JPH02302317A - Preparation of aragonite calcium carbonate - Google Patents
Preparation of aragonite calcium carbonateInfo
- Publication number
- JPH02302317A JPH02302317A JP33145387A JP33145387A JPH02302317A JP H02302317 A JPH02302317 A JP H02302317A JP 33145387 A JP33145387 A JP 33145387A JP 33145387 A JP33145387 A JP 33145387A JP H02302317 A JPH02302317 A JP H02302317A
- Authority
- JP
- Japan
- Prior art keywords
- vaterite
- calcium carbonate
- aragonite
- emulsion
- divalent
- 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.)
- Pending
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 172
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 33
- 239000000839 emulsion Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 7
- -1 fatty acid salts Chemical class 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 239000011651 chromium Substances 0.000 claims 1
- 235000010216 calcium carbonate Nutrition 0.000 abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 15
- 239000013078 crystal Substances 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000001569 carbon dioxide Substances 0.000 abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 8
- 239000000920 calcium hydroxide Substances 0.000 abstract description 7
- 230000007704 transition Effects 0.000 abstract description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 229910021555 Chromium Chloride Inorganic materials 0.000 abstract description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 abstract description 2
- 239000001639 calcium acetate Substances 0.000 abstract description 2
- 229960005147 calcium acetate Drugs 0.000 abstract description 2
- 235000011092 calcium acetate Nutrition 0.000 abstract description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 abstract 1
- 239000000347 magnesium hydroxide Substances 0.000 abstract 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 16
- 229910021532 Calcite Inorganic materials 0.000 description 15
- 229910001629 magnesium chloride Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 235000011116 calcium hydroxide Nutrition 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 244000132059 Carica parviflora Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010027476 Metastases Diseases 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000009401 metastasis Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明はアラゴナイト系炭酸カルシウムをバテライト系
炭酸カルシウムからの結晶転移により製造する方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing aragonite calcium carbonate by crystal transition from vaterite calcium carbonate.
［従来の方法］
一般に、炭酸カルシウムはゴム、プラスチック、紙、食
品、化粧品等の広い分野に利用されているもので、工業
用充填剤として欠くことのできない工業原料となってい
る。炭酸カルシウムの製造方法としては、水酸化カルシ
ウム水懸濁液（以下、石灰乳と言う）に二酸化炭素含有
気体（以下、炭酸ガスと言う）を導入する方法が主であ
るが、他の方法として塩化カルシウムのような水溶性の
カルシウム塩と庚酸ナトリウＪ１等の水溶性の炭酸塩と
を反応させる方法、石灰乳と水溶性炭酸塩との反応によ
る方法もある。[Conventional Method] Calcium carbonate is generally used in a wide range of fields such as rubber, plastics, paper, foods, and cosmetics, and is an indispensable industrial raw material as an industrial filler. The main method for producing calcium carbonate is to introduce carbon dioxide-containing gas (hereinafter referred to as carbon dioxide gas) into a calcium hydroxide aqueous suspension (hereinafter referred to as milk of lime), but other methods include There is also a method of reacting a water-soluble calcium salt such as calcium chloride with a water-soluble carbonate such as sodium chloride J1, and a method of reacting milk of lime with a water-soluble carbonate.
炭酸カルシウムには、結晶工学上、カルサイト、アラゴ
ナイト、バテライトの３ｆｉの同質多像体が存在してお
り、上記の製造方法で温度、濃度等の製造条件を制御す
ることにより、１種あるいは２種以上の結晶構造を有す
る炭酸カルシウムが製造される。Calcium carbonate has 3fi homogeneous polyhedrons of calcite, aragonite, and vaterite in terms of crystal engineering, and by controlling the manufacturing conditions such as temperature and concentration using the above manufacturing method, one type or two types can be produced. Calcium carbonate having more than a seed crystal structure is produced.
カルサイトを製造するにあたっては、カルサイトが他の
結晶構造より安定であるため天然にも石灰石等として産
出されており、また人工的にも純粋なカルサイトが簡単
に製造されている。カルサイトの形状は立方体、紡錘形
が基本形となっており、現在市販されている炭酸カルシ
ウムの多くはこのカルサイトである。In producing calcite, since calcite has a more stable crystal structure than other crystal structures, it is naturally produced as limestone, etc., and pure calcite can also be easily produced artificially. The basic shape of calcite is cubic or spindle-shaped, and most of the calcium carbonate currently on the market is of this type.
