JPS6225607B2 - - Google Patents
Info
- Publication number
- JPS6225607B2 JPS6225607B2 JP56195606A JP19560681A JPS6225607B2 JP S6225607 B2 JPS6225607 B2 JP S6225607B2 JP 56195606 A JP56195606 A JP 56195606A JP 19560681 A JP19560681 A JP 19560681A JP S6225607 B2 JPS6225607 B2 JP S6225607B2
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- calcium carbonate
- slurry
- particles
- type
- 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.)
- Expired
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 51
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 42
- 239000010457 zeolite Substances 0.000 claims description 34
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 32
- 229910021536 Zeolite Inorganic materials 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 159000000007 calcium salts Chemical class 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000003513 alkali Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- -1 alkaline earth metal salt Chemical class 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 235000008733 Citrus aurantifolia 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
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000004571 lime 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
- 239000000203 mixture Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical class O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明はゼオライト粒子表面に微細な炭酸カル
シウム粒子を実質的に沈着被覆させたゼオライト
−炭酸カルシウム複合体の製造方法に関する。更
に言えば炭酸カルシウムをゼオライト表面に被覆
することによつて分散性の良好な粒度調整が可能
でゼオライト特有の粉体特性を有するゼオライト
−炭酸カルシウム複合体の製造方法に関する。
本発明者等は先にゼオライト類懸濁液中で難溶
性アルカリ土類金属塩を形成し沈積させることに
よつてゼオライト−難溶性アルカリ土類金属塩複
合体を得て、これを樹脂添加物として利用する提
案を行なつた。（特願昭55−142012号）これは主
にステアリン酸等高級脂肪酸が樹脂からブルーミ
ングすることを防止する目的であり、又、本来、
分散性が良好でない難溶性アルカリ土類金属塩を
ゼオライトに複合させることによつて適度の塩基
性を保持したまま分散性良好な粉体とすることの
提供にあつた。
本発明は従来より主として樹脂類、紙類等の充
填剤等に利用されている炭酸カルシウムをゼオラ
イトに複合させることによつて、従来一次粒子と
して0.5μｍ以下の微粉末である炭酸カルシウム
粒子を通常0.1〜10μｍのゼオライト粒子に沈着
被覆して所望の粒度の調整が可能な分散性の良好
なゼオライト−炭酸カルシウム複合体を提供する
ことにある。すなわち本発明は、ゼオライト粒子
表面に微細な炭酸カルシウムを沈積被覆させてな
るゼオライト−炭酸カルシウム複合体に関する。
本発明に用いられるゼオライトは、Ｘ線回折に
よつて容易に識別される結晶質の三次元構造を有
するアルミノ珪酸塩であつて、例えばＡ型、Ｘ
型、Ｙ型、Ｐ型の合成ゼオライト、モルデナイ
ト、クリノプチロライト、エリオナイトなど天然
ゼオライト及びソーダライト族アルミノ珪酸塩で
ある。これらは多くの場合カチオンがナトリウム
であるが、そのナトリウムを他の金属たとえばカ
ルシウム、マグネシウム等のアルカリ土類金属の
イオンに置換した金属置換型ゼオライトも含まれ
る。これらゼオライトのうち特に好適なゼオライ
トはＡ型又はＸ型ゼオライト及びそれらの金属置
換ゼオライトである。
この理由は、例えばＡ型ゼオライト又はＸ型ゼ
オライトの如き合成ゼオライトは水性スラリー中
にあつて殆んど一次粒子に分散し易く、またこれ
らのゼオライトは合成条件によつて一次粒子の粒
径のコントロールが容易であり、工業的な用途の
面から、芯材として好適であるからである。
他方、ゼオライトの粒度は、用途や使用目的あ
るいはそれ自体の性状等によつて、一様でない
が、充填剤あるいは樹脂添加剤などに適用する場
合、多くの場合、平均粒子径が10μｍ以下が適当
で、好ましくは0.1〜５μｍの範囲にあるもので
ある。また、ゼオライトは合成条件、結晶型、粉
砕等によつて種々の形状があるが、本発明におい
てはその形状は特に限定なく適用できる。本発明
に係る複合体は、ゼオライトとその一次粒子より
も微細な炭酸カルシウムとの混合物であるが、微
細な炭酸カルシウムがゼオライト粒子表面に沈積
して実質的に被覆状態で存在する関係にある。こ
こに実質的にというのは、両者の量的関係、製造
条件等によつて差異はあるが、走査型又は透過型
の電子顕微鏡写真によつて粒子をみた場合、ゼオ
ライト粒子表面に殆んど遊離の炭酸カルシウムが
認められないで微細な炭酸カルシウムがゼオライ
ト粒子に沈積被覆したものから、多少炭酸カルシ
ウムと思われる微細粒子がゼオライト粒子から遊
離して認められる程度をいい、換言すれば炭酸カ
ルシウムの大半がゼオライト粒子に被覆状態で存
在していることを意味する。
かかる複合体の粒子径は芯材となるゼオライト
粒子径に依存するが、各種の樹脂の改質剤として
使用する場合には、平均粒子径が0.3〜10μｍの
範囲好ましくは0.5〜５μｍの範囲にある。ゼオ
ライトと炭酸カルシウムの量的関係は両者の粒子
径、複合体の用途等に応じて任意に調整されうる
が、多くの場合、ゼオライト100重量部に対して
炭酸カルシウムが５〜100重量部が好適な範囲で
ある。
本発明にかかるゼオライト−炭酸カルシウム複
合体は樹脂添加剤、充填剤あるいは無機発泡体と
して各種の用途が認められる。かかる複合体はア
ルカリ性ゼオライトスラリー中で可溶性カルシウ
ム塩又は／及び石灰乳と炭酸化剤とを接触して反
応させてゼオライト粒子表面上に微細な炭酸カル
