JPH07277734A - Porous zirconium boride - Google Patents
Porous zirconium borideInfo
- Publication number
- JPH07277734A JPH07277734A JP6093830A JP9383094A JPH07277734A JP H07277734 A JPH07277734 A JP H07277734A JP 6093830 A JP6093830 A JP 6093830A JP 9383094 A JP9383094 A JP 9383094A JP H07277734 A JPH07277734 A JP H07277734A
- Authority
- JP
- Japan
- Prior art keywords
- amorphous
- crystalline
- zirconium boride
- zrb2
- porous
- 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
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000005885 boration reaction Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 6
- 229910052796 boron Inorganic materials 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 3
- 239000011707 mineral Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract 3
- 229910007948 ZrB2 Inorganic materials 0.000 abstract 3
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 abstract 3
- 239000003054 catalyst Substances 0.000 description 9
- 238000010304 firing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、触媒担体などとして有
用な多孔体に関するものである。FIELD OF THE INVENTION The present invention relates to a porous material useful as a catalyst carrier and the like.
【０００２】[0002]
【従来の技術】従来、触媒担体などとして用いられる多
孔体として、ＺｒＯ2−Ｎａ2Ｏ−Ｂ2Ｏ3−ＳｉＯ2−Ｒ
Ｏ（Ｒ：アルカリ土金属またはＺｎ）のＺｒＯ2系複合
ガラス、ＳｉＯ2（５５〜８０ｗｔ％）−Ｂ2Ｏ3−Ｎａ2
ＯのＳｉＯ2系複合ガラス、ＳｉＯ2−Ｂ2Ｏ3−ＣａＯ−
ＭｇＯ−Ａｌ2Ｏ3−ＴｉＯ2のＴｉＯ2系複合ガラスなど
が知られており、いずれも耐アルカリ性に優れている
（セラミックスｖｏｌ２８，Ｎｏ．７，６７４−６７８
（１９９３））。（ＺｒＯ2と非晶質ＢまたはＢ2Ｏ3と
Ｍｇとの混合粉末の焼成によるＺｒＢ2粉末の製造法が
Ｊｏｕｒｎａｌ ｏｆ Ｃｅｒａｍｉｃ Ｓｏｃｉｅｔ
ｙ ｏｆ Ｊａｐａｎ１００［２］１７２−１７７（１
９９２）に開示されている）。 2. Description of the Related Art Conventionally, ZrO 2 --Na 2 O--B 2 O 3 --SiO 2 --R has been used as a porous material used as a catalyst carrier.
O: ZrO 2 composite glass (R earth alkali metal or Zn), SiO 2 (55~80wt% ) - B 2 O 3 -Na 2
SiO 2 based composite glass of O, SiO 2 —B 2 O 3 —CaO—
TiO 2 -based composite glass of MgO-Al 2 O 3 -TiO 2 and the like are known, and all have excellent alkali resistance (ceramics vol28, No. 7, 674-678).
(1993)). (A method for producing a ZrB 2 powder by firing a mixed powder of ZrO 2 and amorphous B or B 2 O 3 and Mg is described in the Journal of Ceramic Society.
y of Japan 100 [2] 172-177 (1
992)).
【０００３】[0003]
【発明が解決しようとする課題】しかし、上記の多孔質
ガラスは、いずれも化学的安定性は高いものの、触媒の
作用を高める機能が劣り、耐熱性などが低い。However, all of the above-mentioned porous glasses have a high chemical stability, but have a poor function of enhancing the action of the catalyst and a low heat resistance.
【０００４】本発明は、これらの欠点の解消された、す
なわち触媒の作用を向上させる機能に優れ、かつ耐熱性
の高い多孔体の提供を目的とするものである。An object of the present invention is to provide a porous body which is free from these drawbacks, that is, which has an excellent function of improving the action of the catalyst and has a high heat resistance.
