WO2003000592A1 - Procede servant a produire du carbonate de calcium a base de coquilles - Google Patents

Procede servant a produire du carbonate de calcium a base de coquilles Download PDF

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Publication number
WO2003000592A1
WO2003000592A1 PCT/JP2002/004393 JP0204393W WO03000592A1 WO 2003000592 A1 WO2003000592 A1 WO 2003000592A1 JP 0204393 W JP0204393 W JP 0204393W WO 03000592 A1 WO03000592 A1 WO 03000592A1
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WO
WIPO (PCT)
Prior art keywords
calcium carbonate
shell
shellfish
mass
shells
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/JP2002/004393
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English (en)
Japanese (ja)
Inventor
Tamotsu Yasue
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.)
Nihon University
Original Assignee
Nihon University
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 Nihon University filed Critical Nihon University
Priority to JP2003506801A priority Critical patent/JP4203608B2/ja
Publication of WO2003000592A1 publication Critical patent/WO2003000592A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • 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

Definitions

  • the present invention relates to a method for efficiently producing calcium carbonate having a form derived from shellfish, which can be used as an inorganic material from shellfish.
  • Shells are a tough inorganic-organic composite material with a structure in which 95% by mass of calcium carbonate and 5% by mass of protein are alternately layered.
  • the form of calcium carbonate is needle-like, plate-like, It has various forms such as columnar and tape-like.
  • the landing value of edible shellfish is increasing every year, and the landing value of sea oysters and oysters is 450,000 t / year.
  • the number of discarded shellfish has increased, and they have been left piled up, causing odor and water pollution, and it is urgently necessary to secure a disposal site.
  • the treatment of mussels entering the intakes of thermal power plants has become a new problem.
  • An object of the present invention is to provide a method for efficiently recovering calcium carbonate having a unique form in shellfish in its original form. Disclosure of the invention
  • the present inventors conducted various studies to separate calcium carbonate having a unique form from shellfish as it is. It was found that calcium carbonate in the form described above could be obtained efficiently, and that the obtained calcium carbonate had properties similar to those surface-treated with amino acids, and thus was useful as various types of fillers. The present invention has been completed.
  • the present invention provides a method for producing calcium carbonate having a morphology derived from raw material shellfish, which is characterized in that shellfish is ground in an alkaline aqueous solution under pressure and heating conditions.
  • FIG. 1 is a graph showing the effect of sodium hydroxide concentration on the particle size distribution of calcium carbonate obtained from shellfish.
  • FIG. 2 is a scanning electron micrograph of acicular calcium carbonate obtained from shellfish. BEST MODE FOR CARRYING OUT THE INVENTION
  • the shellfish used in the present invention is not particularly limited, and examples include shellfish, oysters, mussels, clams, anemones, aphids, and evening mussels. Among them, there are needle-shaped calcium carbonate in scallop, tape-like calcium carbonate in iki, plate-like calcium carbonate in abyss, and columnar calcium carbonate in snail mussel. According to the method of the present invention, the form derived from these raw shellfish is A calcium carbonate having a state is obtained. These shells may be used as they are, but it is more efficient to use them after first coarsely grinding with a hammer or the like. In the case of coarse pulverization, it is preferable to carry out, for example, until the particle diameter becomes 1 to 10 mm and further about 1 to 5 m. It is also preferable to use dried shells.
  • the alkaline aqueous solution used in the present invention is not particularly limited as long as it can hydrolyze a protein occupying 5% by mass in shellfish.
  • an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia or the like can be used.
  • concentration of the aqueous alkali solution varies depending on the alkali used, but is preferably 0.1 to 3% by mass, particularly preferably 0.5 to 2% by mass in terms of reaction efficiency.
  • the pressurizing condition may be 10 lkPa (1.03 kgf / cm 2 ) or more, but from the viewpoint of reaction efficiency, 121 to 507 kPa (1.23 to 5.1 5 kgf / cm 2 ), particularly preferably 203 to 405 kPa (2.06 to 4.12 kgf / cm 2 ).
