JPH0348148B2 - - Google Patents
Info
- Publication number
- JPH0348148B2 JPH0348148B2 JP10830782A JP10830782A JPH0348148B2 JP H0348148 B2 JPH0348148 B2 JP H0348148B2 JP 10830782 A JP10830782 A JP 10830782A JP 10830782 A JP10830782 A JP 10830782A JP H0348148 B2 JPH0348148 B2 JP H0348148B2
- Authority
- JP
- Japan
- Prior art keywords
- chromium
- coloring agent
- composition
- weight
- product
- 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
- 239000011651 chromium Substances 0.000 claims description 41
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 38
- 229910052804 chromium Inorganic materials 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 24
- 239000002893 slag Substances 0.000 claims description 22
- 239000003086 colorant Substances 0.000 claims description 21
- 239000000919 ceramic Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 239000004927 clay Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000010433 feldspar Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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
- 239000000571 coke Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005467 ceramic manufacturing process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
Landscapes
- Glass Compositions (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
本発明はセラミツク用着色剤に関するものであ
る。さらに詳述するとクロム鉱石からクロム酸ソ
ーダを製造する際に副生するクロム鉱滓等のクロ
ム含有物質をセラミツクの着色剤として有効利用
すると共に該セラミツク類にチヨコレート色の色
彩を施すことを目的とするものである。
一般にセラミツク類の着色は着色タイル等の様
に素地に着色剤を添加して着色する方法と、素地
の表面に釉をかけるときに着色釉を用いる方法と
に大別される。周知の通り、後者の方法において
釉は素地を液体や気体に対し不透過性とし、同時
に強度を増大し美感を与えるものであるが、これ
に着色剤を混合して着色釉とすれば美感をより一
層向上させることができる。
従来、この様な着色剤として天然に産出する金
属酸化物や塩類が品質的にも安定し、しかも安価
であるために各種の色彩の着色用に用いられてい
るが、これ等の酸化物の中で、所謂チヨコレート
系の着色剤に関しては天然の鉱物や塩類の単独で
は得ることができず、現在全く人工的につくられ
た金属酸化物及びその塩類が用いられている。
しかも、このチヨコレート系色の着色剤の製造
法は特定の原料を窯に入れて焼成を行ない、焼成
後細かく粉砕したものを単独または数種類配合し
所望の色調に配色しているが、得られた製品の純
度及び粉砕による品質の均一性が不充分で、しか
も高価である欠点がある。
一方、一般的にクロム酸ソーダの工業的な製造
法はクロム鉱石にソーダ灰、苛性ソーダなどのア
ルカリ剤を配合し、さらに必要に応じて石灰や不
活性充填剤などを添加した混合物を高温で酸化焙
焼し、次いで焙焼物を水で浸出することによつて
クロム酸ソーダ水溶液として得る方法が採られる
が、この際多量の含クロム浸出残渣である含クロ
ム鉱滓が副生する。
該クロム鉱滓には有害な六価クロムが含有され
ているので、そのまま廃棄すると土壌や水質を汚
染し公害の原因となるために、クロム鉱滓を無害
化する処理方法としてクロム鉱滓に直接還元剤を
添加して六価クロムを三価クロムに還元する方
法、珪酸質物質および還元剤を添加して高温で還
元処理する方法等が行われているが、いずれの方
法を用いても処理生成物は単に廃棄するか、埋立
材或いは骨材として利用されているのが現状であ
る。
本発明者等は前記クロム鉱滓の積極的かつ有効
な利用法について鋭意研究を行つた結果、クロム
鉱滓をセラミツク焼結体に添加すると美しいチヨ
コレート色を呈し、着色剤として優れた特性を示
すことを知見し本発明の完成に至つたものであ
る。
即ち、本発明はCr2O32〜17重量％、CaO0〜40
重量％、Fe2O310〜45重量％、SiO20〜30重量％、
MgO5〜20重量％及びその他の不純物５〜30重量
％のクロム含有組成物よりなるセラミツク用着色
剤である。
本発明において用いられるクロム鉱滓の組成は
前記のクロム酸ソーダの製造の際に副生するもの
であり、クロム酸製造条件、例えばクロム鉱石の
種類、原料の配合組成、焙焼条件及び浸出条件等
により相違するが概ね第１表に示す範囲にある。
The present invention relates to a coloring agent for ceramics. More specifically, the purpose is to effectively utilize chromium-containing substances such as chromium slag, which is a by-product when producing sodium chromate from chromium ore, as a coloring agent for ceramics, and to give the ceramics a thiokolate color. It is something. In general, the coloring of ceramics can be roughly divided into two methods: a method in which a coloring agent is added to the substrate, such as in the case of colored tiles, and a method in which a colored glaze is used when glazing the surface of the substrate. As is well known, in the latter method, the glaze makes the base material impermeable to liquids and gases, and at the same time increases its strength and gives it an aesthetic appearance.If a coloring agent is mixed with this to create a colored glaze, the aesthetic appearance can be improved. This can be further improved. Conventionally, naturally occurring metal oxides and salts have been used as coloring agents in various colors because they are stable in quality and inexpensive. Among these, so-called thiocholate coloring agents cannot be obtained solely from natural minerals or salts, and currently entirely artificially produced metal oxides and their salts are used. In addition, the manufacturing method for this thiocolate coloring agent