JPH02153819A - Production of hollow and spherical vaterite type calcium carbide and stabilization thereof - Google Patents
Production of hollow and spherical vaterite type calcium carbide and stabilization thereofInfo
- Publication number
- JPH02153819A JPH02153819A JP22634088A JP22634088A JPH02153819A JP H02153819 A JPH02153819 A JP H02153819A JP 22634088 A JP22634088 A JP 22634088A JP 22634088 A JP22634088 A JP 22634088A JP H02153819 A JPH02153819 A JP H02153819A
- Authority
- JP
- Japan
- Prior art keywords
- water
- calcium carbonate
- alcohol
- spherical
- hollow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 128
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000005997 Calcium carbide Substances 0.000 title abstract 3
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 title abstract 3
- 230000006641 stabilisation Effects 0.000 title description 4
- 238000011105 stabilization Methods 0.000 title description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001868 water Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000001110 calcium chloride Substances 0.000 claims abstract description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 9
- 239000000839 emulsion Substances 0.000 claims abstract 2
- -1 phosphorus oxoacid Chemical class 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 230000000087 stabilizing effect Effects 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 5
- 239000007900 aqueous suspension Substances 0.000 claims description 3
- 230000005484 gravity Effects 0.000 abstract description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 10
- 238000003756 stirring Methods 0.000 abstract description 8
- 239000000243 solution Substances 0.000 abstract description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 235000017550 sodium carbonate Nutrition 0.000 abstract description 2
- 235000011148 calcium chloride Nutrition 0.000 abstract 2
- 235000010216 calcium carbonate Nutrition 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910021532 Calcite Inorganic materials 0.000 description 6
- 238000000635 electron micrograph Methods 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 159000000007 calcium salts Chemical class 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 3
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical group O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical group [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は中空且つ球状という特徴を有する新規なバテラ
イト型炭酸カルシウムの製造法及びその安定化法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a novel vaterite-type calcium carbonate having the characteristics of being hollow and spherical, and a method for stabilizing the same.
炭酸カルシウムには菱面体晶であるカルサイト（Ｃａｌ
ｃｉｔｅ） ＋棒状のアラゴナイト（Ａｒａｇｏｎｉｔ
ｅ）及び球状のバテライト（Ｖａｔｅｒｉｔａ）の３種
の結晶多形が存在する。Calcium carbonate contains calcite (Cal), which is a rhombohedral crystal.
cite) +rod-shaped aragonite
There are three polymorphs: e) and spherical Vaterita.
従来より粉体を球状化することによって、例えば充填性
や分散性が向上したり、低摩耗性になるなど種々の粉体
物性が改良されることは良く知られており、炭酸カルシ
ウムに於いても球状のバテライト型炭酸カルシウムが注
目され、各種の製造方法が提案されている。It has been well known that by spheroidizing powder, various physical properties of the powder can be improved, such as improved filling and dispersibility, and reduced abrasion. Spherical vaterite-type calcium carbonate has attracted attention, and various production methods have been proposed.
特公昭４３−２５１４８号、特公昭４８−３５１５９号
にはカルシウム塩の水溶液に二酸化炭素を吹込み、球状
バテライト型炭酸カルシウムを合成する方法が示されて
いる。また、特開昭５５−９５６１７号にはカルシウム
塩と炭酸塩との水溶液反応において反応濃度と反応温度
の制御下に球状バテライト型炭酸カルシウムを製造する
方法が示されている。特開昭６１−１６８５２４号には
ポリリン酸塩を溶解して含む水酸化カルシウムに二酸化
炭素を吹込んで球状炭酸カルシウムを製造する方法が示
されている。Japanese Patent Publication No. 43-25148 and Japanese Patent Publication No. 48-35159 disclose a method for synthesizing spherical vaterite-type calcium carbonate by blowing carbon dioxide into an aqueous solution of calcium salt. Further, JP-A-55-95617 discloses a method for producing spherical vaterite-type calcium carbonate in an aqueous reaction between a calcium salt and a carbonate under control of the reaction concentration and reaction temperature. JP-A-61-168524 discloses a method for producing spherical calcium carbonate by blowing carbon dioxide into calcium hydroxide containing a dissolved polyphosphate.