  • the heating condition may be 100 ° C. or higher, but is preferably 100 to 200 ° C., particularly preferably 120 to 18 from the viewpoint of reaction efficiency.
  • the grinding is preferably performed using a pole mill, a roll mill, or the like, but the pole mill is particularly preferred.
  • the pole is not particularly limited as long as it is an alkali-resistant pole.
  • a stainless pole, a zirconia pole, or the like can be used, and the diameter of the pole is preferably about 1 to 10 mm.
  • the number of revolutions of a powder frame processing apparatus is not particularly limited, but is preferably about 20 to 10 OrZmin from the viewpoint of reaction efficiency.
  • the milling time is not particularly limited, but 1 to 6 hours, further 2 to 6 hours, especially 2 to 4 hours is sufficient.
  • the shell shell concentration in the mixture (shell shell suspension) of the shell shell and the alkali aqueous solution is 3% by mass or more, preferably 3 to 15% by mass, and more preferably 5 to 15% by mass. It can be. This concentration is too high to be considered from the concentration in the conventional calcium carbonate synthesis reaction.
  • the autoclave type Preferably, a pole mill reactor is used.
  • the shellfish suspension and the balls are put into the reaction vessel of this reactor, and the mixture is ground by heating at 100 to 200 ° C. and rotating to 20 to 100 rZmin.
  • the inside of the reaction vessel is preferably pressurized to 10 1 kPa or more, preferably 12 1 to 507 kPa.
  • a reaction time of 1 to 6 hours is sufficient.
  • the shell shell suspension is preferably sealed in the reaction vessel at a filling rate of 40 to 60% from the viewpoint of the yield of calcium carbonate having a shell shell derived form.
  • the obtained calcium carbonate has a form such as a needle-like, tape-like, plate-like, column-like or the like present in the raw material shell. Therefore, a desired form of calcium carbonate can be obtained by selecting shellfish.
  • the obtained calcium carbonate contains a small amount of organic substances that are considered to be amino acids obtained by hydrolyzing proteins. Since the calcium carbonate has the same hydrophilicity as calcium carbonate surface-treated with an amino acid, it can be directly used as an inorganic filler for paper, plastic, rubber, paint, and the like.
  • Coarse crushed dried shells of honey scallop from Nemuro, Hokkaido (hammer crushing, particle size: ⁇ 2 mm) 10% by mass and 0 ⁇ 3% by mass aqueous sodium hydroxide solution 90% by mass shell suspension was ground under the following grinding conditions.
  • RSV-TM1 An improved rotary dissolution reactor manufactured by Sanai Kogyo Co., Ltd.
  • One-clave pole mill reactor Reaction vessel internal volume 150 cm 3 , made of Teflon, shellfish suspension filling rate 50%
  • Post-treatment The crushed shell cake suspension was separated into suspended crushed material and unground material precipitated at the bottom of the container by decantation, and the suspended crushed material was filtered, washed and dried.
  • the calcium carbonate obtained was a mixture of extremely fine amorphous and massive particles. Needle-like calcium carbonate derived from shellfish tissue was not obtained. Therefore, when the temperature and pressure were changed, the presence of fine particles of 1 m or less and large unmilled material of 100 m or more can be confirmed when the temperature and pressure were changed at 25 ° C and 365 kPa. However, as the temperature increased, the unmilled material of 100 m or more decreased, and needle-like crystals were newly observed at 120 ° C or more and 365 kPa.
  • Figure 1 shows the particle size distribution of calcium carbonate obtained by milling the shell suspension containing sodium hydroxide at 140 ° C and 365 kPa for 2 hours.
  • the particle size was measured by a laser type particle size distribution measuring method.
  • calcium carbonate was an uncrushed material of 100 xm or more in which the layers between layers were not destroyed.
  • the protein existing between the layers of carbonic acid is hydrolyzed, causing tissue destruction, and about 1 O ⁇ m of needle-like calcium carbonate derived from the shell of the sea mussel. Generation of a peak was confirmed.
  • Fig. 2 shows a scanning electron micrograph of the sample.
  • the particle size of the obtained calcium carbonate is acicular or fibrous with a width of 1 m, a thickness of 0.1 lm, and a length of about 10 to 30 zm. It was about 12 m 2 Zg.
  • the calcium carbonate contained about 3% by mass of organic matter. Furthermore, the decomposition temperature was about 800 ° C, which was extremely stable. Industrial applicability
  • calcium carbonate having a morphology derived from shellfish can be efficiently produced.

