JP3780398B2 - How to use refractories - Google Patents

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JP3780398B2
JP3780398B2 JP35760998A JP35760998A JP3780398B2 JP 3780398 B2 JP3780398 B2 JP 3780398B2 JP 35760998 A JP35760998 A JP 35760998A JP 35760998 A JP35760998 A JP 35760998A JP 3780398 B2 JP3780398 B2 JP 3780398B2
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refractory
weight
basicity
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melting
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淳 矢野
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Hitachi Zosen Corp
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  • Furnace Housings, Linings, Walls, And Ceilings (AREA)

Description

【０００１】
【発明の属する技術分野】
この発明は、たとえば産業廃棄物等を溶融して減容化する溶融炉の炉材等として用いられる耐火物の使用方法に関する。
【０００２】
【従来の技術】
従来、上記溶融炉の炉材としては、Ｃｒ２ Ｏ３ １０重量％を含み、残部Ａｌ２ Ｏ３ からなる耐火物が用いられていた。Ｃｒ２ Ｏ３ は、この耐火物の耐食性を向上させるために含有させられている。
【０００３】
【発明が解決しようとする課題】
しかしながら、従来の耐火物はＣｒ２ Ｏ３ を含んでいるので、この耐火物からなる炉材を用いた溶融炉で産業廃棄物等を溶融する際に、毒性を有する６価のクロムが発生する可能性があり、しかも６価のクロムが発生するため耐火物の廃棄処理についても苦慮しているのが現状である。
【０００４】
この発明の目的は、上記問題を解決し、Ｃｒ２ Ｏ３ を含有せず、しかも従来の耐火物と同等の耐食性を有する耐火物の使用方法を提供することにある。
【０００５】
【課題を解決するための手段と発明の効果】
請求項１の発明による耐火物の使用方法は、ＭｇＡｌ２ Ｏ４ ５〜２０重量％およびＺｒＯ２ ５〜２０重量％を含み、残部Ｍｇ２ ＳｉＯ４ からなる耐火物を、塩基度が０．７〜２．０の範囲である被溶融物を溶融する溶融炉の炉材に用いるものである。但し、上記耐火物には、不可避不純物が含まれていてもよい。
【０００６】
請求項１の発明で使用される耐火物において、ＭｇＡｌ２ Ｏ４ （スピネル）は、溶融物の塩基度（ＣａＯ／ＳｉＯ２ ）が０．７以上の領域において、耐火物の溶損を少なくして耐食性を向上させる効果を有するが、その含有量が５重量％未満であるとこの効果は得られず、２０重量％を越えるとかえって溶損が大きくなり、耐食性が低下する。したがって、ＭｇＡｌ２ Ｏ４ の含有量は５〜２０重量％の範囲内で選ぶべきである。ＺｒＯ２ は、溶融される被溶融物の塩基度が０．３〜２．０の領域において、溶融物の耐火物組織内への浸透を抑制する効果を有するが、その含有量が５重量％未満であるとこの効果は得られず、２０重量％を越えると溶損が大きくなり、耐食性が低下する。したがって、ＺｒＯ２ の含有量は５〜２０重量％の範囲内で選ぶべきである。また、Ｍｇ２ ＳｉＯ４ （フォルステライト）は、耐溶損性および耐浸透性に優れたベース材料である。
【０００７】