シウムを沈積させることにより製造することがで
きる。可溶性カルシウム塩としては塩化カルシウ
ムが好適であるが、その他、硝酸カルシウムのよ
うなものであつてもよい。炭酸化剤としては、
CO2ガス、炭酸水が好適であるが、必要に応じて
炭酸アルカリ又は重炭酸アルカリなどを用いても
よい。
かかる製法の具体的態様として次の３つの方法
を代表的にあげるが、特にこれらの方法に限定さ
れるものでない。
(1) 適度の粒度に調整されたゼオライト水性スラ
リーに水溶性カルシウム塩水溶液を添加したの
ちアルカリを添加し水酸化カルシウム−ゼオラ
イトスラリーを調製し、これに炭酸ガス又は炭
酸水を添加する。なお、この場合、アルカリを
添加しないで直接炭酸ガス等を導入してもよ
い。
(2) 適度の粒度に調整されたゼオライト水性スラ
リーに水溶性カルシウム塩水溶液を添加したの
ち、水溶性炭酸カルシウム又は重炭酸アルカリ
を添加するか、又は水溶性カルシウム塩水溶液
と水溶性炭酸アルカリと水溶性重炭酸アルカリ
を同時に添加する。
(3) 予め石灰乳スラリーを調製しこれをゼオライ
ト水性スラリーに添加したのち炭酸ガス又は炭
酸水を添加する。
これらいずれの方法によつてもゼオライト粒子
表面は炭酸カルシウム粒子によつて沈着被覆され
るが、その反応条件としては反応温度は40℃以上
が必要であり、望ましくは60℃以上とし、反応終
了時のスラリーのPHは８ないし10とすることが重
要である。温度設定が40℃以下であると乾燥時に
凝集傾向が大となり分散不良を起す原因となり、
反応終了時のスラリーのPHが８以下となるゼオラ
イト表面に沈着被覆された炭酸カルシウム層が脱
離し易くなる。
このようにして得られたゼオライト−炭酸カル
シウム水性スラリーは常法により過及び水によ
る洗浄を行なつたのち、温風乾燥、真空乾燥によ
り脱水し、必要に応じて粉砕して製品とする。
以下に本発明を実施例を挙げて説明する。
実施例 １
表１に示す粒度分布のCa置換Ａ型ゼオライト
200ｇを水800ｇに分散したのち、塩化カルシウム
水溶液（CaCl2100ｇ／ｌ）456mlを添加して60℃
に加温したのち、５重量％水酸化ナトリウム水溶
液640mlを加えた。このスラリーを撹拌しながら
炭酸ガスを毎分50mlで導入しスラリーのPHが9.5
となるまでつづけた。約30分、60℃で撹拌を継続
したのち過し、過ケーキを水洗、120℃の温
風乾燥を施し粉砕してゼオライト−炭酸カルシウ
ム複合体を得た。性状を表−１に示す。
The present invention relates to a method for producing a zeolite-calcium carbonate composite in which the surfaces of zeolite particles are substantially deposited and coated with fine calcium carbonate particles. More specifically, the present invention relates to a method for producing a zeolite-calcium carbonate composite having powder characteristics unique to zeolite, in which particle size can be adjusted with good dispersibility by coating the surface of the zeolite with calcium carbonate. The present inventors first formed and precipitated a sparingly soluble alkaline earth metal salt in a zeolite suspension to obtain a zeolite-poorly soluble alkaline earth metal salt complex, which was then added to a resin additive. We made a proposal for its use as a (Patent Application No. 55-142012) This is mainly for the purpose of preventing higher fatty acids such as stearic acid from blooming from the resin, and originally,
The present invention aims to provide a powder with good dispersibility while maintaining appropriate basicity by compounding a poorly soluble alkaline earth metal salt with poor dispersibility into zeolite. The present invention has been developed by combining calcium carbonate, which has conventionally been mainly used as a filler for resins, papers, etc., with zeolite, thereby converting calcium carbonate particles, which are normally fine powders of 0.5 μm or less in size, as primary particles. The object of the present invention is to provide a zeolite-calcium carbonate composite with good dispersibility, which can be deposited and coated on zeolite particles of 0.1 to 10 μm to adjust the desired particle size. That is, the present invention relates to a zeolite-calcium carbonate composite formed by depositing and coating the surface of zeolite particles with fine calcium carbonate. The zeolite used in the present invention is an aluminosilicate having a crystalline three-dimensional structure that can be easily identified by X-ray diffraction, such as type A, type
