JPH01282148A - Melted siliceous refractory brick resistant to gaseous chlorine - Google Patents

Melted siliceous refractory brick resistant to gaseous chlorine

Info

Publication number
JPH01282148A
JPH01282148A JP10909588A JP10909588A JPH01282148A JP H01282148 A JPH01282148 A JP H01282148A JP 10909588 A JP10909588 A JP 10909588A JP 10909588 A JP10909588 A JP 10909588A JP H01282148 A JPH01282148 A JP H01282148A
Authority
JP
Japan
Prior art keywords
alginate
refractory brick
chlorine gas
gaseous chlorine
water
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
Application number
JP10909588A
Other languages
Japanese (ja)
Other versions
JPH0547503B2 (en
Inventor
Keiichi Nobuhara
延原 敬一
Hideaki Nishiyama
西山 英昭
Ryuichi Hosaka
保坂 隆一
Kensaku Matsuda
松田 研作
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shinagawa Refractories Co Ltd
Original Assignee
Shinagawa Refractories Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shinagawa Refractories Co Ltd filed Critical Shinagawa Refractories Co Ltd
Priority to JP10909588A priority Critical patent/JPH01282148A/en
Publication of JPH01282148A publication Critical patent/JPH01282148A/en
Publication of JPH0547503B2 publication Critical patent/JPH0547503B2/ja
Granted legal-status Critical Current

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Abstract

PURPOSE:To obtain a refractory brick wherein the service life of a chlorine furnace is prolonged and both maintenance and controlling thereof are made easy and cost reduction is enabled by molding a specified refractory raw material while utilizing water-soluble alginate as a binder and calcining the molded article and impregnating the calcined article with gaseous chlorine resistant substance. CONSTITUTION:A refractory raw material which consists of both >=99.0% SiO2 and trace quantity of the content of Al2O3 and Fe2O3 and has particle size distribution of several micron -5.0mm diameter is molded by a slurry casting method while utilizing 0.1-0.3wt.% water-soluble alginate as a binder. Then this molded article is calcined at 1200-1350 deg.C and the calcined article is impregnated with gaseous chlorine resistant substance and a melted siliceous refractory brick having <=5% apparent porosity is obtained. As the utilized water-soluble alginate, ammonium alginate, sodium alginate and potassium alginate are shown. SiO2 content must be regulated to >=99.0% because impurities especially Al2O3 and Fe2O3, etc., easy-to react with gaseous chlorine are made little.

Description

【発明の詳細な説明】 産業上の利用分野 本発明は耐塩素ガス、特に塩化炉及び付帯設備に好適な
耐塩素ガス用溶融シリカ質耐火煉瓦に関する。
DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a fused siliceous refractory brick for chlorine gas, particularly suitable for chlorination furnaces and auxiliary equipment.

従来の技術 TiO2原料と炭素原料を用い、 700〜1000℃
に加熱しながら塩素ガスを送入し、スポンジ金属チタニ
ウム製造用原料であるTiCJ24を生成する塩化炉が
知られている。この種塩化炉の内張耐火物は塩素ガスの
影響が比較的軽微な部位は5i0250〜55%、A1
20340〜45%とから主としてなる粘土質煉瓦を用
い、塩素ガスとの反応が大きい部位にはSin、95%
以上含有する溶融シリカ買煉瓦が一般使用されている。
Conventional technology: 700-1000℃ using TiO2 raw material and carbon raw material
A chlorination furnace is known that generates TiCJ24, which is a raw material for producing titanium sponge metal, by feeding chlorine gas while heating the material. The lining refractories of this type of chlorination furnace are 5i0250-55%, A1
Using clay bricks mainly consisting of 20340-45%, and 95% Sin in areas where there is a large reaction with chlorine gas.
Fused silica bricks containing the above are commonly used.

しかしながら、従来の塩化炉内張りに用いられている煉
瓦は何れも10〜15%の見掛気孔率を有しているため
に、気孔に沿って塩素ガスが煉瓦内に侵入し組織脆弱化
を生起したり、内張耐火物と炉内反応生成物との摩耗を
生じ、煉瓦の損傷が大きく、短命となっていることが知
られている。
However, since the bricks used for conventional chlorination furnace linings all have an apparent porosity of 10 to 15%, chlorine gas penetrates into the bricks along the pores, causing tissue weakening. It is known that the refractory lining and the reaction products in the furnace wear out, causing significant damage to the bricks and shortening their lifespan.

発明が解決しようとする課題 前述した如き従来方式の諸欠陥を解決し、塩化炉の寿命
の延命化並びに保守、管理を容易とし、コストダウンを
意図するものである。
Problems to be Solved by the Invention It is an object of the present invention to solve the various deficiencies of the conventional system as described above, to extend the life of a chlorination furnace, to facilitate maintenance and management, and to reduce costs.