involves putting specific raw materials in a kiln, firing them, and then finely pulverizing them after firing, singly or blending several kinds of them, to achieve the desired color tone. The drawbacks are that the purity of the product and the uniformity of quality due to grinding are insufficient, and it is expensive. On the other hand, the general industrial method for producing sodium chromate is to mix chromium ore with an alkaline agent such as soda ash or caustic soda, and then oxidize the mixture at high temperature by adding lime and inert fillers as necessary. A method is adopted in which a sodium chromate aqueous solution is obtained by roasting and then leaching the roasted product with water, but at this time, a large amount of chromium-containing slag, which is a chromium-containing leaching residue, is produced as a by-product. The chromium slag contains hexavalent chromium, which is harmful, and if it is disposed of as it is, it will contaminate soil and water and cause pollution. Therefore, as a treatment method to make the chromium slag harmless, it is necessary to apply a reducing agent directly to the chromium slag. Methods of reducing hexavalent chromium to trivalent chromium by adding siliceous substances and reducing agents at high temperatures have been used, but no matter which method is used, the treatment product is Currently, it is simply discarded or used as landfill material or aggregate. The inventors of the present invention have conducted extensive research into the active and effective use of chromium slag, and have discovered that when chromium slag is added to ceramic sintered bodies, it exhibits a beautiful tyokolate color and exhibits excellent properties as a coloring agent. This knowledge led to the completion of the present invention. That is, the present invention contains 2 to 17% by weight of Cr 2 O 3 and 0 to 40% of CaO.
wt%, Fe2O3 10-45 wt% , SiO2 0-30 wt%,
A coloring agent for ceramics comprising a chromium-containing composition containing 5 to 20% by weight of MgO and 5 to 30% by weight of other impurities. The composition of the chromium slag used in the present invention is a by-product during the production of sodium chromate, and depends on the chromic acid production conditions, such as the type of chromium ore, the composition of raw materials, roasting conditions, leaching conditions, etc. Although it differs depending on the situation, it is generally within the range shown in Table 1.
【表】
これ等のうちCr2O3成分は主として三価クロム
として存在するが六価クロムが2000〜15000ppm
程度含有されている。その他の不純物は原料であ
るクロム鉱石の種類により異るが、その組成は
Na2O、Ｓ、Ｖ、Ni等の混合物で一定していない
が着色剤として用いることにおいて何ら不都合を
生じない。
本発明に係るセラミツク用着色剤は前記組成の
クロム含有組成物であることが必要であり、この
組成以外では所望の色調に着色することはできな
い。
従つて、上記第１表から明らかな様にクロム鉱
滓もそのまま適用できる場合があり、更にその着
色剤の使用態様又は用途目的に応じて前記組成の
範囲内で該鉱滓の組成を他の原料を補助的に配合
して所定の着色剤を調製することができる。
しかも、上記組成を有するクロム含有組成物で
あればクロム鉱滓に限らず他のいかなる原料の配
合により得られたものでも用いることが可能であ
り、セラミツクを所望のチヨコレート色に着色す
ることができる。
本発明の着色剤であるクロム鉱滓はセラミツク
製造工程において原料中に添加混合すれば良く、
具体的には窯業用原料として用いられる珪石、珪
砂、粘土類、ろう石、陶石、長石その他の１種又
は２種以上の混合物からなる素地、或いはその主
成分である原料から分類した長石釉、陶石釉、そ
の他の石灰釉等の基礎釉に添加混合して用いる
が、その添加量は素地或いは基礎釉に対し0.5〜
50重量％の範囲が好ましく、0.5重量％未満では
着色効果が薄れ、50重量％をこえると六価クロム
が還元されないので不適当である。
この様な使用方法を採用するために本発明の着
色剤であるクロム鉱滓に含有されている六価クロ
ムは少量であるので素地或いは基礎釉に含有して
いる珪酸質と反応し、加熱分解して六価クロムは
実質的に三価クロムに還元され無害化される。
又、六価クロムを含有するクロム鉱滓をあらか
じめ珪酸質物質及びコークス等の還元剤を添加し
加熱還元処理して、実質上３価クロムに還元し各
組成分がクロム含有組成物の前記組成範囲内にな
る様に調整した処理鉱滓をそのまま使用してもよ
い。
セラミツクの製造において本発明の着色剤を原
料に添加混合して通常の方法により窯で焼成する
と容易に美しいチヨコレート色の製品を得ること
が出来、又着色剤の配合量を変えることにより濃
淡任意の色調のものを得ることも可能である。
この様に本発明の着色剤を用いると従来にない
色調であるチヨコレート色の興趣ある陶磁器を得
ることが出来ると共にクロム鉱滓及びその還元処
理物を再利用することが出来るので本発明の工業
的意義は極めて大きいものである。
以下、実施例を挙げて本発明を具体的に説明す
る。但し、実施例において部及び％は各々重量部
及び重量％を示す。
実施例 １
第２表に示す組成を有するクロム鉱滓（六価ク
ロム4000ppmを含有する）20部、ろう石70部、粘
土10部を100メツシユ全通の粒径に混合粉砕し、
若干の水を加えて金型を用いてタイル状にプレス
成形した。乾燥後、焼成窯にて除々に加熱し最高
1230℃で30分焼成後加熱を停止しそのまま除冷し
た。
一連の所要時間は約10時間である。得られた焼
成品は、美しい表面を呈し従前にない色調のチヨ
コレート色で興趣豊かな格調の高いものである。
焼成品中に六価クロムは検出されなかつた。[Table] Of these, the Cr 2 O 3 component mainly exists as trivalent chromium, but hexavalent chromium is 2000 to 15000 ppm.
