recovered in 4 is subjected to a treatment with heated water, for example by means of steam ( more than 120 ° C), this treatment being able to decompose all traces of hydroxylamine.
- EXAMPLE 1 A milk of lime was prepared by reaction of quicklime and water.
- the lime used contained 510 ppm of Fe expressed in the form of Fe 2 0 3 and 125 ppm of Mn expressed in the form of MnO.
- the solid content of the milk was 10% by weight for example. Other contents of calcium hydroxide are possible.
- the pH of the lime milk thus formed was approximately 12.
- additives according to the invention were added in an amount corresponding to 0.2% of the weight of quicklime used.
- the whiteness index measured at 457 nm (R 457) and the yellowness index (I.J.) were measured on an Elrepho 2000 device from DATACOLOR.
- Example 1 was repeated, except that quicklime with different Fe and Mn contents (expressed as Fe 2 0 3 and MnO) was used, and hydrazine was used as an additive in an amount of 0.2% by weight of quicklime.
- the following table gives the whiteness index of the calcium carbonate particles prepared without hydrazine (R457 reference) and with hydrazine (R457 hydrazine).
- Example 2 was repeated except that 0.1% hydrazine was used.
- the particles can be subjected to treatment with an aqueous solution containing sodium hypochlorite.
- Example 2 was repeated, except that a quicklime containing 910 ppm of Fe expressed in the form of Fe 2 O 3 and 175 ppm of Mn expressed in the form of MnO was used.
- the additives used were hydrazine (HZ) at 0.1 and 0.2% by weight of quicklime, hydroxylamine hydrochloride (CHA) at 0.1 and 0.2% by weight of lime quicklime, hydroxylamine sulfate (SHA) at 0.2% by weight of quicklime, and mixtures of these additives.
- HZ hydrazine
- CHA hydroxylamine hydrochloride
- SHA hydroxylamine sulfate
- the following table gives the whiteness index and the yellowness index of calcium carbonate particles with an average diameter of between 2 and 2.5 ⁇ m.
- the particles of calcium carbonate produced by the process according to the invention in particular the particles having:
- MnO an Mn content expressed as MnO of between 80 ppm and 500 ppm, preferably of between 90 and 250 ppm, more precisely between 100 and 200 ppm,
- MnO an Mn content expressed as MnO of between 50 ppm and 500 ppm, preferably of between 90 and 250 ppm, more precisely between 100 and 200 ppm,
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU10150/99A AU1015099A (en) | 1997-11-06 | 1998-11-06 | Method for making calcium carbonate |
EP98952452A EP1028916A1 (en) | 1997-11-06 | 1998-11-06 | Method for making calcium carbonate |
BR9813975-4A BR9813975A (en) | 1997-11-06 | 1998-11-06 | Calcium carbonate manufacturing process |
SK629-2000A SK6292000A3 (en) | 1997-11-06 | 1998-11-06 | Method for making calcium carbonate |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE9700894 | 1997-11-06 | ||
BE9700894A BE1011538A4 (en) | 1997-11-06 | 1997-11-06 | METHOD FOR MANUFACTURING Calcium Carbonate. |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999024361A1 true WO1999024361A1 (en) | 1999-05-20 |
Family
ID=3890824
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/BE1998/000171 WO1999024361A1 (en) | 1997-11-06 | 1998-11-06 | Method for making calcium carbonate |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP1028916A1 (en) |
AR (1) | AR017571A1 (en) |
AU (1) | AU1015099A (en) |
BE (1) | BE1011538A4 (en) |
BR (1) | BR9813975A (en) |
PL (1) | PL340094A1 (en) |
SK (1) | SK6292000A3 (en) |
WO (1) | WO1999024361A1 (en) |
ZA (1) | ZA9810169B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7105139B2 (en) | 2002-04-25 | 2006-09-12 | Imerys Pigments, Inc. | Stabilization of the viscosity of formamidine sulfinic acid bleached calcium carbonate slurries |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0197327A2 (en) * | 1985-03-23 | 1986-10-15 | Hoechst Aktiengesellschaft | Process for the preparation of fine, very pure calcium carbonate with a high degree of whiteness |