請求項１の発明の耐火物の使用方法によれば、上述した耐火物を、産業廃棄物等の溶融炉の炉材として使用した場合、毒性を呈することなく、しかも毒性を呈さないために廃棄処理を容易に行うことができる。さらに、塩基度が０．７〜２．０の範囲内にある溶融物に対して、従来の耐火物と同等の耐食性を有する。
【０００８】
請求項２の発明による耐火物の使用方法は、３Ａｌ２ Ｏ３ ・２ＳｉＯ２ ５〜２０重量％およびＺｒＯ２ ５〜２０重量％を含み、残部Ｍｇ２ ＳｉＯ４ からなる耐火物を、塩基度が０．３以上でかつ０．７未満である被溶融物を溶融する溶融炉の炉材に用いるものである。但し、上記耐火物には、不可避不純物が含まれていてもよい。
【０００９】
請求項２の発明で使用される耐火物において、３Ａｌ２ Ｏ３ ・２ＳｉＯ２ （ムライト）は、溶融物の塩基度が０．７未満の領域において、耐火物の溶損を少なくして耐食性を向上させる効果を有するが、その含有量が５重量％未満であるとこの効果は得られず、２０重量％を越えるとかえって溶損が大きくなり、耐食性が低下する。したがって、３Ａｌ２ Ｏ３ ・２ＳｉＯ２ の含有量は５〜２０重量％の範囲内で選ぶべきである。ＺｒＯ２ は、溶融される被溶融物の塩基度が０．３〜２．０の領域において、溶融物の耐火物組織内への浸透を抑制する効果を有するが、その含有量が５重量％未満であるとこの効果は得られず、２０重量％を越えると溶損が大きくなり、耐食性が低下する。したがって、ＺｒＯ２ の含有量は５〜２０重量％の範囲内で選ぶべきである。また、Ｍｇ２ ＳｉＯ４ （フォルステライト）は、耐溶損性および耐浸透性に優れたベース材料である。
【００１０】
請求項２の発明の耐火物の使用方法によれば、上述した耐火物を、産業廃棄物等の溶融炉の炉材として使用した場合、毒性を呈することなく、しかも毒性を呈さないために廃棄処理を容易に行うことができる。さらに、塩基度が０．３以上でかつ０．７未満である溶融物に対して、従来の耐火物と同等の耐食性を有する。
【００１１】
請求項１または２の発明の耐火物の使用方法において、ＺｒＯ２ のうちの少なくとも一部をＺｒＳｉＯ４ （ジルコン）で置換することができる。この場合も、作用効果は変わることがない。
【００１２】
一般の産業廃棄物等の塩基度は０．３〜２．０の範囲内であり、塩基度が０．３以上でかつ０．７未満である被溶融物に対して、請求項２の発明において使用される耐火物、またはこの耐火物中のＺｒＯ２ のうちの少なくとも一部をＺｒＳｉＯ４ で置換した耐火物は十分な耐食性を有する。また、塩基度が０．７〜２．０の範囲内にある被溶融物に対して、請求項１の発明において使用される耐火物、またはこの耐火物中のＺｒＯ２ のうちの少なくとも一部をＺｒＳｉＯ４ で置換した耐火物は十分な耐食性を有する。
【００１３】
【発明の実施の形態】
以下、この発明の具体的実施例を比較例とともに示す。
【００１４】
実施例１〜６および比較例１〜１６
ＭｇＡｌ２ Ｏ４ 粉末、３Ａｌ２ Ｏ３ ・２ＳｉＯ２ 粉末、ＺｒＯ２ 粉末、ＺｒＳｉＯ４ 粉末と、Ｍｇ２ ＳｉＯ４ 粉末、Ｃｒ２ Ｏ３ 粉末およびＡｌ２ Ｏ３ 粉末を用意した。全ての粉末の平均粒径はそれぞれ５０μｍである。ついで、これらの粉末のうち２種以上を表１に示す割合で混合した混合粉末、または単体粉末に、バインダーとしてポリビニルアルコール粉末を、混合粉末または単体粉末１００重量部に対して３重量部の割合で添加した。ついで、バインダー添加粉末を、水を用いてボールミルで２４時間攪拌混合した後乾燥器にて１２０℃で２４時間乾燥させた。ついで、この乾燥粉末を３００ｋｇ／ｃｍ２ の圧力でプレス成形し、さらに大気中において１５００℃×２時間の焼結を行い、縦２００ｍｍ、横１００ｍｍ、高さ５０ｍｍの試料を得た。
【００１５】
評価試験１
各試料の溶損速度および浸透深さを、回転浸食法により測定した。すなわち、各試料を回転ドラム中にセットし、プロパンガスバーナで１５００℃に加熱した後、表２に示す浸食剤を投入し、浸食剤を３０分毎に交換しつつ８時間経過した後の試料の平均減肉量を求め、この減肉量から溶損速度を算出した。また、浸透深さは、最大浸透深さで評価した。なお、浸食剤は産業廃棄物と同じ組成を有するものである。