Contains to some extent. Other impurities vary depending on the type of chromium ore used as the raw material, but their composition is
Although it is a mixture of Na 2 O, S, V, Ni, etc. and is not constant, it does not cause any inconvenience when used as a coloring agent. The coloring agent for ceramics according to the present invention must be a chromium-containing composition having the above composition, and it is not possible to color the ceramic to a desired color tone with a composition other than this composition. Therefore, as is clear from Table 1 above, chromium slag can be applied as is in some cases, and the composition of the chromium slag may be changed by adding other raw materials within the above composition range depending on the usage mode or purpose of the colorant. A predetermined coloring agent can be prepared by supplementary blending. Furthermore, as long as the chromium-containing composition has the above-mentioned composition, it is possible to use not only chromium slag but also those obtained by blending any other raw materials, and ceramic can be colored in a desired color. The chromium slag, which is the coloring agent of the present invention, may be added and mixed into the raw materials during the ceramic manufacturing process.
Specifically, a base made of silica stone, silica sand, clays, waxite, pottery stone, feldspar, and a mixture of one or more types used as raw materials for the ceramic industry, or feldspar glaze classified based on the raw material that is the main component. It is used by adding and mixing it to basic glazes such as pottery stone glazes and other lime glazes, but the amount added is 0.5 to 0.5 to 100% of the base or basic glaze.
A range of 50% by weight is preferable; if it is less than 0.5% by weight, the coloring effect will be weakened, and if it exceeds 50% by weight, hexavalent chromium will not be reduced, which is inappropriate. In order to adopt this method of use, since the hexavalent chromium contained in the chromium slag, which is the coloring agent of the present invention, is a small amount, it reacts with the silicic acid contained in the base material or basic glaze, and is thermally decomposed. Hexavalent chromium is substantially reduced to trivalent chromium and rendered harmless. In addition, chromium slag containing hexavalent chromium is heated and reduced by adding a silicic acid substance and a reducing agent such as coke in advance to substantially reduce it to trivalent chromium, so that each component is within the above composition range of the chromium-containing composition. You may use the treated slag that has been adjusted so that the In the production of ceramics, if the coloring agent of the present invention is added to the raw materials and fired in a kiln using the usual method, a product with a beautiful tyokolate color can be easily obtained, and by changing the amount of the coloring agent mixed, it is possible to create a product with any desired shade or shade. It is also possible to obtain colored ones. As described above, by using the coloring agent of the present invention, it is possible to obtain interesting ceramics with a color tone that is unprecedented, and it is also possible to reuse chromium slag and its reduced product, which is the industrial significance of the present invention. is extremely large. The present invention will be specifically described below with reference to Examples. However, in the examples, parts and % indicate parts by weight and % by weight, respectively. Example 1 20 parts of chromium slag (containing 4000 ppm of hexavalent chromium) having the composition shown in Table 2, 70 parts of waxite, and 10 parts of clay were mixed and ground to a particle size of 100 mesh.
A small amount of water was added and press molded into a tile shape using a mold. After drying, it is heated gradually in a firing kiln until it reaches its peak.