一方、アラゴナイトは天然に純粋なものがサンゴ石灰岩
等として産出されてはいるが、人工的に純粋なアラゴナ
イトを生成することは未だ困難で、カルサイトの混入が
どうしても避けられないのが現状である。アラゴナイト
の形状としては、針状あるいは柱状をなしており製紙用
塗工顔料として一部製造販売されている。On the other hand, although naturally pure aragonite is produced as coral limestone, it is still difficult to produce pure aragonite artificially, and contamination with calcite is unavoidable. . Aragonite has an acicular or columnar shape, and some of it is manufactured and sold as a coating pigment for paper manufacturing.
バテライトにおいては、基本的には球状粒子でその表面
は非常に活性に富んでいる。しかしながら全く天然には
産出されず、結晶構造も他より極めて不安定であるため
水の存在下で容易に安定なカルサイトに結晶転移する。Vaterite is basically a spherical particle whose surface is highly active. However, it is not produced naturally and its crystal structure is much more unstable than others, so it easily undergoes a crystal transition to stable calcite in the presence of water.
本発明は、これらの同質多像体の中でも、紙の塗工剤等
に優れた特性を示すアラゴナイトを、表面活性に富むバ
テライトから純粋に製造することを目的にしたものであ
る。The object of the present invention is to produce aragonite, which exhibits excellent properties as a paper coating agent among these homogeneous polymorphs, purely from vaterite, which is rich in surface activity.
アラゴナイトの製造方法として、■石灰乳に反応温度、
炭酸ガス供給量、炭酸化率を３段階で制御しながら製造
する方法（特開昭５４−５０４９９） 、■水酸化アン
モニウムでアルカリ性にした塩化カルシウム水溶液に密
閉式反応容器（オートクレーブ）中で炭酸ガスを導入す
る方法（特公昭４３・２２７８３）、■あらかじめアラ
ゴナイトを１０％以上含有させた石灰乳に炭酸ガス供給
量を制御して製造する方法が（特開昭５９−２３２９１
６ ）挙げられる。As for the production method of aragonite, ■ Reaction temperature to milk of lime,
A method for manufacturing while controlling the amount of carbon dioxide gas supplied and the carbonation rate in three stages (Japanese Patent Application Laid-Open No. 54-50499). ■ Carbon dioxide gas is added to an aqueous calcium chloride solution made alkaline with ammonium hydroxide in a closed reaction vessel (autoclave). (Japanese Patent Publication No. 43-22783), and (Japanese Patent Publication No. 59-23291), there is a method of manufacturing by controlling the amount of carbon dioxide gas supplied to milk of lime containing 10% or more of aragonite in advance.
6) Listed.
■の方法では、反応温度、炭酸ガス供給量、炭酸化率を
３段階で変化させるという煩雑な操作が必要であるばか
りか、その条件設定が難しくアラゴナイトではなくカル
サイトが生成する要素が多い。次に、■の方法では特殊
製造装置であるオートクレーブ中で加圧せねばならず、
水酸化アンモニウムも塩化カルシウムに対して２倍モル
添加せねばならない、■の方法では、あらかじめアラゴ
ナイトを５５％以上含有する炭酸カルシウムを合成せね
ばならないし、生成したアラゴナイトも純粋なものでは
ない。また、いずれの方法においてもカルサイトの混入
が避けられず、カルサイトを１０％以上含むもので、そ
れぞれ多くの問題が残っている。Method (2) not only requires complicated operations such as changing the reaction temperature, the amount of carbon dioxide gas supplied, and the carbonation rate in three stages, but it is also difficult to set the conditions, which often results in the formation of calcite instead of aragonite. Next, in method (■), pressure must be applied in an autoclave, which is a special manufacturing equipment.
Ammonium hydroxide must also be added in twice the molar amount relative to calcium chloride. In method (2), calcium carbonate containing 55% or more of aragonite must be synthesized in advance, and the aragonite produced is not pure. Furthermore, in any of the methods, the contamination of calcite is unavoidable, and each method has many problems as they contain 10% or more of calcite.