【０００５】[0005]
【課題を解決するための手段】本発明は、実質的に結晶
質ＺｒＢ2および非晶質Ｂのみからなり、非晶質のＢ／
結晶質のＺｒＢ2のモル比が０．４／１〜４／１であ
る、ホウ化ジルコニウム系多孔体を提供するものであ
る。SUMMARY OF THE INVENTION The present invention consists essentially of crystalline ZrB 2 and amorphous B.
The present invention provides a zirconium boride-based porous body having a crystalline ZrB 2 molar ratio of 0.4 / 1 to 4/1.
【０００６】上記の非晶質のＢ／結晶質のＺｒＢ2のモ
ル比を０．４／１〜４／１とするのは、下記の製造法上
の制約による。すなわち、その方法を、非晶質のＢ／結
晶質のＺｒＢ2のモル比が０．４／１に満たないものと
なる条件で実施すると多孔質のものがえられず、いっぽ
う、４／１をこえるものとなる条件で実施すると不純物
を含む製品がえられる。The above-mentioned amorphous B / crystalline ZrB 2 molar ratio of 0.4 / 1 to 4/1 is due to the following manufacturing method restrictions. That is, when the method is carried out under the condition that the molar ratio of amorphous B / crystalline ZrB 2 is less than 0.4 / 1, a porous one cannot be obtained, and on the other hand, 4/1 Product containing impurities can be obtained by carrying out under conditions that exceed the above.
【０００７】本発明のホウ化ジルコニウム系多孔体は、
ＺｒＯ2粉末と非晶質Ｂ粉末と金属Ｍｇ粉末とを、Ｚｒ
Ｏ2／Ｂ／Ｍｇモル比１／（２．４〜６）／（２〜３）
の割合で混合し、Ａｒ，Ｎ2などの非酸化性雰囲気で７
００〜１４００℃で焼成してＺｒＯ2＋２Ｂ＋２Ｍｇ→
ＺｒＢ2＋２ＭｇＯで表される反応を行わせ、１Ｎの塩
酸などの鉱酸と接触させて生成したＭｇＯおよび過剰の
Ｍｇを溶解させて除去することにより製造することがで
きる。原料混合粉末中のＢ／ＺｒＯ2モル比が２．４／
１に満たないと、多孔質のものがえられない。それが６
／１をこえると、Ｂの一部がＭｇと反応して鉱酸で除去
されないＭｇＢ2、ＭｇＢ4、ＭｇＢ6などが副生し、製
品の純度を低下させる。Ｍｇ／ＺｒＯ2モル比が２に達
しないと、上記の式から明らかなように、製品中にＺｒ
Ｏ2が残存することになる。それが３をこえると、製品
が微粉化し、多孔質のものとならない。焼成温度が７０
０℃に達しないと、反応が完結せず、製品中にＺｒＯ2
が残存することになる。それが１４００℃をこえると、
結晶の粒成長が進み製品の多孔性が損なわれる。雰囲気
を酸化性のものとすると、それがＭｇと反応して、上記
の式による反応が十分に進まず、製品中にＺｒＯ2が残
存することになる。The zirconium boride-based porous material of the present invention is
ZrO 2 powder, amorphous B powder and metallic Mg powder
O 2 / B / Mg molar ratio of 1 / (2.4 to 6) / (2-3)
And mixed in a non-oxidizing atmosphere such as Ar or N 2.
ZrO 2 + 2B + 2Mg by firing at 00 to 1400 ° C.
It can be produced by carrying out a reaction represented by ZrB 2 + 2MgO and dissolving and removing MgO and excess Mg produced by contacting with a mineral acid such as 1N hydrochloric acid. B / ZrO 2 molar ratio in the raw material mixed powder is 2.4 /
If it is less than 1, a porous material cannot be obtained. It is 6
When it exceeds / 1, a part of B reacts with Mg and MgB 2 , MgB 4 , MgB 6 and the like which are not removed by the mineral acid are by-produced and the purity of the product is lowered. If the Mg / ZrO 2 molar ratio does not reach 2, the Zr content in the product is
O 2 will remain. If it exceeds 3, the product is pulverized and does not become porous. Firing temperature is 70
If the temperature does not reach 0 ° C, the reaction will not be completed and ZrO 2 will be contained in the product.