【００１６】
これらの結果も表１に示す。
【００１７】
【表１】

Figure 0003780398
なお、表１の評価の欄において、○は比較例１３〜１６と同等の特性を有することを表し、×は比較例１３〜１６よりも劣る特性を有することを表す。
【００１８】
【表２】
Figure 0003780398
表１に示す結果から、請求項１の発明の組成範囲の耐火物、またはこの耐火物中のＺｒＯ２ のうちの少なくとも一部をＺｒＳｉＯ４ で置換した耐火物によれば、塩基度が０．７〜２．０の範囲である浸食剤に対する耐食性が、従来のＣｒ２ Ｏ３ １０重量％を含み、残部Ａｌ２ Ｏ３ からなる耐火物と同等、もしくはそれ以上であることが分かる（実施例４〜６）。また、請求項２の発明の組成範囲の耐火物によれば、塩基度が０．３以上でかつ０．７未満である浸食剤に対する耐食性が、従来のＣｒ２ Ｏ３ １０重量％を含み、残部Ａｌ２ Ｏ３ からなる耐火物と同等、もしくはそれ以上であることが分かる（実施例１〜３）。
【００１９】
また、ＭｇＡｌ２ Ｏ４ 、ＺｒＯ２ およびＭｇ２ ＳｉＯ４ からなる耐火物であっても、ＭｇＡｌ２ Ｏ４ の含有量が、５重量％未満あるいは２０重量％を越えたものは、塩基度０．７〜２．０の範囲である浸食剤に対して溶損が大きくなるとともに（比較例１５および１３）、ＺｒＯ２ の含有量が５重量％未満のものは塩基度０．７〜２．０の範囲である浸食剤に対して浸透深さが大きくなり（比較例１６）、同じく２０重量％を越えたものは塩基度０．７〜２．０の範囲である浸食剤に対して溶損が大きくなる（比較例１４）。
【００２０】
さらに、３Ａｌ２ Ｏ３ ・２ＳｉＯ２ 、ＺｒＯ２ およびＭｇ２ ＳｉＯ４ からなる耐火物であっても、３Ａｌ２ Ｏ３ ・２ＳｉＯ２ の含有量が、５重量％未満あるいは２０重量％を越えたものは塩基度０．７未満の浸食剤に対して溶損が大きくなるとともに（比較例１１および９）、ＺｒＯ２ の含有量が５重量％未満のものは塩基度０．７未満である浸食剤に対して浸透深さが大きくなり（比較例１２）、同じく２０重量％を越えたものは塩基度０．７未満である浸食剤に対して溶損が大きくなる（比較例１０）。
【００２１】
したがって、いずれの場合も産業廃棄物の溶融炉に用いるのに適していないことが分かる。
【００２２】
評価試験２
実施例２と同じ組成の耐火物から４００ｍｍ×４００ｍｍ×２００ｍｍのブロックを作製し、このブロックを塩基度０．５である産業廃棄物の溶融炉に組み込み、２００時間の連続運転を行った。運転終了後上記ブロックを溶融炉から取出し、溶融炉に組み込まれている従来のＣｒ２ Ｏ３ １０重量％を含み、残部Ａｌ２ Ｏ３ からなる耐火物と比較した。その結果、従来の耐火物は２０ｍｍ溶損したのに対し、上記ブロックの溶損は１５ｍｍであり、従来の耐火物に比べて耐食性に優れていることが判明した。
【００２３】
評価試験３
実施例６と同じ組成の耐火物から４００ｍｍ×４００ｍｍ×２００ｍｍのブロックを作製し、このブロックを塩基度１．１である産業廃棄物の溶融炉に組み込み、２００時間の連続運転を行った。運転終了後上記ブロックを溶融炉から取出し、溶融炉に組み込まれている従来のＣｒ２ Ｏ３ １０重量％を含み、残部Ａｌ２ Ｏ３ からなる耐火物と比較した。その結果、従来の耐火物は２３ｍｍ溶損したのに対し、上記ブロックの溶損は１７ｍｍであり、従来の耐火物に比べて耐食性に優れていることが判明した。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method of using a refractory material used as a furnace material or the like of a melting furnace that melts and reduces volume of industrial waste, for example.