［発明が解決しようとする問題点］
今までのアラゴナイトの製造方法は、その製造条件であ
る反応温度、炭酸ガス供給量等の制御が容易ではなく、
しかもアラゴナイトの他にもカルサイトが゛混入する等
純粋なアラゴナイトを製造するのが困難である。[Problems to be solved by the invention] In the conventional methods for producing aragonite, it is not easy to control the production conditions such as the reaction temperature and the amount of carbon dioxide gas supplied.
Moreover, it is difficult to produce pure aragonite because calcite is mixed in with the aragonite.
［問題を解決するための手段］
そこで、本発明者らは、鋭意研究の結果、非常に不安定
な結晶構造であるバテライトをアラゴナイトへ結晶転移
させることにより、純粋なアラゴナイトを製造できるこ
とを見出した。すなわち、バテライト乳液に２価あるい
は３価の金属塩を添加するか、２価あるいは３価の金属
塩を含有させたバテライトを乳液として、４０℃以上で
加熱処理することによりバテライトを純粋なアラゴナイ
トへ転移させる方法である。[Means for solving the problem] As a result of intensive research, the present inventors discovered that pure aragonite can be produced by crystallizing vaterite, which has an extremely unstable crystal structure, into aragonite. . That is, by adding a divalent or trivalent metal salt to a vaterite emulsion, or using vaterite containing a divalent or trivalent metal salt as an emulsion and heat-treating it at 40°C or higher, vaterite is converted to pure aragonite. This is a method of metastasis.
２価あるいは３価の金属塩は、マグネシウム、亜鉛、ニ
ッケル、コバルト、クロＪ１のハロゲン化物、硫酸塩、
硝酸塩、酸化物、水酸化物、アルミン酸塩、炭酸塩、酢
酸塩で代表される脂肪酸塩等の１種あるいは２種以上の
ものでなくてはならない。それ以外の金属塩、例えばバ
リウム、ストロンチウム、鉛、カドニウム等の金属塩で
はアラゴナイトは全く生成せずカルサイトが生成する。Divalent or trivalent metal salts include magnesium, zinc, nickel, cobalt, chloride J1 halides, sulfates,
It must be one or more of fatty acid salts represented by nitrates, oxides, hydroxides, aluminates, carbonates, and acetates. With other metal salts, such as barium, strontium, lead, and cadmium, aragonite is not produced at all, but calcite is produced.
バテライト製造の際に添加、あるいはバテライト乳液に
添加する２価あるいは３価の金属塩の量は炭酸カルシウ
ムに対し０．００１モル％以上であればよく、それ以下
だとアラゴナイトは全く生成せずカルサイトが生成する
。２価あるいは３価の金属塩の添加時期は、バテライト
合成前、合成中あるいは合成後であってもよく、また加
熱処理前であればよい。ただ加熱開始後であると、バテ
ライトが水に対し不安定な物質で高温域においては特に
カルサイトへの転移速度が速まるため、カルサイト単味
あるいはカルサイトとアラゴナイトの混合物となる。し
たがって、加熱処理前には、すでに２価あるいは３価の
金属塩を添加した状態にしておかねばならない。The amount of divalent or trivalent metal salt added during vaterite production or added to vaterite emulsion should be 0.001 mol% or more based on calcium carbonate; if it is less than that, no aragonite will be formed and no calcium carbonate will be formed. Site generated. The divalent or trivalent metal salt may be added before, during, or after the vaterite synthesis, or may be added before the heat treatment. However, if heating is started, vaterite is an unstable substance with respect to water, and the rate of transition to calcite is particularly rapid in high temperature ranges, so the result is a single calcite substance or a mixture of calcite and aragonite. Therefore, a divalent or trivalent metal salt must be added before the heat treatment.
また加熱処理温度は４０℃以上が望ましく、それ以下だ
と逆に２価−あるいは３価の金属塩がバテライトの安定
化に寄与するため、アラゴナイトへの転化速度が極端に
低下してバテライト多量の炭酸カルシウムとなる。In addition, the heat treatment temperature is preferably 40℃ or higher; if it is lower than that, divalent or trivalent metal salts will contribute to the stabilization of vaterite, so the conversion rate to aragonite will be extremely reduced and a large amount of vaterite will be lost. Becomes calcium carbonate.