しかし之等の方法では、球状バテライト型炭酸カルシウ
ムを製造することは出来ても本発明の特徴である中空の
構造にすることは出来ない。However, with these methods, although it is possible to produce spherical vaterite-type calcium carbonate, it is not possible to form it into a hollow structure, which is a feature of the present invention.
球状バテライト型炭酸カルシウムであり、中空構造にな
る可能性がある製造方法としては界面反応法（中原、多
沢、宮田：日本化学会誌、 ５．７３２（１９７６））
があるが遠心分離操作が必要であるため工業的な製造方
法としては煩雑過ぎる欠点を有している。The interfacial reaction method (Nakahara, Tazawa, Miyata: Journal of the Chemical Society of Japan, 5.732 (1976)) is a production method that is spherical vaterite-type calcium carbonate and may have a hollow structure.
However, since it requires a centrifugal separation operation, it has the drawback of being too complicated as an industrial production method.
以上述べた様に中空且つ球状のバテライト型炭酸カルシ
ウムの工業的な製造方法は未だ確立されていないのが現
状である。As mentioned above, at present, an industrial method for producing hollow, spherical vaterite-type calcium carbonate has not yet been established.
一方１球状のバテライト型炭酸カルシウムは水が存在し
なければ常温・常圧では結晶形の変化は起こらない、し
かし水が存在すると容易に球状形態を損ない、安定相で
ある菱面体晶のカルサイトへ転移するという性質がある
。このため球状バテライト型炭酸カルシウムの安定化方
法が種々提案されている。On the other hand, the crystal form of monospherical vaterite-type calcium carbonate does not change at room temperature and pressure in the absence of water.However, in the presence of water, the spherical form is easily lost, and the stable phase is rhombohedral calcite. It has the property of transferring to. For this reason, various methods for stabilizing spherical vaterite-type calcium carbonate have been proposed.
特開昭５５−９５６１７号には球状バテライト型炭酸カ
ルシウムの表面を高級脂肪酸で処理し安定化する方法が
示されているが高級脂肪酸で処理すると水への分散性が
非常に悪化するという問題が生じる。JP-A-55-95617 discloses a method of stabilizing the surface of spherical vaterite-type calcium carbonate by treating it with higher fatty acids, but there is a problem that the treatment with higher fatty acids greatly deteriorates the dispersibility in water. arise.
また特開昭５７−９２５２０号にはカルシウム塩と炭酸
塩との水溶液反応により球状バテライト型炭酸カルシウ
ムを製造するに際し、カルシウム以外の２価金属イオン
を添加する方法が示されているが、安定化の効果が不充
分である。Furthermore, JP-A No. 57-92520 discloses a method of adding divalent metal ions other than calcium when producing spherical vaterite-type calcium carbonate through an aqueous reaction between calcium salt and carbonate. The effect is insufficient.
また特開昭５７−９２５２１号には球状バテライト型炭
酸カルシウムを４００〜８００℃の温度で熱処理し球状
の侭カルサイトに転移させる方法が示されているが、高
温処理のため球状粒子の融着の問題や熱処理コストが高
くなるなどの問題がある。Furthermore, JP-A No. 57-92521 discloses a method of heat-treating spherical vaterite-type calcium carbonate at a temperature of 400 to 800°C to transform it into spherical lateral calcite. There are problems such as problems and increased heat treatment costs.
以上述べた様に球状バテライト型炭酸カルシウムを経済
的に実施し得る工業的な安定化方法は未だ確立されてい
ない実情にある。As mentioned above, an economically viable industrial stabilization method for spherical vaterite calcium carbonate has not yet been established.
以上述べた様に中空であり且つ球状のバテライト型炭酸
カルシウムの工業的な製造法及びその安定化法に就いて
は未だ確立されていない。As mentioned above, an industrial method for producing hollow and spherical vaterite-type calcium carbonate and a method for stabilizing the same have not yet been established.
本発明は球状であるため充填性や分散性に優れ、低摩耗
性であり、しかも粒子内部が中空であるため低比重であ
るという特徴を有し、しかも化学的に安定なバテライト
型炭酸カルシウムの工業的な製造法を提供し様とするも
のである。The present invention is made of vaterite-type calcium carbonate, which is spherical, has excellent filling properties and dispersibility, has low abrasion properties, and has a low specific gravity because the inside of the particle is hollow, and is chemically stable. The aim is to provide an industrial manufacturing method.