課題を解決するための手段 本出願人会社の商品SLIBMAX−5は5i0299
.+i%含有の溶融シリカ質耐火煉瓦であって、浸漬ノ
ズル用として開発販売されているが、この煉瓦の見掛気
孔率は11.0%前後であり、塩化炉内張煉瓦としては
見掛気孔率が大であって塩素ガスによる組織の脆化はま
ぬがれない。
Means for solving the problem The product SLIBMAX-5 of the applicant company is 5i0299
.. This is a fused silica refractory brick containing +i%, which has been developed and sold for use in immersion nozzles, but the apparent porosity of this brick is around 11.0%, and the apparent porosity of this brick is approximately 11.0%. The rate is high, and tissue embrittlement due to chlorine gas is unavoidable.

本発明者等はこの種塩化炉用内張耐火物に好適な耐火煉
瓦の開発に成功したものであり、その技術的構成は前記
特許請求の範囲各項に明記したとおりであるが、各必須
の技術的構成について以下に詳述する。
The present inventors have succeeded in developing a refractory brick suitable for lining refractories for this type of chlorination furnace, and the technical configuration thereof is as specified in each of the claims above, but each essential The technical configuration of the system is detailed below.

Sin、含有量は高い程不純物、特に塩素ガスと易反応
性のAl1203 、Fe2us等が少なくなるため、
Sin、含有量は99.0%以上としなければならない
The higher the Sin content, the less impurities, especially Al1203, Fe2us, etc., which are easily reactive with chlorine gas, will be reduced.
The Sin content must be 99.0% or more.

粒度分布は微細粒度の原料を用いることにより見掛気孔
率の低下に有用であり、連続した粒度分布の材料を用い
ることにより、より緻密な鋳込品を得ることができ、5
.On+m径より大なる粒子の存在は泥漿鋳込の際に偏
析する傾向があり、均一拡散組織が得られない。
Particle size distribution is useful for reducing apparent porosity by using raw materials with fine particle size, and denser cast products can be obtained by using materials with continuous particle size distribution.
.. The presence of particles with a diameter larger than On+m tends to segregate during slurry casting, making it impossible to obtain a uniformly diffused structure.

バインダーとして用いる水溶性アルギン酸塩は、アルギ
ン酸アンモニウム、アルギン酸ナトリウム又はアルギン
酸カリウムであり添加量は0.1〜0.3重量%であり
、0.1重量%未満では所要の結合が得られず、0.3
重量%をこえる必要がない。上記上限をこえて添加する
と、クリストバライト転移の促進剤として働き、煉瓦組
織の緻密化を阻害するばかりか、塩素ガスとの反応を助
長し、またTi14等による摩耗が促進される。
The water-soluble alginate used as a binder is ammonium alginate, sodium alginate, or potassium alginate, and the amount added is 0.1 to 0.3% by weight, and if it is less than 0.1% by weight, the required bond cannot be obtained, and 0. .3
There is no need to exceed the weight percentage. If it is added in excess of the above upper limit, it acts as a promoter of cristobalite transformation and not only inhibits the densification of the brick structure, but also promotes the reaction with chlorine gas and accelerates wear caused by Ti14 and the like.

焼成温度は1200’〜1350℃とし、1350℃を
超えると、煉瓦組織中にクリストバライトの転移が起り
、組織の緻密化が阻害される。従って、従来品に比しは
y  too−tso℃高い焼成温度範囲が必要である
The firing temperature is 1200' to 1350°C, and if it exceeds 1350°C, cristobalite transition occurs in the brick structure and densification of the structure is inhibited. Therefore, a firing temperature range that is y too-tso degrees Celsius higher than that of conventional products is required.

更に、焼成品は耐塩素ガス物質により含浸させ、見掛気
孔率の低下を図り、耐塩素ガス含浸物質としてはシリカ
ゾル、ケイ酸ソーダ等が好適かつ効果的である。
Furthermore, the fired product is impregnated with a chlorine gas-resistant substance to reduce the apparent porosity, and silica sol, sodium silicate, etc. are suitable and effective as the chlorine gas-resistant impregnated substance.

実施例 見掛気孔率の異なる溶融シリカ買焼成れんが及び粘土質
れんがの耐塩素ガス特性を第1表に示す。第1表から見
掛気孔率1.3%のれんが試料歯1はNo2,3,4.
5に比較して塩素ガスによる重量減が少なくシリカ質耐
火煉瓦特性が向上していることが明らかである。
Examples Table 1 shows the chlorine gas resistance properties of fused silica fired bricks and clay bricks with different apparent porosity. From Table 1, brick sample tooth 1 with an apparent porosity of 1.3% has Nos. 2, 3, and 4.
It is clear that compared to No. 5, the weight loss due to chlorine gas is smaller and the siliceous firebrick properties are improved.

第1表 *2;サンドブラスト法;圧力3.5Kgf/cm2 
 珪石粒、3分間吹付中3 、1000℃空冷 発明の効果 (1)気孔率が低いので塩素ガスの侵入が少ない。
Table 1 *2; Sandblasting method; Pressure 3.5Kgf/cm2
Silica stone grains, sprayed for 3 minutes, air cooled at 1000°C Effects of the invention (1) Low porosity, so less chlorine gas enters.