バテライト乳液の濃度は、乳液の状態を保てる濃度、お
よそ３０％前後以下の濃度であれば何ら問題なく、極め
て低い濃度においても充分純粋なアラゴナイトが得られ
る。 。There is no problem with the concentration of the vaterite emulsion as long as it is at a concentration that maintains the state of an emulsion, approximately 30% or less, and sufficiently pure aragonite can be obtained even at extremely low concentrations. .
［発明の効果］
本発明は従来の方法に比べて煩雑な製造条件の制御を要
せず、しかも製造された炭酸カルシウムはほとんどアラ
ゴナイトであるため、工業的にも大きな意義がある。[Effects of the Invention] Compared to conventional methods, the present invention does not require complicated control of production conditions, and the produced calcium carbonate is mostly aragonite, so it has great industrial significance.
［実施例］
参考例 ｌ
水酸化カルシウム２５８と酢酸カルシウム５９ｇを秤り
取り、水を２５０ｇ、メタノールを１６６ ｇ添加し１
０分間よく攪）半するとともに、乳液の温度を約２５℃
に！Ｉｌ！整した。この乳液に攪拌しながら１００％の
炭酸カスを２４！／ｍｉｎで供給していった。炭酸化の
反応終了点は乳１ａの温度上昇が終わり下降し始めて３
分経過した時点とした。反応終了後、ろ過し、４．５回
水洗し、最後にメタノールで２回洗浄した。約１００℃
で１０時間以上乾燥させ生成物３２ｇを得た。得られた
炭酸カルシウムはＸ線回折の測定結果からすべてバテラ
イトであった。図−１にＸ線回折結果を示した。[Example] Reference example l Weighed 258 g of calcium hydroxide and 59 g of calcium acetate, added 250 g of water and 166 g of methanol, and prepared 1
(Stir well for 0 minutes) and reduce the temperature of the emulsion by about 25℃.
To! Il! I arranged it. Add 100% carbonated scum to this emulsion while stirring for 24 hours! /min. The end point of the carbonation reaction is when the temperature of milk 1a stops rising and begins to fall.
The time point was set as the time when minutes had elapsed. After the reaction was completed, it was filtered, washed 4.5 times with water, and finally washed twice with methanol. Approximately 100℃
After drying for over 10 hours, 32 g of product was obtained. All of the obtained calcium carbonate was vaterite based on the results of X-ray diffraction measurements. Figure 1 shows the X-ray diffraction results.
参考例 ２
約６０℃に調整した２０％の炭酸ナトリウム水溶液５０
０ｇに攪拌しながら、やはり約６０℃に調整した１５％
の塩化カルシウム水溶Ｍ？００ｇを１分間におよそ１５
０ｇの割り合いで滴下していった。滴下終了後、素速く
ろ過し２，３回水洗およびメタノールで２回洗浄し、約
１００℃で１０時間以上乾燥させ約９３ｇの生成物を得
た。得られた炭酸カルシウムはＸ線回折の測定結果から
すへてバテライトであった。Reference example 2 20% sodium carbonate aqueous solution adjusted to about 60°C 50%
15%, also adjusted to about 60°C while stirring to 0g
Calcium chloride water soluble M? Approximately 15 00g per minute
It was dropped at a rate of 0g. After the dropwise addition was completed, the mixture was quickly filtered, washed with water two or three times and twice with methanol, and dried at about 100° C. for more than 10 hours to obtain about 93 g of a product. The obtained calcium carbonate was determined to be vaterite based on the results of X-ray diffraction measurements.
実施例 １
参考例１で得たバテライト６０ｇに塩化カルシウム・６
水塩をバテライトの１モル％にあたる１．２２ｇ加え水
で２００８とした。１０分間程室温で攪拌した後９０℃
で３時間保持させ、ろ過、２，３回の水洗および２回の
メタノール洗浄を行い１００℃で１０時間以上乾燥させ
た。生成物の収量は５９ｇであった。Example 1 Calcium chloride 60g was added to 60g of vaterite obtained in Reference Example 1.