〔課題を解決するための手段及び作用〕本発明者等は中
空・球状炭酸カネシウムの製造法の研究を鋭意続けた結
果、水に対する溶解度が無いか、または小さな特定のア
ルコール中に塩化カルシウム或いは硝酸カルシウムを溶
解させ、この中に炭酸塩水溶液を滴下・混合し、連続相
がアルコール、分散相が水である油中水型エマルジョン
を造り、アルコールと水との界面で炭酸カルシウムを生
成させるという方法により、中空・球状炭酸カルシウム
を容易に１１Ｉ造呂来ることを見い出した。[Means and effects for solving the problem] As a result of intensive research into the method for producing hollow and spherical canesium carbonate, the present inventors have found that calcium chloride or nitric acid has no solubility in water or has little solubility in water. A method in which calcium is dissolved and an aqueous carbonate solution is added dropwise and mixed into the solution to create a water-in-oil emulsion in which the continuous phase is alcohol and the dispersed phase is water, and calcium carbonate is generated at the interface between alcohol and water. It was discovered that hollow and spherical calcium carbonate can be easily formed into 11I.
本発明に於いて使用するアルコールとしては。Alcohols used in the present invention include:
塩化カルシウム、或いは硝酸カルシウムを溶解出来、し
かも水に対する溶解度が無いか、または小さなアルコー
ルに限られ、具体的には、ブタノール（１−ブタノール
、２−ブタノール、インブタノール）、ペンタノール（
１−ペンタノール、２−ペンタノール、３−ペンタノー
ル、２−メチル−１−ブタノール、２−メチル−２−ブ
タノール。Alcohols that can dissolve calcium chloride or calcium nitrate but have no solubility in water or are limited to small alcohols, specifically butanol (1-butanol, 2-butanol, imbutanol), pentanol (
1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol.
３−メチル−１−ブタノール、３−メチル−２−ブタノ
ール）が使用される。3-methyl-1-butanol, 3-methyl-2-butanol) are used.
炭酸塩としては、炭酸ナトリウム、炭酸カリウム、炭酸
アンモニウム、炭酸水素ナトリウムなどが使用出来る。As the carbonate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, etc. can be used.
塩化カルシウムまたは硝酸カルシウムが溶解しているア
ルコールを攪拌器付き反応容器に入れ、攪拌しながら炭
酸塩水溶液を滴下する。アルコールと炭酸水溶液の容積
比はアルコールが連続相を維持出来る範囲内で任意の容
積比とすることが出来る。Alcohol in which calcium chloride or calcium nitrate is dissolved is placed in a reaction vessel equipped with a stirrer, and an aqueous carbonate solution is added dropwise while stirring. The volume ratio of the alcohol to the carbonic acid aqueous solution can be set to any desired volume ratio within a range where the alcohol can maintain a continuous phase.
水中の炭酸イオン／アルコール中のカルシウムイオン
のモル比はＯ０１〜１０が好ましい、最適なモル比は１
である。Carbonate ions in water/calcium ions in alcohol
The molar ratio is preferably O01 to 10, the optimal molar ratio is 1
It is.
この中空・球状バテライト型炭酸カルシウムの生成反応
に於いて乳化剤は必ずしも必要ではないが、ＨＬＢ＝６
〜１５の乳化剤を使用することが出来る。Although an emulsifier is not necessarily necessary in the reaction for producing hollow/spherical vaterite type calcium carbonate, HLB=6
~15 emulsifiers can be used.
本発明の炭酸カルシウムの粒子径は、アルコール／水
の容積比、攪拌の程度および添加する乳化剤の種類と量
を変えることにより、制御することが出来る。また中空
の程度は、アルコール中のカルシウムイオン濃度と水中
の炭酸イオン濃度を変えることにより制御８来るし、ア
ルコール／水の容積比、攪拌の程度及び添加する乳化剤
の種類と量の変化によっても制御することが出来る。The particle size of calcium carbonate of the present invention is alcohol/water
It can be controlled by changing the volume ratio of , the degree of stirring, and the type and amount of emulsifier added. The degree of hollowness can be controlled by changing the concentration of calcium ions in the alcohol and the concentration of carbonate ions in the water8, and can also be controlled by changing the volume ratio of alcohol/water, the degree of stirring, and the type and amount of emulsifier added. You can.