[0002]
[Prior art]
Conventionally, as the furnace material of the melting furnace, a refractory material containing 10% by weight of Cr 2 O 3 and the balance being Al 2 O 3 has been used. Cr 2 O 3 is contained in order to improve the corrosion resistance of the refractory.
[0003]
[Problems to be solved by the invention]
However, since conventional refractories contain Cr 2 O 3 , toxic hexavalent chromium is generated when melting industrial wastes in a melting furnace using a furnace material made of this refractory. There is a possibility, and since hexavalent chromium is generated, it is difficult to dispose of refractories.
[0004]
An object of the present invention is to solve the above problems and provide a method of using a refractory that does not contain Cr 2 O 3 and has corrosion resistance equivalent to that of a conventional refractory.
[0005]
[Means for Solving the Problems and Effects of the Invention]
Using refractory according the invention of claim 1 includes a MgAl 2 O 4 5 to 20 wt% and ZrO 2 5 to 20 wt%, a refractory material and the balance Mg 2 SiO 4, basicity 0.7 It is used for a furnace material of a melting furnace for melting a material to be melted in a range of ~ 2.0 . However, the above-mentioned refractory, may contain inevitable impurities.
[0006]
In the refractory used in the invention of claim 1, MgAl 2 O 4 (spinel) reduces the refractory melting loss in the region where the melt basicity (CaO / SiO 2 ) is 0.7 or more. However, if the content is less than 5% by weight, this effect cannot be obtained. If the content exceeds 20% by weight, the melting loss increases, and the corrosion resistance decreases. Therefore, the content of MgAl 2 O 4 should be selected within the range of 5 to 20% by weight. ZrO 2 has the effect of suppressing penetration of the melt into the refractory structure in the region where the basicity of the melted material is 0.3 to 2.0, but the content is 5% by weight. If the amount is less than 20%, this effect cannot be obtained. If the amount exceeds 20% by weight, the melting loss increases and the corrosion resistance decreases. Therefore, the ZrO 2 content should be selected within the range of 5 to 20% by weight. Mg 2 SiO 4 (forsterite) is a base material that is excellent in resistance to melting and penetration.
[0007]
According to the method of using the refractory of the invention of claim 1, when the above-mentioned refractory is used as a furnace material of a melting furnace such as industrial waste, it is discarded because it does not exhibit toxicity and does not exhibit toxicity. Processing can be performed easily. Furthermore, it has a corrosion resistance equivalent to that of a conventional refractory against a melt having a basicity in the range of 0.7 to 2.0.
[0008]
Using refractory according the invention of claim 2 comprises a 3Al 2 O 3 · 2SiO 2 5~20 wt% and ZrO 2 5 to 20 wt%, a refractory material and the balance Mg 2 SiO 4, basicity It is used for a furnace material of a melting furnace that melts a material to be melted that is 0.3 or more and less than 0.7 . However, the above-mentioned refractory, may contain inevitable impurities.
[0009]
In refractories used in the invention of claim 2, 3Al 2 O 3 · 2SiO 2 ( mullite), in the region of basicity is less than 0.7 of the melt, the corrosion resistance with less erosion of the refractory Although it has an effect of improving, if the content is less than 5% by weight, this effect cannot be obtained, and if it exceeds 20% by weight, the melting loss becomes rather large and the corrosion resistance decreases. Accordingly, the content of 3Al 2 O 3 · 2SiO 2 should be chosen in the range of 5 to 20 wt%. ZrO 2 has the effect of suppressing penetration of the melt into the refractory structure in the region where the basicity of the melted material is 0.3 to 2.0, but the content is 5% by weight. If the amount is less than 20%, this effect cannot be obtained. If the amount exceeds 20% by weight, the melting loss increases and the corrosion resistance decreases. Therefore, the ZrO 2 content should be selected within the range of 5 to 20% by weight. Mg 2 SiO 4 (forsterite) is a base material that is excellent in resistance to melting and penetration.