1.22 g of aqueous salt corresponding to 1 mol % of vaterite was added and the mixture was made into 2008 with water. After stirring at room temperature for about 10 minutes, 90℃
The mixture was kept at 100° C. for 3 hours, filtered, washed with water a few times and washed with methanol twice, and dried at 100° C. for 10 hours or more. Product yield was 59g.
Ｘ線回折の結果から生成した炭酸カルシウムはすべてア
ラゴナイトであった。図−２にＸ線回折の測定結果を、
写真−１に走査型電子顕ｙ＆鏡写真を示した。All calcium carbonate produced from the results of X-ray diffraction was aragonite. Figure 2 shows the measurement results of X-ray diffraction.
Photo 1 shows a scanning electron microscope and mirror photo.
実施例 ２〜１１
参考例１で得たバテライトをバテライト乳液として、そ
の濃度を１０．５．２．５．０．５％のいずれかに、ま
たバテライト乳液量２００ ｇに設定し、バテライトに
対し１モル％の塩化亜鉛、塩化ニッケル、塩化コバルト
、塩化クロム、硫酸亜鉛、酢酸亜鉛、臭化亜鉛、硝酸亜
鉛、酸化亜鉛、塩基性炭酸亜鉛を加え、以下実施例１と
同様にしてバテライトの結晶転移実験を行った。実施条
件および結果を表−１に示した。Examples 2 to 11 The vaterite obtained in Reference Example 1 was used as a vaterite emulsion, and the concentration was set to 10, 5, 2, 5, or 0.5%, and the amount of vaterite emulsion was set to 200 g. Adding 1 mol% of zinc chloride, nickel chloride, cobalt chloride, chromium chloride, zinc sulfate, zinc acetate, zinc bromide, zinc nitrate, zinc oxide, and basic zinc carbonate, the following procedure was repeated in the same manner as in Example 1 to obtain vaterite crystals. We conducted a transfer experiment. The implementation conditions and results are shown in Table-1.
実施例 １２
参考例１で得たバテライトをバテライト乳液として、バ
テライト乳液濃度を５％、バテライト乳ｌｆｆ１２００
ｇに設定した。これに、バテライトに対して０．５％の
塩化亜鉛と同じ＜０．５％の塩化マグネシウムを加え、
以下実施例１と同様にしてバテライトの結晶転移実験を
行った。実施条件および結果を表−１に示した。Example 12 The vaterite obtained in Reference Example 1 was used as a vaterite emulsion, the vaterite emulsion concentration was 5%, and the vaterite milk lff1200.
It was set to g. To this, add 0.5% zinc chloride and <0.5% magnesium chloride to vaterite,
Hereinafter, a vaterite crystal transition experiment was conducted in the same manner as in Example 1. The implementation conditions and results are shown in Table-1.
実施例 １３
参考例１で得たバテライトをバテライト乳液として、バ
テライト乳液濃度を５％、バテライト乳液量２００ｇに
設定した。これに、バテライトに対し１モル％の塩化マ
グネシウム加え、約４０°Ｃで２４時間加熱処理した以
外は実施例１と同様にして行った。実施条件および結果
を表−１に示した。Example 13 The vaterite obtained in Reference Example 1 was used as a vaterite emulsion, and the concentration of the vaterite emulsion was set to 5% and the amount of vaterite emulsion was set to 200 g. The same procedure as in Example 1 was carried out except that 1 mol % of magnesium chloride based on the vaterite was added to this, and the mixture was heat-treated at about 40°C for 24 hours. The implementation conditions and results are shown in Table-1.
比較例 ｌ
実施例１３の約４０℃で２４時間の加熱処理を、約２５
℃で２４時間の条件に変えて行った。実施条件および結
果を表−１に示した。Comparative Example l The heat treatment of Example 13 at about 40°C for 24 hours was performed for about 25 hours.
The conditions were changed to 24 hours at ℃. The implementation conditions and results are shown in Table-1.