Synthetic zeolites of type, Y type, P type, natural zeolites such as mordenite, clinoptilolite, erionite, and sodalite group aluminosilicates. In many cases, the cation of these zeolites is sodium, but metal-substituted zeolites are also included in which sodium is replaced with ions of other metals, such as alkaline earth metals such as calcium and magnesium. Among these zeolites, particularly preferred zeolites are A-type or X-type zeolites and metal-substituted zeolites thereof. The reason for this is that synthetic zeolites, such as A-type zeolite or This is because it is easy to use and is suitable as a core material from the viewpoint of industrial use. On the other hand, the particle size of zeolite varies depending on its use, intended use, or its own properties, but in most cases, when it is used as a filler or resin additive, an average particle size of 10 μm or less is appropriate. The thickness is preferably in the range of 0.1 to 5 μm. Moreover, zeolite has various shapes depending on synthesis conditions, crystal type, pulverization, etc., but in the present invention, the shape can be applied without particular limitation. The composite according to the present invention is a mixture of zeolite and calcium carbonate which is finer than its primary particles, and the fine calcium carbonate is deposited on the surface of the zeolite particles and exists in a substantially coated state. Here, "substantially" means that there are differences depending on the quantitative relationship between the two, manufacturing conditions, etc., but when looking at the particles with a scanning or transmission electron microscope, there is almost nothing on the surface of the zeolite particles. This refers to the extent to which fine particles of calcium carbonate, which are thought to be calcium carbonate, are observed as being free from the zeolite particles, ranging from cases in which no free calcium carbonate is observed and fine particles of calcium carbonate are deposited and coated on the zeolite particles. This means that most of the zeolite particles are coated with the zeolite particles. The particle size of such a composite depends on the particle size of the zeolite core material, but when used as a modifier for various resins, the average particle size is in the range of 0.3 to 10 μm, preferably in the range of 0.5 to 5 μm. be. The quantitative relationship between zeolite and calcium carbonate can be arbitrarily adjusted depending on the particle size of both, the use of the composite, etc., but in most cases, it is preferable that calcium carbonate is 5 to 100 parts by weight per 100 parts by weight of zeolite. This is a range. The zeolite-calcium carbonate composite according to the present invention can be used in various ways as a resin additive, filler, or inorganic foam. Such a composite can be produced by contacting and reacting a soluble calcium salt or/and milk of lime with a carbonating agent in an alkaline zeolite slurry to deposit fine calcium carbonate on the surface of the zeolite particles. Calcium chloride is suitable as the soluble calcium salt, but other salts such as calcium nitrate may also be used. As a carbonating agent,