次に、請求項１で得られる中空・球状型炭酸カルシウム
はバテライト型であり、水分が無い方面への用途が考え
られる。しかし水分が存在する場合には菱面体晶のカル
サイト型へ転移し７、本発明の炭酸カルシウムの特徴で
ある中空・球状の形態が損なねれるという欠点があり、
用途が限定される。Next, the hollow and spherical calcium carbonate obtained in claim 1 is of the vaterite type, and can be used in areas where there is no moisture. However, in the presence of water, calcium carbonate transforms to a rhombohedral calcite type7, and the hollow, spherical shape characteristic of the calcium carbonate of the present invention is lost.
Uses are limited.
本発明者等は中空・球状バテライト型炭酸カルシウムの
安定化に就いて鋭意検討した結果、該炭酸カルシウムの
表面を特定の酸で処理し表面を不活性にすることによっ
て、水中に於いても中空・球状の形態を維持出来ること
を見い出した。As a result of intensive research into stabilizing hollow and spherical vaterite-type calcium carbonate, the inventors of the present invention found that by treating the surface of the calcium carbonate with a specific acid to make the surface inactive, it is possible to stabilize hollow and spherical vaterite-type calcium carbonate even in water.・We discovered that the spherical shape can be maintained.
具体的には、オルトリン酸、ピロリン酸２次亜すン酸、
亜リン酸、ピロ亜すン酸９次すン酸、ポリリン酸、メタ
リン酸、ウルトラリン酸などのリンのオキソ酸が使用出
来る。Specifically, orthophosphoric acid, pyrophosphoric acid secondary hyposulfite,
Phosphorous oxoacids such as phosphorous acid, pyrophosphorous acid, 9th phosphorous acid, polyphosphoric acid, metaphosphoric acid, and ultraphosphoric acid can be used.
中空・球状バテライト型炭酸カルシウムの水懸濁液にリ
ンのオキソ酸水溶液を滴下、混合することで安定化が達
成される。リンのオキソ酸の添加量は、中空・球状バテ
ライト型炭酸カルシウムの絶乾重量に対して０．１重量
％以上が好ましい。０．１重量％未満の場合には安定化
の効果が小さい、中空・球状バテライト型炭酸カルシウ
ムの表層部分がリンのオキソ酸と反応し、難溶性或いは
不溶性であるリンのオキソ酸カルシウム塩に変化するた
めに安定化されるものと考えられる。Stabilization is achieved by dropping an aqueous phosphorus oxoacid solution into an aqueous suspension of hollow/spherical vaterite-type calcium carbonate and mixing it. The amount of the phosphorus oxoacid added is preferably 0.1% by weight or more based on the absolute dry weight of the hollow/spherical vaterite type calcium carbonate. When the amount is less than 0.1% by weight, the stabilizing effect is small.The surface layer of the hollow/spherical vaterite type calcium carbonate reacts with the phosphorus oxoacid and changes to a poorly soluble or insoluble phosphorus oxoacid calcium salt. It is thought that it is stabilized due to the
以下１本発明を実施例により具体的に説明する。 The present invention will be specifically explained below using examples.
ただし、本発明は実施例に示した内容により何等制限を
受けるものではない。However, the present invention is not limited in any way by the contents shown in the examples.
実施例１
実施例１−１〜１−７では、所定量の塩化カルシウムを
溶解させたペンタノールまたはブタノールの７００ｍ１
２をホモジナイザーに入れ、ホモジナイザーで攪拌しな
がら所定量の炭酸ナトリウムを溶解した水３００−を滴
下し、滴下終了後５分間攪拌を続けた。カルシウムイオ
ン／炭酸イオン のモル比は１とした。生成した炭酸カ
ルシウムを炉別し無水メタノールで洗浄後、風乾し、そ
の形状と結晶型を調査した。Example 1 In Examples 1-1 to 1-7, 700 ml of pentanol or butanol in which a predetermined amount of calcium chloride was dissolved
2 was placed in a homogenizer, and while stirring with the homogenizer, 300ml of water in which a predetermined amount of sodium carbonate was dissolved was added dropwise, and stirring was continued for 5 minutes after the dropwise addition was completed. The molar ratio of calcium ions/carbonate ions was set to 1. The produced calcium carbonate was separated in a furnace, washed with anhydrous methanol, air-dried, and its shape and crystal type were investigated.