実施例 １４
参考例２で得たバテライトをバテライト乳液として、バ
テライト乳液濃度を５％、バテライト乳液ｊ１２００ｇ
に設定した。これに、バテライトに対し０．０００１モ
ル％の塩化亜鉛を加え、９０℃で５時間加熱処理をし、
以下実施例１と同様に行った。実施条件および結果を表
−２に示した。Example 14 The vaterite obtained in Reference Example 2 was used as a vaterite emulsion, the vaterite emulsion concentration was 5%, and the vaterite emulsion j was 1200 g.
It was set to To this, 0.0001 mol% of zinc chloride was added to the vaterite and heat treated at 90°C for 5 hours.
The following steps were carried out in the same manner as in Example 1. The implementation conditions and results are shown in Table-2.
比較例 ２
実施例１４の添加した塩化亜鉛量をバテライトに対して
５ｘｌＯ−’モル％に変えて行った。実施条件および結
果を表−２に示した。Comparative Example 2 The same procedure as in Example 14 was carried out by changing the amount of zinc chloride added to 5xlO-' mol % based on vaterite. The implementation conditions and results are shown in Table-2.
実施例 １５．１６
参考例２で得たバテライトをバテライト乳液として、バ
テライト乳液濃度を５％、バテライト乳液量２００ｇに
設定した。これに、バテライトに対し１モル％の酸化マ
グネシウムおよび塩化マグネシウムを加え、約１３０℃
で５時間および約１６０℃で５時間加熱処理をし、以下
実施例１と同様に行った。実施条件および結果を表−２
に示した。Example 15.16 The vaterite obtained in Reference Example 2 was used as a vaterite emulsion, and the concentration of the vaterite emulsion was set to 5% and the amount of vaterite emulsion was set to 200 g. To this, 1 mol% of magnesium oxide and magnesium chloride were added to the vaterite, and the temperature was raised to about 130°C.
Heat treatment was performed for 5 hours at about 160° C. and for 5 hours at about 160° C., and the same procedure as in Example 1 was carried out. Table 2 shows the implementation conditions and results.
It was shown to.
実施例 １７〜１９
参考例１のバテライト合成の段階で、合成前、合成中、
合成後に、バテライトに対して１モル％となるように塩
化マグネシウムを添加し、参考例１と同様な条件で、ろ
過、乾燥を行った。得られたバテライトを５％のバテラ
イト乳液２００ｇに何も添加せずに約９０℃で３時間加
熱処理し、以下実施例１と同様にして行った。実施条件
および結果を表−３に示した。Examples 17 to 19 At the stage of vaterite synthesis in Reference Example 1, before and during synthesis,
After the synthesis, magnesium chloride was added to the vaterite in an amount of 1 mol %, and filtration and drying were performed under the same conditions as in Reference Example 1. The obtained vaterite was heat-treated at about 90° C. for 3 hours without adding anything to 200 g of a 5% vaterite emulsion, and the same procedure as in Example 1 was carried out. The implementation conditions and results are shown in Table 3.
実施例 ２０〜２２
参考例２のバテライト合成の段階で、合成前、合成中、
合成後に、バテライトに対して１モル％となるように塩
化マグネシウムを添加し、参考例２と同様な条件で、ろ
過、乾燥を行った。得られたバテライトを５％のバテラ
イト乳液２００ｇに何も添加せずに約９０℃で６時間加
熱処理し、以下実施例１と同様にして行った。実施条件
および結果を表−３に示した。Examples 20 to 22 At the stage of vaterite synthesis in Reference Example 2, before and during synthesis,
After the synthesis, magnesium chloride was added to the vaterite in an amount of 1 mol %, and filtration and drying were performed under the same conditions as in Reference Example 2. The obtained vaterite was heat-treated at about 90° C. for 6 hours without adding anything to 200 g of a 5% vaterite emulsion, and the same procedure as in Example 1 was carried out. The implementation conditions and results are shown in Table 3.