Although CO 2 gas and carbonated water are preferable, alkali carbonate or alkali bicarbonate may be used as necessary. The following three methods are typically cited as specific embodiments of such a manufacturing method, but the method is not particularly limited to these methods. (1) Add a water-soluble calcium salt aqueous solution to a zeolite aqueous slurry adjusted to an appropriate particle size, then add an alkali to prepare a calcium hydroxide-zeolite slurry, and add carbon dioxide gas or carbonated water to this. In this case, carbon dioxide gas or the like may be directly introduced without adding an alkali. (2) After adding a water-soluble calcium salt aqueous solution to a zeolite aqueous slurry adjusted to an appropriate particle size, water-soluble calcium carbonate or alkali bicarbonate is added, or a water-soluble calcium salt aqueous solution and a water-soluble alkali carbonate are added. Add alkaline bicarbonate at the same time. (3) Prepare a lime milk slurry in advance, add it to the zeolite aqueous slurry, and then add carbon dioxide gas or carbonated water. In any of these methods, the surface of the zeolite particles is deposited and coated with calcium carbonate particles, but the reaction conditions require a reaction temperature of 40°C or higher, preferably 60°C or higher, and at the end of the reaction. It is important that the pH of the slurry is between 8 and 10. If the temperature setting is below 40℃, there will be a strong tendency to agglomerate during drying, causing poor dispersion.
When the pH of the slurry at the end of the reaction is 8 or less, the calcium carbonate layer deposited and coated on the zeolite surface becomes easily detached. The zeolite-calcium carbonate aqueous slurry thus obtained is washed with filtration and water in a conventional manner, dehydrated by hot air drying and vacuum drying, and crushed as necessary to obtain a product. The present invention will be explained below by giving examples. Example 1 Ca-substituted type A zeolite with the particle size distribution shown in Table 1
After dispersing 200g in 800g of water, 456ml of calcium chloride aqueous solution (CaCl 2 100g/l) was added and heated at 60°C.
After heating to , 640 ml of 5% by weight aqueous sodium hydroxide solution was added. While stirring this slurry, carbon dioxide gas was introduced at a rate of 50ml per minute until the pH of the slurry was 9.5.
I continued until. Stirring was continued at 60°C for about 30 minutes, and then filtered, and the filter cake was washed with water, dried with hot air at 120°C, and pulverized to obtain a zeolite-calcium carbonate composite. The properties are shown in Table-1.
【表】
実施例 ２
表−２に示す粒度分布のNaA型ゼオライト200
ｇを水800ｇに分散して撹拌しながら75℃に加温
した。75℃に加温した炭酸ナトリウム水溶液
（106ｇ Na2CO3／−1M）及び75℃に加温した
塩化カルシウム水溶液（111ｇ CaCl2／−
1M）を各々、10ml／分で滴加し、各々500ml消費
した。こののち引きつづいて炭酸ガスを用いスラ
リーのPHを10.0となるまで加え過、水洗、乾
燥、粉砕し表−２に示すNaA型ゼオライト−炭酸
カルシウム複合体を得た。[Table] Example 2 NaA type zeolite 200 with particle size distribution shown in Table-2
g was dispersed in 800 g of water and heated to 75° C. with stirring. Sodium carbonate aqueous solution (106g Na 2 CO 3 /-1M) heated to 75°C and calcium chloride aqueous solution (111g CaCl 2 /-1M) heated to 75°C
1M) were added dropwise at 10 ml/min, consuming 500 ml each. Thereafter, carbon dioxide gas was added until the pH of the slurry reached 10.0, followed by filtration, washing with water, drying, and pulverization to obtain the NaA type zeolite-calcium carbonate composite shown in Table 2.