CN85103821A (en) * | 1985-05-13 | 1986-11-12 | 陈学廉 | Increase the method for whiteness of low density calcium carbonate |
EP0257458A2 (en) * | 1986-08-22 | 1988-03-02 | Akira Matsuzaki | Scrubbing agent and process for producing the same |
US4900533A (en) * | 1981-02-24 | 1990-02-13 | English Clays Lovering Pochin & Company | Alkaline earth metal carbonates |
RO105941B1 (en) * | 1990-04-20 | 1993-01-30 | Centrul Chim Timisoara | Preparation process of a calcium carbonate assortment of high purity and fine granulation |
EP0558275A1 (en) * | 1992-02-26 | 1993-09-01 | Pretoria Portland Cement Company Limited | Production of purified calcium carbonate |
JPH0641892A (en) * | 1992-07-20 | 1994-02-15 | New Oji Paper Co Ltd | Production of light calcium carbonate |
US5290353A (en) * | 1990-07-24 | 1994-03-01 | Lhoist Recherche Et Developpement S.A. | Vaterite and production method |
-
1997
- 1997-11-06 BE BE9700894A patent/BE1011538A4/en not_active IP Right Cessation
-
1998
- 1998-11-06 WO PCT/BE1998/000171 patent/WO1999024361A1/en not_active Application Discontinuation
- 1998-11-06 ZA ZA9810169A patent/ZA9810169B/en unknown
- 1998-11-06 SK SK629-2000A patent/SK6292000A3/en unknown
- 1998-11-06 EP EP98952452A patent/EP1028916A1/en not_active Withdrawn
- 1998-11-06 BR BR9813975-4A patent/BR9813975A/en not_active Application Discontinuation
- 1998-11-06 AR ARP980105624 patent/AR017571A1/en unknown
- 1998-11-06 AU AU10150/99A patent/AU1015099A/en not_active Abandoned
- 1998-11-06 PL PL34009498A patent/PL340094A1/en unknown
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4900533A (en) * | 1981-02-24 | 1990-02-13 | English Clays Lovering Pochin & Company | Alkaline earth metal carbonates |
EP0197327A2 (en) * | 1985-03-23 | 1986-10-15 | Hoechst Aktiengesellschaft | Process for the preparation of fine, very pure calcium carbonate with a high degree of whiteness |
CN85103821A (en) * | 1985-05-13 | 1986-11-12 | 陈学廉 | Increase the method for whiteness of low density calcium carbonate |
EP0257458A2 (en) * | 1986-08-22 | 1988-03-02 | Akira Matsuzaki | Scrubbing agent and process for producing the same |
RO105941B1 (en) * | 1990-04-20 | 1993-01-30 | Centrul Chim Timisoara | Preparation process of a calcium carbonate assortment of high purity and fine granulation |
US5290353A (en) * | 1990-07-24 | 1994-03-01 | Lhoist Recherche Et Developpement S.A. | Vaterite and production method |
EP0558275A1 (en) * | 1992-02-26 | 1993-09-01 | Pretoria Portland Cement Company Limited | Production of purified calcium carbonate |
JPH0641892A (en) * | 1992-07-20 | 1994-02-15 | New Oji Paper Co Ltd | Production of light calcium carbonate |
Non-Patent Citations (3)
Title |
---|
CHEMICAL ABSTRACTS, vol. 107, no. 20, 16 November 1987, Columbus, Ohio, US; abstract no. 179493, CHEN, XUELIAN ET AL: "Method of increasing whiteness of low density calcium carbonate" XP002069022 * |
DATABASE WPI Section Ch Week 9406, Derwent World Patents Index; Class A60, AN 1994-046250, XP002069325 * |
DATABASE WPI Section Ch Week 9411, Derwent World Patents Index; Class F09, AN 1994-089787, XP002069023 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7105139B2 (en) | 2002-04-25 | 2006-09-12 | Imerys Pigments, Inc. | Stabilization of the viscosity of formamidine sulfinic acid bleached calcium carbonate slurries |
Also Published As
Publication number | Publication date |
---|---|
AU1015099A (en) | 1999-05-31 |
BR9813975A (en) | 2000-09-26 |
PL340094A1 (en) | 2001-01-15 |
BE1011538A4 (en) | 1999-10-05 |
SK6292000A3 (en) | 2000-12-11 |
ZA9810169B (en) | 1999-05-07 |
EP1028916A1 (en) | 2000-08-23 |
AR017571A1 (en) | 2001-09-12 |
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