走査型電子顕微鏡で形状を観察し、ｘ１ｉＡ回折装置で
結晶形を調べた。The shape was observed using a scanning electron microscope, and the crystal form was examined using an x1iA diffractometer.
実施例１−８では１−ペンタノールに溶解させるカルシ
ウム塩を硝酸カルシウムに変えた以外は実施例１−１と
同様に行なった。Example 1-8 was carried out in the same manner as Example 1-1 except that the calcium salt dissolved in 1-pentanol was changed to calcium nitrate.
実施例１−９．１０．１１では水に溶解させるＪＡＮ＆
塩を炭酸カリウム、炭酸アンモニウム、炭酸水素ナトリ
ウムに変えた以外は実施例１−１と同様に行なった。In Example 1-9.10.11, JAN&
The same procedure as in Example 1-1 was carried out except that the salt was changed to potassium carbonate, ammonium carbonate, or sodium hydrogen carbonate.
電子顕微蔑観察とＸ線回折装置で分析した結果、第１表
に示す様に実施例１−１〜１−ＩＪの全てで球状バテラ
イト型炭酸カルシウムが生成した６以下余白
実施例２
実施例２−１〜２−９では実施例１−１で生成した球状
バテライト型炭酸カルシウムの水懸濁液に各種のリンの
オキソ酸を滴下混合し炭酸カルシウムの安定化処理を行
なった。処理後、炭酸カルシウムを炉則し、之を８０℃
の温水中に投入し、所定時間毎にサンプリングしてＸ線
回折によりバテライト型からカルサイト型への転移率を
調べ、バテライト型炭酸カルシウムの残存率を求めた。As a result of electron microscope observation and analysis using an X-ray diffraction device, as shown in Table 1, spherical vaterite-type calcium carbonate was produced in all of Examples 1-1 to 1-IJ. In -1 to 2-9, various phosphorus oxoacids were added dropwise to the aqueous suspension of spherical vaterite type calcium carbonate produced in Example 1-1 to stabilize the calcium carbonate. After treatment, heat the calcium carbonate to 80°C.
The samples were sampled at predetermined time intervals to examine the transition rate from vaterite type to calcite type by X-ray diffraction, and the residual rate of vaterite type calcium carbonate was determined.
バテライト残存率は下記の式より算出した。The vaterite residual rate was calculated using the following formula.
ｆ（Ｃ）”＝Ｉ１０４（Ｃ）／１１□。（ｖ）＋Ｉ、１
２ （Ｖ） ＋ Ｌｘｎ （Ｖ） ＋ １１０４ （Ｃ
）ｆ（ｖ）＝Ｉ−ｆ（ｃ）
バテライト残存率（％）＝１００Ｘｆ（ｖ）なお、例え
ば工、。４（ｃ）はカルサイトの１０４面に於けるＸ線
ピーク強度、■、１゜（Ｖ）はバテライトの１１０面に
於けるＸ線ピーク強度である。f(C)”=I104(C)/11□.(v)+I,1
2 (V) + Lxn (V) + 1104 (C
)f(v)=I-f(c) Vaterite residual rate (%)=100Xf(v)For example, 4(c) is the X-ray peak intensity at the 104 plane of calcite, and 1° (V) is the X-ray peak intensity at the 110 plane of vaterite.
第１図は実施例２−１で得られた中空・球状バテライト
型炭酸カルシウムの５０００倍電子顕微鏡写真であり、
第２図は実施例２−１で得られた中空・球状バテライト
型炭酸カルシウムを超音波粉砕したものの１００００倍
電子顕微鏡写真であり、中央の粒子が一部破壊され内部
の空隙が観察される。FIG. 1 is a 5000x electron micrograph of hollow and spherical vaterite-type calcium carbonate obtained in Example 2-1.
