JPH01282148A - Melted siliceous refractory brick resistant to gaseous chlorine - Google Patents
Melted siliceous refractory brick resistant to gaseous chlorineInfo
- 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
Links
- 239000011449 brick Substances 0.000 title claims abstract description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title abstract 5
- 239000000460 chlorine Substances 0.000 title abstract 5
- 229910052801 chlorine Inorganic materials 0.000 title abstract 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 7
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940072056 alginate Drugs 0.000 claims abstract description 6
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 6
- 229920000615 alginic acid Polymers 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims abstract description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000728 ammonium alginate Substances 0.000 claims abstract description 3
- 235000010407 ammonium alginate Nutrition 0.000 claims abstract description 3
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 claims abstract description 3
- 235000010408 potassium alginate Nutrition 0.000 claims abstract description 3
- 239000000737 potassium alginate Substances 0.000 claims abstract description 3
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 claims abstract description 3
- 238000007582 slurry-cast process Methods 0.000 claims abstract description 3
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 3
- 239000000661 sodium alginate Substances 0.000 claims abstract description 3
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 17
- 239000005350 fused silica glass Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000012423 maintenance Methods 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000005660 chlorination reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011451 fired brick Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
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)
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.
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.
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.
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)
| 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 |
-
1988
- 1988-05-06 JP JP10909588A patent/JPH01282148A/en active Granted
Cited By (6)
| 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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