After firing at 1230°C for 30 minutes, heating was stopped and the mixture was allowed to cool down. The series takes approximately 10 hours. The resulting fired product has a beautiful surface, an unprecedented color tone of Chiyocolate, and is of high quality and interest.
No hexavalent chromium was detected in the fired product.
【表】
但し、六価クロム4000ppm含有、その他の不純
物はNa2O、Ｓ、Ｖ、Niである。
実施例 ２
第２表に示す組成のクロム鉱滓80部、珪石15
部、コークス15部からなる混合物を1200℃で焼成
し六価クロムを三価クロムに還元したクロム鉱滓
還元処理物を得た。
該クロム鉱滓還元処理物20部、ろう石70部、粘
土10部からなる混合物を粉砕し、実施例１と同様
の方法で成形、乾燥、焼成処理した所、実施例１
と同等の焼成品が得られた。
焼成品中６価クロムは検出されなかつた。
実施例 ３
長石粉末55部、珪石粉末35部、第２表の組成の
クロム鉱滓粉末10部に少量の水を加え混合して釉
を調整した。この釉をあらかじめプレス加工した
粘土瓦素地にぬり、実施例１と同様の方法で乾
燥、焼成処理した所、表面が美しいチヨコレート
色に施釉された粘土瓦が得られた。
焼成品中６価クロムは検出されなかつた。[Table] However, it contains 4000 ppm of hexavalent chromium, and other impurities are Na 2 O, S, V, and Ni. Example 2 80 parts of chromium slag with the composition shown in Table 2, 15 parts of silica
15 parts of coke was calcined at 1200°C to obtain a reduced chromium slag product in which hexavalent chromium was reduced to trivalent chromium. A mixture consisting of 20 parts of the reduced chromium slag, 70 parts of waxite, and 10 parts of clay was pulverized, molded, dried, and fired in the same manner as in Example 1. Example 1
A fired product equivalent to that was obtained. No hexavalent chromium was detected in the fired product. Example 3 A small amount of water was added to and mixed with 55 parts of feldspar powder, 35 parts of silica powder, and 10 parts of chromium slag powder having the composition shown in Table 2 to prepare a glaze. This glaze was applied to a pre-pressed clay tile base, dried and fired in the same manner as in Example 1, resulting in a clay tile whose surface was glazed in a beautiful chiyocolate color. No hexavalent chromium was detected in the fired product.
Claims (1)
Fe2O310〜45重量％、SiO20〜30重量％、MgO5
〜20重量％及びその他の不純物５〜30重量％のク
ロム含有組成物よりなるセラミツク用着色剤。 ２ クロム含有組成物がクロム酸ソーダの製造工
程から副生するクロム鉱滓である特許請求の範囲
第１項記載のセラミツク用着色剤。[Claims] 1 Cr 2 O 3 2 to 17% by weight, CaO 0 to 40% by weight,
Fe2O3 10 ~45wt%, SiO2 0 ~30wt%, MgO5
A coloring agent for ceramics consisting of a composition containing ~20% by weight of chromium and 5-30% by weight of other impurities. 2. The coloring agent for ceramics according to claim 1, wherein the chromium-containing composition is chromium slag produced as a by-product from the manufacturing process of sodium chromate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10830782A JPS58225158A (en) | 1982-06-25 | 1982-06-25 | Colorant for ceramic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10830782A JPS58225158A (en) | 1982-06-25 | 1982-06-25 | Colorant for ceramic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58225158A JPS58225158A (en) | 1983-12-27 |
| JPH0348148B2 true JPH0348148B2 (en) | 1991-07-23 |
Family
ID=14481380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10830782A Granted JPS58225158A (en) | 1982-06-25 | 1982-06-25 | Colorant for ceramic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58225158A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5065231B2 (en) * | 2007-11-21 | 2012-10-31 | ダント−ホ−ルディングス株式会社 | Low heat storage ceramics and manufacturing method thereof |
| US20100064942A1 (en) * | 2008-09-15 | 2010-03-18 | Ferro Corporation | Corundum Crystal Structure Pigments With Reduced Soluble Chromium Content |
| EP2682370A1 (en) | 2012-07-06 | 2014-01-08 | LANXESS Deutschland GmbH | Method for reducing hexavalent chromium in oxidic solids |
| EP2918564A1 (en) | 2014-03-13 | 2015-09-16 | LANXESS Deutschland GmbH | Refractory materials containing a mixed crystal with spinel structure |
| EP3020690A1 (en) | 2014-11-13 | 2016-05-18 | LANXESS Deutschland GmbH | Method for reducing hexavalent chromium in oxidic solids |
-
1982
- 1982-06-25 JP JP10830782A patent/JPS58225158A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58225158A (en) | 1983-12-27 |
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