FIG. 2 is a 10,000x electron micrograph of the hollow and spherical vaterite-type calcium carbonate obtained in Example 2-1 that was ultrasonically pulverized, and the central particles are partially destroyed and internal voids are observed.
実施例２−１０．１１ではリンのオキソ酸の添加量を変
えた以外は実施例２−１と同様に行なった。Example 2-10.11 was carried out in the same manner as Example 2-1 except that the amount of phosphorus oxoacid added was changed.
第２表の結果に示す様に各種のリンのオキソ酸で処理す
ることにより球状バテライト型炭酸カルシウムが安定化
されることが判る。なお実施例１−２〜１−１１で得ら
れた球状バテライト型炭酸力ルシウ゛ムも同様の処理で
安定化出来た。As shown in the results in Table 2, it can be seen that spherical vaterite type calcium carbonate is stabilized by treatment with various phosphorus oxoacids. The spherical vaterite-type calcium carbonate obtained in Examples 1-2 to 1-11 could also be stabilized by the same treatment.
以下余白
実施例３
所定量の塩化カルシウムを溶解して含む１−ペンタノー
ル７００−をホモジナイザーに入れ攪拌しながら所定量
の炭酸ナトリウムを溶解した水３００−を滴下し、滴下
終了後、５分間攪拌を続けた。Below is the margin Example 3 1-Pentanol 700- containing a predetermined amount of dissolved calcium chloride is placed in a homogenizer, and while stirring, water 300- in which a predetermined amount of sodium carbonate is dissolved is added dropwise, and after the dropwise addition is completed, stir for 5 minutes. continued.
カルシウムイオン／炭酸イオン のモル比は１とした。The molar ratio of calcium ions/carbonate ions was set to 1.
実施例３−１〜３−４では塩化カルシウム及び炭酸ナト
リウムの溶解量を変えて球状バテライト型炭酸カルシウ
ムを調製した。調製した炭酸カルシウムを濾過し、再び
水でスラリー化した後。In Examples 3-1 to 3-4, spherical vaterite-type calcium carbonate was prepared by changing the dissolved amounts of calcium chloride and sodium carbonate. After filtering the prepared calcium carbonate and slurrying it with water again.
オルトリン酸を加え安定化処理を施した。処理後、乾燥
し、この球状炭酸カルシウムの嵩比重を測定した。嵩比
重の測定は粘度ハンドブック（技報堂）に記載された真
比重の測定方法（ｐ４９５）に従った。Stabilization treatment was performed by adding orthophosphoric acid. After the treatment, it was dried and the bulk specific gravity of this spherical calcium carbonate was measured. The bulk specific gravity was measured according to the method for measuring true specific gravity (p495) described in the Viscosity Handbook (Gihodo).
比較例２では市販のカルサイト型重質炭酸カルシウム（
商品名：ニスカロン＃ ８００ 、三共精粉株式会社製
）の真比重を測定した。In Comparative Example 2, commercially available calcite-type heavy calcium carbonate (
The true specific gravity of Niscalon #800 (trade name, manufactured by Sankyo Seifun Co., Ltd.) was measured.
比較例３では水溶液反応（特開昭５７−９２５２０号）
で得られた球状バテライト型炭酸カルシウムの真比重を
測定した。In Comparative Example 3, an aqueous solution reaction (Japanese Unexamined Patent Publication No. 57-92520)
The true specific gravity of the spherical vaterite-type calcium carbonate obtained was measured.
第３表に示す様に本発明で得られる球状バテライト型炭
酸カルシウムの嵩比重は比較例の真比重よりも小さく中
空構造になっていることが判る。As shown in Table 3, it can be seen that the bulk specific gravity of the spherical vaterite type calcium carbonate obtained by the present invention is smaller than the true specific gravity of the comparative example and has a hollow structure.
以下余白
〔発明の効果〕
本発明は球状パイライト型であり、しかも中空であるた
めに比重が小さいという特徴を有する炭酸カルシウムの
新規な製造法とその安定化法に関するものであり、工業
的価値は極めて高いものである。The following margins [Effects of the Invention] The present invention relates to a new method for producing and stabilizing calcium carbonate, which is of a spherical pyrite type and has a characteristic of having a low specific gravity due to its hollowness, and has an industrial value. This is extremely high.