実施例 ２３
参考例２のバテライト合成の段階で合成前に、バテライ
トに対して０．５モル％となるように塩化マグネシウム
を添加し、参考例２と同様な条件で、ろ過、乾燥を行っ
た。得られたバテライトを５％のバテライト乳液２００
ｇに、バテライトに対して０．５モル％の塩化マグネシ
ウムを添加し、約９０℃で５時間加熱処理し、以下実施
例１と同様に行った。実施条件および結果を表−３に示
した。Example 23 At the stage of vaterite synthesis in Reference Example 2, before synthesis, magnesium chloride was added to the vaterite at a concentration of 0.5 mol%, and filtration and drying were performed under the same conditions as in Reference Example 2. . 5% vaterite emulsion 200% of the obtained vaterite
0.5 mol % of magnesium chloride based on vaterite was added to g, and the mixture was heat-treated at about 90° C. for 5 hours, and the same procedure as in Example 1 was carried out. The implementation conditions and results are shown in Table 3.
実施例 ２４
参考例２のバテライト合成の段階で、合成前にバテライ
トに対して１モル％となるように塩化マグネシウムを添
加し、参考例２と同様な条件でバテライトの合成を行っ
た。反応終了後、反応乳液をそのまま素速く約９０℃ま
で上昇させ、５１時間保温した。以下、実施例１と同様
にろ過、乾燥を行った。実施条件および結果を表−３に
示した。Example 24 At the stage of vaterite synthesis in Reference Example 2, magnesium chloride was added to the vaterite in an amount of 1 mol % before synthesis, and vaterite was synthesized under the same conditions as in Reference Example 2. After the reaction was completed, the reaction emulsion was quickly raised to about 90° C. and kept at that temperature for 51 hours. Thereafter, filtration and drying were performed in the same manner as in Example 1. The implementation conditions and results are shown in Table 3.
図面の浄書
第１図
第２図
第３図
・ 氾２−
手 続 袖 正 ！ （方式 ）％式％
１、事件の表示 昭ｆ０６２年特訂霧第３３目５３号２
、発明の名称 アラゴナイト系炭酸カルシウムの製造方
法
３、補正をする者
事件との関係 特許出願人
（ｒ所 大分県津久見市型浦３４９番地の１住所 大分
県大分市大字羽田８９２１１地の１（・−・７
（１）明細書の図面の簡単な説明の追加（２）図面
、補正の内容
（１）明細書第１４頁３行目から吹の文章を追加します
。Engraving of the drawings Figure 1 Figure 2 Figure 3 Flood 2- Procedure Sleeve correct! (Method) % formula % 1, Incident display 1986 Special Edition Kiri No. 33 No. 53 2
, Title of the invention Process for producing aragonite-based calcium carbonate 3, Relationship with the amended case Patent applicant (r Address: 349-1 Kataura, Tsukumi City, Oita Prefecture Address: 1-1 Haneda, Oaza, Oita City, Oita Prefecture) -・7 (1) Addition of a brief explanation of the drawings in the specification (2) Contents of the drawings and amendments (1) Add a blank text from line 3 on page 14 of the specification.
第１図は参考例１で得られたバテライ
トのＸ線回折パターン図である。第２図は実１１で帰ら
れたアラゴナイトのＸ
線回折パターン図である。第３図は実施例１で得られた
アラゴナイトの走査型電子Ｉ＃ｐ＆鐘写真で結晶の（清
遊を示したものである。」
（２）図面の図−１、図−２、写１％−１を別紙の通り
第１図、爪２因、第３図に訂正します。FIG. 1 is an X-ray diffraction pattern diagram of vaterite obtained in Reference Example 1. Figure 2 shows the X-ray diffraction pattern of the aragonite obtained in Experiment 11. Figure 3 is a scanning electron I#p and bell photograph of the aragonite obtained in Example 1, showing the clearness of the crystals. (2) Figures 1 and 2 of the drawings, 1% -1 is corrected to Figure 1, Nail 2, and Figure 3 as per the attached sheet.