Will remain. When it exceeds 1400 ℃,
Grain growth of crystals progresses and the porosity of the product is impaired. When the atmosphere is made oxidizing, it reacts with Mg, the reaction according to the above formula does not proceed sufficiently, and ZrO 2 remains in the product.
【０００８】原料であるＺｒＯ2と非晶質Ｂと金属Ｍｇ
との混合方法には特に制限はなく、水またはエタノ−ル
中ボ−ルミル混合を行うかメノウ乳鉢を用いて混合すれ
ば十分に均一に混合することが可能である。Raw materials ZrO 2 , amorphous B and metallic Mg
There is no particular limitation on the method of mixing with, and it is possible to achieve a sufficiently uniform mixing by performing ball mill mixing in water or ethanol or by mixing using an agate mortar.
【０００９】焼成時間には特に制限はないが、あまり長
く焼成してもそれなりの効果が得られないので３０分〜
１時間で十分である。The firing time is not particularly limited, but if the firing time is too long, a certain effect cannot be obtained.
One hour is enough.
【００１０】[0010]
【作用】本発明の多孔体は、上記の製造条件から明らか
なように１０００℃以上で安定であり、多孔質であり、
かつ、成分のＺｒＢ2が高い電子伝導性を有する（Ｚｒ
Ｂ2の電気抵抗は１．０×１０-5であって、金属Ｚｒに
くらべてもその４．１×１０-5の約１／４にすぎない
（セラミックスｖｏｌ２４，Ｎｏ６，５２６−５３２
（１９８９）））ことから担持した触媒上に電子を供給
して触媒表面の触媒作用を向上させる可能であるので、
触媒担体などとして効果的に用いうるものと期待され
る。The porous material of the present invention is stable and porous at 1000 ° C. or higher, as is clear from the above production conditions.
In addition, the component ZrB 2 has high electronic conductivity (Zr
The electrical resistance of B 2 is 1.0 × 10 −5 , which is only about 1/4 of 4.1 × 10 −5 of metal Zr (ceramics vol24, No6, 526-532).
(1989))), it is possible to improve the catalytic action of the catalyst surface by supplying electrons onto the supported catalyst.
It is expected that it can be effectively used as a catalyst carrier.
【００１１】[0011]
【発明の効果】以上説明したように、本発明の多孔体
は、触媒の作用を向上させる機能に優れ、かつ耐熱性が
高いので、触媒担体などとして利用することにより高機
能が発揮されることが期待される。As described above, the porous body of the present invention is excellent in the function of improving the action of the catalyst and has high heat resistance. Therefore, when it is used as a catalyst carrier or the like, a high function is exhibited. There is expected.
【００１２】[0012]
実施例１〜６，比較例１〜５ ＺｒＯ2と非晶質Ｂと金属Ｍｇとを、エタノ−ル中ボ−
ルミルを用いて１２時間混合し、エバポレ−タ−を用い
て乾燥し、Ａｒ雰囲気下において１時間焼成し、１規定
の塩酸水溶液中において洗浄した。Examples 1 to 6 and Comparative Examples 1 to 5 ZrO 2 , amorphous B and metallic Mg were mixed in an ethanol medium ball.
The mixture was mixed for 12 hours using a rumill, dried using an evaporator, baked for 1 hour under an Ar atmosphere, and washed in a 1N aqueous hydrochloric acid solution.