第１図は実施例２−１で得られた中空・球状バテライト
型炭酸カルシウの５０００倍電子顕微鏡写真であり、第
２図は実施例２−１で得られた中空・球状バテライト型
炭酸カルシウムを超音波粉砕したものの１００００倍電
子顕微鏡写真である。
特
許
出
願
人
山陽国策パルプ株式会社
苓 １ 図
手続補正書
昭和６３年１１月３０日Figure 1 is a 5000x electron micrograph of the hollow and spherical vaterite type calcium carbonate obtained in Example 2-1, and Figure 2 is a 5000x electron micrograph of the hollow and spherical vaterite type calcium carbonate obtained in Example 2-1. This is a 10,000x electron micrograph of the ultrasonically pulverized product. Patent Applicant: Sanyo Kokusaku Pulp Co., Ltd. 1 Amendment to Figure Procedures November 30, 1988
Claims (1)
ルシウムまたは硝酸カルシウムを溶解させ、この中に炭
酸塩水溶液を滴下・混合し連続相がアルコール、分散相
が水であるエマルジョンのアルコールと水との界面で炭
酸カルシウムを生成させることを特徴とする中空・球状
のバテライト型炭酸カルシウムの製造法。 ２ アルコールがブタノールまたはペンタノールである
請求項１記載の中空・球状のバテライト型炭酸カルシウ
ムの製造法。 ３ 請求項１、２項記載の中空・球状のバテライト型炭
酸カルシウムの水懸濁液にリンのオキソ酸を添加するこ
とを特徴とするバテライト型炭酸カルシウムの結晶の安
定化法。[Claims] 1. An emulsion in which calcium chloride or calcium nitrate is dissolved in alcohol that is insoluble or sparingly soluble in water, and an aqueous carbonate solution is added dropwise and mixed therein, with the continuous phase being alcohol and the dispersed phase being water. A method for producing hollow, spherical vaterite-type calcium carbonate, which is characterized by producing calcium carbonate at the interface between alcohol and water. 2. The method for producing hollow, spherical vaterite-type calcium carbonate according to claim 1, wherein the alcohol is butanol or pentanol. 3. A method for stabilizing vaterite-type calcium carbonate crystals, which comprises adding a phosphorus oxoacid to the aqueous suspension of the hollow and spherical vaterite-type calcium carbonate according to claims 1 and 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22634088A JPH02153819A (en) | 1988-09-12 | 1988-09-12 | Production of hollow and spherical vaterite type calcium carbide and stabilization thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22634088A JPH02153819A (en) | 1988-09-12 | 1988-09-12 | Production of hollow and spherical vaterite type calcium carbide and stabilization thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02153819A true JPH02153819A (en) | 1990-06-13 |
| JPH0451488B2 JPH0451488B2 (en) | 1992-08-19 |
Family
ID=16843637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22634088A Granted JPH02153819A (en) | 1988-09-12 | 1988-09-12 | Production of hollow and spherical vaterite type calcium carbide and stabilization thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02153819A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5292495A (en) * | 1991-05-27 | 1994-03-08 | Kowa-Chemical Industry Co., Ltd. | Porous particles of calcium carbonate and method for the preparation thereof |
| JP2005200282A (en) * | 2004-01-16 | 2005-07-28 | Okutama Kogyo Co Ltd | Hollow columnar calcium carbonate and method of manufacturing the same |
| JP2005281034A (en) * | 2004-03-29 | 2005-10-13 | Nagoya Kogyo Univ | Hollow/spherical calcium carbonate particles and method for manufacturing the same |
| JP2006008662A (en) * | 2004-06-18 | 2006-01-12 | Unilever Nv | Method for growing crystal |
| EP1652818A1 (en) * | 2004-10-26 | 2006-05-03 | Dr. Zinkeisen, Behrmann & Co.m.b.H. | High purity calcium carbonate |
| JP2008115053A (en) * | 2006-11-07 | 2008-05-22 | Nagoya Institute Of Technology | Hollow calcium carbonate particles which is synthesized in non-equilibrium situation and method for synthesis of the same |