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)
  • Processing Of Solid Wastes (AREA)
  • Crushing And Grinding (AREA)

Abstract

Procédé servant à produire du carbonate de calcium à base de coquilles, ce qui consiste à utiliser ces coquilles en tant que matériau de départ et à les broyer dans une solution aqueuse basique sous une pression élevée accompagnée d'un réchauffement. Ce procédé permet de produire de façon efficace du carbonate de calcium.
PCT/JP2002/004393 2001-06-05 2002-05-02 Procede servant a produire du carbonate de calcium a base de coquilles Ceased WO2003000592A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2003506801A JP4203608B2 (ja) 2001-06-05 2002-05-02 貝がら由来の形態を有する炭酸カルシウムの製造法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001169752 2001-06-05
JP2001-169752 2001-06-05

Publications (1)

Publication Number Publication Date
WO2003000592A1 true WO2003000592A1 (fr) 2003-01-03

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2002/004393 Ceased WO2003000592A1 (fr) 2001-06-05 2002-05-02 Procede servant a produire du carbonate de calcium a base de coquilles

Country Status (2)

Country Link
JP (1) JP4203608B2 (fr)
WO (1) WO2003000592A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007063080A (ja) * 2005-08-31 2007-03-15 Nippon Tennen Sozai Kk 貝殻を原料とする高分散性炭酸カルシウム粉末とその製造方法
JP2016536250A (ja) * 2013-11-08 2016-11-24 オムヤ インターナショナル アーゲー 炭酸カルシウム含有材料の粒度分布を改善するための方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS616011B2 (fr) * 1977-01-19 1986-02-22 Inguritsushu Kureizu Rabaaringu Hoochin Ando Co Ltd
JPS62148320A (ja) * 1985-12-20 1987-07-02 Catalysts & Chem Ind Co Ltd 鱗片状炭酸カルシウムの製造方法
JPS62153210A (ja) * 1985-12-26 1987-07-08 Catalysts & Chem Ind Co Ltd 化粧品組成物
JPH02202957A (ja) * 1989-02-02 1990-08-13 Horubein Kogyo Kk 胡粉製造及び精製法
JPH0745324B2 (ja) * 1990-04-05 1995-05-17 広島県 繊維状炭酸カルシウムの製造方法
JP2000239017A (ja) * 1999-02-17 2000-09-05 Nippon Paper Industries Co Ltd 軽質炭酸カルシウムの粉砕方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS616011B2 (fr) * 1977-01-19 1986-02-22 Inguritsushu Kureizu Rabaaringu Hoochin Ando Co Ltd
JPS62148320A (ja) * 1985-12-20 1987-07-02 Catalysts & Chem Ind Co Ltd 鱗片状炭酸カルシウムの製造方法
JPS62153210A (ja) * 1985-12-26 1987-07-08 Catalysts & Chem Ind Co Ltd 化粧品組成物
JPH02202957A (ja) * 1989-02-02 1990-08-13 Horubein Kogyo Kk 胡粉製造及び精製法
JPH0745324B2 (ja) * 1990-04-05 1995-05-17 広島県 繊維状炭酸カルシウムの製造方法
JP2000239017A (ja) * 1999-02-17 2000-09-05 Nippon Paper Industries Co Ltd 軽質炭酸カルシウムの粉砕方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007063080A (ja) * 2005-08-31 2007-03-15 Nippon Tennen Sozai Kk 貝殻を原料とする高分散性炭酸カルシウム粉末とその製造方法
JP2016536250A (ja) * 2013-11-08 2016-11-24 オムヤ インターナショナル アーゲー 炭酸カルシウム含有材料の粒度分布を改善するための方法
KR101901500B1 (ko) * 2013-11-08 2018-09-21 옴야 인터내셔널 아게 탄산칼슘 함유 물질의 입도 분포 개선 방법
US10344168B2 (en) 2013-11-08 2019-07-09 Omya International Ag Process for improving the particle size distribution of a calcium carbonate-containing material

Also Published As

Publication number Publication date
JP4203608B2 (ja) 2009-01-07
JPWO2003000592A1 (ja) 2004-10-07

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