【００１３】えられた製品を、一点法ＢＥＴ測定による
比表面積，Ｘ線回折試験による結晶相の同定ならびに走
査電子顕微鏡による粒子形状の観察を行った。また、実
施例１〜６および比較例４では、Ｚｒ，ＢおよびＭｇの
元素分析を行ったが、Ｍｇは検出されなかった。その分
析値から製品における非晶質のＢ／結晶質のＺｒＢ2の
モル比を求めた。The obtained product was observed for specific surface area by BET measurement by one-point method, identification of crystal phase by X-ray diffraction test, and observation of particle shape by scanning electron microscope. In Examples 1 to 6 and Comparative Example 4, Zr, B and Mg were subjected to elemental analysis, but Mg was not detected. From the analytical value, the molar ratio of amorphous B / crystalline ZrB 2 in the product was determined.
【００１４】その他の条件および結果を表１に示す。Table 1 shows other conditions and results.
【００１５】実施例の１および５の製品の走査電子顕微
鏡による観察結果は、図１および２にそれぞれ示す。The observation results of the products of Examples 1 and 5 by a scanning electron microscope are shown in FIGS. 1 and 2, respectively.
【００１６】[0016]
【表１】 [Table 1]
【図１】実施例１でえられた製品の粒子構造を示す走査
電子顕微鏡の写真である。FIG. 1 is a scanning electron microscope photograph showing the particle structure of the product obtained in Example 1.
【図２】実施例５でえられた製品の粒子構造を示す走査
電子顕微鏡の写真である。FIG. 2 is a scanning electron microscope photograph showing the particle structure of the product obtained in Example 5.
Claims (1)
みからなり、非晶質のＢ／結晶質のＺｒＢ2のモル比が
０．４／１〜４／１である、ホウ化ジルコニウム系多孔
体。1. Boration, which consists essentially of crystalline ZrB 2 and amorphous B, and has a molar ratio of amorphous B / crystalline ZrB 2 of 0.4 / 1 to 4/1. Zirconium based porous material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6093830A JPH07277734A (en) | 1994-04-08 | 1994-04-08 | Porous zirconium boride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6093830A JPH07277734A (en) | 1994-04-08 | 1994-04-08 | Porous zirconium boride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07277734A true JPH07277734A (en) | 1995-10-24 |
Family
ID=14093317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6093830A Pending JPH07277734A (en) | 1994-04-08 | 1994-04-08 | Porous zirconium boride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07277734A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006038406A1 (en) * | 2004-10-07 | 2006-04-13 | Nippon Mining & Metals Co., Ltd. | HIGH PURITY ZrB2 POWDER AND METHOD FOR PRODUCTION THEREOF |
| WO2017131108A1 (en) | 2016-01-27 | 2017-08-03 | 第一稀元素化学工業株式会社 | Zirconium boride and method for producing same |
-
1994
- 1994-04-08 JP JP6093830A patent/JPH07277734A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006038406A1 (en) * | 2004-10-07 | 2006-04-13 | Nippon Mining & Metals Co., Ltd. | HIGH PURITY ZrB2 POWDER AND METHOD FOR PRODUCTION THEREOF |
| JPWO2006038406A1 (en) * | 2004-10-07 | 2008-05-15 | 日鉱金属株式会社 | High purity ZrB2 powder and method for producing the same |
| JP2011088819A (en) * | 2004-10-07 | 2011-05-06 | Jx Nippon Mining & Metals Corp | HIGH PURITY ZrB2 POWDER AND METHOD FOR PRODUCING THE SAME |
| JP4685023B2 (en) * | 2004-10-07 | 2011-05-18 | Ｊｘ日鉱日石金属株式会社 | High purity ZrB2 powder and method for producing the same |
| WO2017131108A1 (en) | 2016-01-27 | 2017-08-03 | 第一稀元素化学工業株式会社 | Zirconium boride and method for producing same |
| US10974966B2 (en) | 2016-01-27 | 2021-04-13 | Daiichi Kigenso Kagaku Kogyo Co., Ltd. | Zirconium boride and method of its manufacture |
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