| JP2009073686A (en) * | 2007-09-20 | 2009-04-09 | Oita Univ | Calcium carbonate having macaroni-like shape and its manufacturing method |
| JP2011051834A (en) * | 2009-09-02 | 2011-03-17 | Taiheiyo Cement Corp | Method of producing high purity vaterite-type spherical calcium carbonate |
| JP2011144056A (en) * | 2010-01-12 | 2011-07-28 | National Institute Of Advanced Industrial Science & Technology | Substance-encapsulated calcium carbonate, and production method and use of the same |
| JP2011157245A (en) * | 2010-02-03 | 2011-08-18 | Univ Of Miyazaki | Method for producing spherical calcium carbonate |
| JP2013053125A (en) * | 2011-09-06 | 2013-03-21 | Nagasaki Univ | Nucleic-acid introducing agent containing abrasive |
| CN104324674A (en) * | 2014-10-09 | 2015-02-04 | 哈尔滨工业大学宜兴环保研究院 | Method for preparation of inorganic mineralized microcapsule based on liquid drops obtained by dissolution of ethanol's crystal nucleuses in water |
| CN105585041A (en) * | 2016-01-26 | 2016-05-18 | 广西科技大学 | Preparation method of orange slice type calcium carbonate particles |
-
1988
- 1988-09-12 JP JP22634088A patent/JPH02153819A/en active Granted
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5292495A (en) * | 1991-05-27 | 1994-03-08 | Kowa-Chemical Industry Co., Ltd. | Porous particles of calcium carbonate and method for the preparation thereof |
| JP4515780B2 (en) * | 2004-01-16 | 2010-08-04 | 奥多摩工業株式会社 | Hollow columnar calcium carbonate and method for producing the same |
| JP2005200282A (en) * | 2004-01-16 | 2005-07-28 | Okutama Kogyo Co Ltd | Hollow columnar calcium carbonate and method of manufacturing the same |
| JP2005281034A (en) * | 2004-03-29 | 2005-10-13 | Nagoya Kogyo Univ | Hollow/spherical calcium carbonate particles and method for manufacturing the same |
| JP4660745B2 (en) * | 2004-03-29 | 2011-03-30 | 国立大学法人 名古屋工業大学 | Hollow / spherical calcium carbonate particles and method for producing the same |
| JP2006008662A (en) * | 2004-06-18 | 2006-01-12 | Unilever Nv | Method for growing crystal |
| EP1652818A1 (en) * | 2004-10-26 | 2006-05-03 | Dr. Zinkeisen, Behrmann & Co.m.b.H. | High purity calcium carbonate |
| JP2008115053A (en) * | 2006-11-07 | 2008-05-22 | Nagoya Institute Of Technology | Hollow calcium carbonate particles which is synthesized in non-equilibrium situation and method for synthesis of the same |
| JP2009073686A (en) * | 2007-09-20 | 2009-04-09 | Oita Univ | Calcium carbonate having macaroni-like shape and its manufacturing method |
| JP2011051834A (en) * | 2009-09-02 | 2011-03-17 | Taiheiyo Cement Corp | Method of producing high purity vaterite-type spherical calcium carbonate |
| JP2011144056A (en) * | 2010-01-12 | 2011-07-28 | National Institute Of Advanced Industrial Science & Technology | Substance-encapsulated calcium carbonate, and production method and use of the same |
| JP2011157245A (en) * | 2010-02-03 | 2011-08-18 | Univ Of Miyazaki | Method for producing spherical calcium carbonate |
| JP2013053125A (en) * | 2011-09-06 | 2013-03-21 | Nagasaki Univ | Nucleic-acid introducing agent containing abrasive |
| CN104324674A (en) * | 2014-10-09 | 2015-02-04 | 哈尔滨工业大学宜兴环保研究院 | Method for preparation of inorganic mineralized microcapsule based on liquid drops obtained by dissolution of ethanol's crystal nucleuses in water |
| CN105585041A (en) * | 2016-01-26 | 2016-05-18 | 广西科技大学 | Preparation method of orange slice type calcium carbonate particles |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0451488B2 (en) | 1992-08-19 |
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