(2)従って、塩化炉内張材として使用すると、内張り
の損傷が極めて少なく、内張りの寿命が延長され、作業
性が改良される。
(2) Therefore, when used as a chlorination furnace lining material, damage to the lining is extremely small, the life of the lining is extended, and workability is improved.

Claims (3)

【特許請求の範囲】[Claims] (1)SiO_299.0%以上でAl_2O_3及び
Fe_2O_3の含有量が微量であり、粒度分布が数ミ
クロン〜5.0mm径である耐火物原料を0.1〜0.
3重量%の水溶性アルギン酸塩をバインダーとして泥漿
鋳込法により成型し、1200゜〜1350℃で焼成し
、該焼成品を耐塩素ガス物質で含浸し、見掛気孔率を5
%以下とした、ことを特徴とする耐塩素ガス用溶融シリ
カ質耐火煉瓦。
(1) A refractory raw material with a SiO_299.0% or more, a trace amount of Al_2O_3 and Fe_2O_3, and a particle size distribution of several microns to 5.0 mm in diameter is 0.1 to 0.
It is molded by slurry casting using 3% by weight of water-soluble alginate as a binder, fired at 1200° to 1350°C, and the fired product is impregnated with a chlorine gas-resistant material to reduce the apparent porosity to 5.
% or less, a fused silica refractory brick for chlorine gas resistance.
(2)前記水溶性アルギン酸塩が、アルギン酸アンモニ
ウム、アルギン酸ナトリウム又はアルギン酸カリウムで
ある請求項1記載の耐塩素ガス用溶融シリカ質耐火煉瓦
(2) The fused siliceous refractory brick for chlorine gas resistance according to claim 1, wherein the water-soluble alginate is ammonium alginate, sodium alginate, or potassium alginate.
(3)前記耐塩素ガス物質がシリカゾル又はケイ酸ソー
ダである請求項1記載の耐塩素ガス用溶融シリカ質耐火
煉瓦。
(3) The chlorine gas resistant fused siliceous refractory brick according to claim 1, wherein the chlorine gas resistant substance is silica sol or sodium silicate.
JP10909588A 1988-05-06 1988-05-06 Melted siliceous refractory brick resistant to gaseous chlorine Granted JPH01282148A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP10909588A JPH01282148A (en) 1988-05-06 1988-05-06 Melted siliceous refractory brick resistant to gaseous chlorine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP10909588A JPH01282148A (en) 1988-05-06 1988-05-06 Melted siliceous refractory brick resistant to gaseous chlorine

Publications (2)

Publication Number Publication Date
JPH01282148A true JPH01282148A (en) 1989-11-14
JPH0547503B2 JPH0547503B2 (en) 1993-07-16

Family

ID=14501459

Family Applications (1)

Application Number Title Priority Date Filing Date
JP10909588A Granted JPH01282148A (en) 1988-05-06 1988-05-06 Melted siliceous refractory brick resistant to gaseous chlorine

Country Status (1)

Country Link
JP (1) JPH01282148A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2559678A1 (en) * 2011-08-16 2013-02-20 Siemens Aktiengesellschaft Pressure-cast slip and fire-resistant ceramic for gas turbine assemblies produced using the same
RU2650970C1 (en) * 2017-05-04 2018-04-20 Акционерное общество "Научно-производственное объединение Государственный оптический институт им. С.И. Вавилова" (АО "НПО ГОИ им. С.И. Вавилова") Method of quartz ceramics production
WO2019054222A1 (en) * 2017-09-12 2019-03-21 Jfeスチール株式会社 Refractory for siliconizing furnaces

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2559678A1 (en) * 2011-08-16 2013-02-20 Siemens Aktiengesellschaft Pressure-cast slip and fire-resistant ceramic for gas turbine assemblies produced using the same
WO2013023913A3 (en) * 2011-08-16 2013-05-16 Siemens Aktiengesellschaft Pressure casting slip and refractory ceramic produced therefrom for gas turbine units
US9221718B2 (en) 2011-08-16 2015-12-29 Siemens Aktiengesellschaft Pressure casting slip and refractory ceramic produced therefrom for gas turbine units
RU2650970C1 (en) * 2017-05-04 2018-04-20 Акционерное общество "Научно-производственное объединение Государственный оптический институт им. С.И. Вавилова" (АО "НПО ГОИ им. С.И. Вавилова") Method of quartz ceramics production
WO2019054222A1 (en) * 2017-09-12 2019-03-21 Jfeスチール株式会社 Refractory for siliconizing furnaces
KR20200039740A (en) * 2017-09-12 2020-04-16 제이에프이 스틸 가부시키가이샤 Refractory for impregnation treatment furnace

Also Published As

Publication number Publication date
JPH0547503B2 (en) 1993-07-16

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