Claims (1)
ライト乳液と言う）に２価あるいは３価の金属塩を添加
し４０℃以上でこのバテライト乳液を加熱処理し、バテ
ライト系炭酸カルシウムをアラゴナイト系炭酸カルシウ
ムに結晶転移させることによるアラゴナイト系炭酸カル
シウムの製造方法。 ２）２価あるいは３価の金属塩が亜鉛、マグネシウム、
コバルト、ニッケル、クロムで、これらのハロゲン化物
、硝酸塩、硫酸塩、酸化物、水酸化物、炭酸塩、アルミ
ン酸塩、酢酸塩で代表される脂肪酸塩等の１種もしくは
２種以上から選択される特許請求の範囲第１項に記載の
方法。 ３）バテライト系炭酸カルシウムの合成前、合成中ある
いは合成後とバテライト系炭酸カルシウムの加熱処理前
に添加する２価あるいは３価の金属塩の量が、最終的に
バテライト系炭酸カルシウム１モルに対し０．０００１
モル以上である特許請求の範囲第１、２項に記載の方法
。[Scope of Claims] 1) A divalent or trivalent metal salt is added to a vaterite-based calcium carbonate aqueous suspension (hereinafter referred to as vaterite emulsion), and the vaterite emulsion is heat-treated at 40°C or higher to produce a vaterite-based calcium carbonate aqueous suspension (hereinafter referred to as vaterite emulsion). A method for producing aragonite calcium carbonate by crystallizing calcium carbonate into aragonite calcium carbonate. 2) Divalent or trivalent metal salts include zinc, magnesium,
Cobalt, nickel, and chromium, selected from one or more of these halides, fatty acid salts represented by nitrates, sulfates, oxides, hydroxides, carbonates, aluminates, and acetates. A method according to claim 1. 3) The amount of divalent or trivalent metal salt added before, during, or after the synthesis of vaterite calcium carbonate and before heat treatment of vaterite calcium carbonate is the final amount per mole of vaterite calcium carbonate. 0.0001
The method according to claims 1 and 2, wherein the amount is mol or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33145387A JPH02302317A (en) | 1987-12-25 | 1987-12-25 | Preparation of aragonite calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33145387A JPH02302317A (en) | 1987-12-25 | 1987-12-25 | Preparation of aragonite calcium carbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02302317A true JPH02302317A (en) | 1990-12-14 |
Family
ID=18243821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33145387A Pending JPH02302317A (en) | 1987-12-25 | 1987-12-25 | Preparation of aragonite calcium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02302317A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6156286A (en) * | 1997-05-21 | 2000-12-05 | Imerys Pigments, Inc. | Seeding of aragonite calcium carbonate and the product thereof |
| WO2013165600A1 (en) * | 2012-05-03 | 2013-11-07 | Calera Corporation | Non-cementitious compositions comprising vaterite and methods thereof |
| EP2831120A4 (en) * | 2012-03-29 | 2015-08-26 | Calera Corp | Methods and systems for utilizing carbide lime |
| US9902652B2 (en) | 2014-04-23 | 2018-02-27 | Calera Corporation | Methods and systems for utilizing carbide lime or slag |
| US11377363B2 (en) | 2020-06-30 | 2022-07-05 | Arelac, Inc. | Methods and systems for forming vaterite from calcined limestone using electric kiln |
| US11577965B2 (en) | 2020-02-25 | 2023-02-14 | Arelac, Inc. | Methods and systems for treatment of lime to form vaterite |
| GB2613216A (en) * | 2021-04-19 | 2023-05-31 | Arelac Inc | Compositions, methods, and systems to form vaterite with magnesium oxide |
-
1987
- 1987-12-25 JP JP33145387A patent/JPH02302317A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6156286A (en) * | 1997-05-21 | 2000-12-05 | Imerys Pigments, Inc. | Seeding of aragonite calcium carbonate and the product thereof |
| EP2831120A4 (en) * | 2012-03-29 | 2015-08-26 | Calera Corp | Methods and systems for utilizing carbide lime |
| WO2013165600A1 (en) * | 2012-05-03 | 2013-11-07 | Calera Corporation | Non-cementitious compositions comprising vaterite and methods thereof |
| US9902652B2 (en) | 2014-04-23 | 2018-02-27 | Calera Corporation | Methods and systems for utilizing carbide lime or slag |
| US11577965B2 (en) | 2020-02-25 | 2023-02-14 | Arelac, Inc. | Methods and systems for treatment of lime to form vaterite |
| US11377363B2 (en) | 2020-06-30 | 2022-07-05 | Arelac, Inc. | Methods and systems for forming vaterite from calcined limestone using electric kiln |
| GB2613216A (en) * | 2021-04-19 | 2023-05-31 | Arelac Inc | Compositions, methods, and systems to form vaterite with magnesium oxide |
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