[0010]
According to the method of using the refractory of the invention of claim 2, when the above-mentioned refractory is used as a furnace material of a melting furnace such as industrial waste, it is discarded because it does not exhibit toxicity and does not exhibit toxicity. Processing can be performed easily. Furthermore, it has a corrosion resistance equivalent to that of a conventional refractory against a melt having a basicity of 0.3 or more and less than 0.7.
[0011]
In the method for using a refractory according to the first or second aspect of the present invention, at least a part of ZrO 2 can be replaced with ZrSiO 4 (zircon). Also in this case, the operational effect does not change.
[0012]
The basicity of general industrial waste or the like is within a range of 0.3 to 2.0, and the invention according to claim 2 for a material to be melted having a basicity of 0.3 or more and less than 0.7. Or a refractory obtained by substituting at least a part of ZrO 2 in the refractory with ZrSiO 4 has sufficient corrosion resistance. Moreover, with respect to the to-be-melted material in which the basicity is in the range of 0.7 to 2.0, at least a part of the refractory used in the invention of claim 1 or ZrO 2 in the refractory The refractory in which is replaced with ZrSiO 4 has sufficient corrosion resistance.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, specific examples of the present invention will be described together with comparative examples.
[0014]
Examples 1-6 and Comparative Examples 1-16
MgAl 2 O 4 powder, 3Al 2 O 3 · 2SiO 2 powder were prepared ZrO 2 powder, and ZrSiO 4 powder, Mg 2 SiO 4 powder, the Cr 2 O 3 powder and Al 2 O 3 powder. The average particle size of all powders is 50 μm. Next, a mixed powder obtained by mixing two or more of these powders at a ratio shown in Table 1, or a simple powder, and a polyvinyl alcohol powder as a binder at a ratio of 3 parts by weight with respect to 100 parts by weight of the mixed powder or single powder. Added at. Next, the binder-added powder was stirred and mixed with water in a ball mill for 24 hours and then dried at 120 ° C. for 24 hours in a dryer. Next, this dry powder was press-molded at a pressure of 300 kg / cm 2 and further sintered in the atmosphere at 1500 ° C. for 2 hours to obtain a sample having a length of 200 mm, a width of 100 mm, and a height of 50 mm.
[0015]
Evaluation test 1
The erosion rate and penetration depth of each sample were measured by the rotary erosion method. That is, each sample was set in a rotating drum, heated to 1500 ° C. with a propane gas burner, then the erodant shown in Table 2 was added, and the sample after 8 hours had passed while changing the erodant every 30 minutes. The average thinning amount was obtained, and the rate of melting loss was calculated from this thinning amount. The penetration depth was evaluated by the maximum penetration depth. In addition, an erosion agent has the same composition as industrial waste.
[0016]
These results are also shown in Table 1.
[0017]
[Table 1]
Figure 0003780398
In addition, in the column of evaluation of Table 1, (circle) represents having a characteristic equivalent to Comparative Examples 13-16, and x represents having a characteristic inferior to Comparative Examples 13-16.
[0018]
[Table 2]
Figure 0003780398
From the results shown in Table 1, according to the refractory having the composition range of the invention of claim 1 or the refractory in which at least a part of ZrO 2 in the refractory is substituted with ZrSiO 4 , the basicity is 0. corrosion resistance to erosion agent in the range of 7 to 2.0 comprises a conventional Cr 2 O 3 10 wt%, it can be seen at equivalent refractory the balance being Al 2 O 3, or more (example 4-6). Further, according to the refractory having the composition range of the invention of claim 2, the corrosion resistance to an erodant having a basicity of 0.3 or more and less than 0.7 includes 10% by weight of conventional Cr 2 O 3 , It turns out that it is equivalent to or more than the refractory consisting of the balance Al 2 O 3 (Examples 1 to 3).