【表】
実施例 ３
１級試薬の炭酸カルシウム80ｇを1100℃で２時
間焼成し、冷後水500mlに分散、消化させた石灰
乳スラリーを325メツシユの篩を通したのち、表
−３に示す性状のNaX型ゼオライトを80℃の水に
分散させたNaX型ゼオライト水性スラリー（NaX
型ゼオライト100ｇ／含有）１を撹拌しなが
らこれに毎分10mlで添加したのち、炭酸ガスを毎
分50ml／分で添加しスラリーのPHを9.0とした。
この後80℃で撹拌しながら30分熟成した。このス
ラリーを過、水洗、乾燥、粉砕し表−３に示す
NaX型ゼオライト−炭酸カルシウム複合体を得
た。[Table] Example 3 80g of calcium carbonate, a first-class reagent, was calcined at 1100°C for 2 hours, cooled, dispersed in 500ml of water, and the digested lime milk slurry was passed through a 325-mesh sieve, as shown in Table 3. NaX type zeolite aqueous slurry (NaX
Type zeolite (100 g/containing) 1 was added thereto at a rate of 10 ml/min with stirring, and then carbon dioxide gas was added at a rate of 50 ml/min to adjust the pH of the slurry to 9.0.
Thereafter, the mixture was aged at 80°C for 30 minutes while stirring. This slurry was filtered, washed with water, dried, and pulverized as shown in Table 3.
A NaX type zeolite-calcium carbonate composite was obtained.
【表】【table】
【表】【table】
Claims (1)
ルシウム塩又は石灰乳と、炭酸化剤とを反応させ
て、ゼオライト粒子表面に微細な炭酸カルシウム
を沈積させることを特徴とするゼオライト−炭酸
カルシウム複合体の製造方法。 ２ ゼオライトがＡ型又はＸ型のゼオライトであ
る特許請求の範囲第１項記載のゼオライト−炭酸
カルシウム複合体の製造方法。 ３ ゼオライトがナトリウムゼオライトのナトリ
ウムをアルカリ土類金属で置換してなるゼオライ
トである特許請求の範囲第１項又は第２項記載の
ゼオライト−炭酸カルシウム複合体の製造方法。 ４ 反応はスラリーの温度が40℃以上であり、か
つ少なくともPHが８以上において行う特許請求の
範囲第１項記載のゼオライト−炭酸カルシウム複
合体の製造方法。[Claims] 1. A zeolite-calcium carbonate composite characterized in that fine calcium carbonate is deposited on the surface of zeolite particles by reacting a soluble calcium salt or milk of lime with a carbonating agent in an alkaline zeolite slurry. How the body is manufactured. 2. The method for producing a zeolite-calcium carbonate composite according to claim 1, wherein the zeolite is an A-type or an X-type zeolite. 3. The method for producing a zeolite-calcium carbonate composite according to claim 1 or 2, wherein the zeolite is a zeolite obtained by replacing sodium in sodium zeolite with an alkaline earth metal. 4. The method for producing a zeolite-calcium carbonate composite according to claim 1, wherein the reaction is carried out at a temperature of the slurry of 40° C. or higher and a pH of at least 8 or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19560681A JPS5899117A (en) | 1981-12-07 | 1981-12-07 | Zeolite-calcium carbide composite body and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19560681A JPS5899117A (en) | 1981-12-07 | 1981-12-07 | Zeolite-calcium carbide composite body and its manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5899117A JPS5899117A (en) | 1983-06-13 |
| JPS6225607B2 true JPS6225607B2 (en) | 1987-06-04 |
Family
ID=16343949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19560681A Granted JPS5899117A (en) | 1981-12-07 | 1981-12-07 | Zeolite-calcium carbide composite body and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5899117A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02149421A (en) * | 1988-06-16 | 1990-06-08 | Komeshiyou Sekkai Kogyo Kk | Deformed calcium carbonate |
| JP5083748B2 (en) * | 2006-05-23 | 2012-11-28 | 独立行政法人物質・材料研究機構 | Method for producing calcium carbonate / zeolite compound composite |
| JP5578376B2 (en) * | 2012-01-16 | 2014-08-27 | 独立行政法人物質・材料研究機構 | Calcium carbonate / zeolite compound composite and article using the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5767021A (en) * | 1980-10-13 | 1982-04-23 | Nippon Chem Ind Co Ltd:The | Composite body of zeolite and alkaline earth metallic salt, its manufacture and additive for high molecular compound |
-
1981
- 1981-12-07 JP JP19560681A patent/JPS5899117A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5767021A (en) * | 1980-10-13 | 1982-04-23 | Nippon Chem Ind Co Ltd:The | Composite body of zeolite and alkaline earth metallic salt, its manufacture and additive for high molecular compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5899117A (en) | 1983-06-13 |
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