[0019]
Further, even if the refractory is composed of MgAl 2 O 4 , ZrO 2 and Mg 2 SiO 4 , the basicity of the refractory whose MgAl 2 O 4 content is less than 5% by weight or more than 20% by weight is 0.8. While the erosion with respect to the erodant in the range of 7 to 2.0 is increased (Comparative Examples 15 and 13), those having a ZrO 2 content of less than 5% by weight have a basicity of 0.7 to 2.0. The penetration depth was increased with respect to the erodant in the range of (Comparative Example 16), and the amount exceeding 20% by weight was also damaged by the erodant in the range of basicity of 0.7 to 2.0. Increases (Comparative Example 14).
[0020]
Even more, even refractory consisting 3Al 2 O 3 · 2SiO 2, ZrO 2 and Mg 2 SiO 4, the content of 3Al 2 O 3 · 2SiO 2 is, beyond the or 20 wt% less than 5 wt% Has a large dissolution loss with respect to an erosion agent having a basicity of less than 0.7 (Comparative Examples 11 and 9), and an erosion agent having a ZrO 2 content of less than 5% by weight has a basicity of less than 0.7. In contrast, the penetration depth becomes larger (Comparative Example 12), and when the amount exceeds 20% by weight, the erosion with respect to the erodant having a basicity of less than 0.7 becomes larger (Comparative Example 10).
[0021]
Therefore, it turns out that it is not suitable to use for the melting furnace of industrial waste in any case.
[0022]
Evaluation test 2
A 400 mm × 400 mm × 200 mm block was made from a refractory having the same composition as in Example 2, and this block was incorporated into an industrial waste melting furnace having a basicity of 0.5, and was continuously operated for 200 hours. After completion of the operation, the block was taken out from the melting furnace and compared with a refractory material containing 10% by weight of conventional Cr 2 O 3 incorporated in the melting furnace and the balance being Al 2 O 3 . As a result, the conventional refractory was melted by 20 mm, whereas the above-mentioned block had a melt damage of 15 mm, which was found to be superior to the conventional refractory in corrosion resistance.
[0023]
Evaluation test 3
A 400 mm × 400 mm × 200 mm block was prepared from a refractory having the same composition as in Example 6, and this block was incorporated into an industrial waste melting furnace having a basicity of 1.1, followed by continuous operation for 200 hours. After completion of the operation, the block was taken out from the melting furnace and compared with a refractory material containing 10% by weight of conventional Cr 2 O 3 incorporated in the melting furnace and the balance being Al 2 O 3 . As a result, the conventional refractory was melted by 23 mm, whereas the block had a melt damage of 17 mm, which was found to be superior to the conventional refractory in corrosion resistance.

Claims (3)

ＭｇＡｌ２ Ｏ４ ５〜２０重量％およびＺｒＯ２ ５〜２０重量％を含み、残部Ｍｇ２ ＳｉＯ４ からなる耐火物を、塩基度が０．７〜２．０の範囲である被溶融物を溶融する溶融炉の炉材に用いる耐火物の使用方法。 Melting a refractory material containing 5 to 20% by weight of MgAl 2 O 4 and 5 to 20% by weight of ZrO 2 and the balance Mg 2 SiO 4, and a material to be melted having a basicity in the range of 0.7 to 2.0 How to use refractories used in furnace materials for melting furnaces . ３Ａｌ２ Ｏ３ ・２ＳｉＯ２ ５〜２０重量％およびＺｒＯ２ ５〜２０重量％を含み、残部Ｍｇ２ ＳｉＯ４ からなる耐火物を、塩基度が０．３以上でかつ０．７未満である被溶融物を溶融する溶融炉の炉材に用いる耐火物の使用方法。3Al include 2 O 3 · 2SiO 2 5~20 wt% and ZrO 2 5 to 20 wt%, a refractory material and the balance Mg 2 SiO 4, the basicity is and less than 0.7 0.3 or more A method of using a refractory used for a furnace material of a melting furnace for melting a melt . 耐火物中のＺｒＯ２ のうちの少なくとも一部をＺｒＳｉＯ４ で置換した請求項１または２記載の耐火物の使用方法。 The method for using a refractory according to claim 1 or 2, wherein at least a part of ZrO 2 in the refractory is substituted with ZrSiO 4 .
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