JP2017000907A - Slag suppressed with component elution - Google Patents
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- JP2017000907A JP2017000907A JP2015113953A JP2015113953A JP2017000907A JP 2017000907 A JP2017000907 A JP 2017000907A JP 2015113953 A JP2015113953 A JP 2015113953A JP 2015113953 A JP2015113953 A JP 2015113953A JP 2017000907 A JP2017000907 A JP 2017000907A
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- 239000002893 slag Substances 0.000 title claims abstract description 91
- 238000010828 elution Methods 0.000 title abstract description 37
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000003723 Smelting Methods 0.000 claims abstract description 20
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 13
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000012360 testing method Methods 0.000 abstract description 19
- 229910052785 arsenic Inorganic materials 0.000 abstract description 16
- 229910052745 lead Inorganic materials 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 6
- 229910052742 iron Inorganic materials 0.000 abstract 3
- 239000013078 crystal Substances 0.000 description 17
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000007922 dissolution test Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- -1 ferrous metals Chemical class 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000000383 hazardous chemical Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 238000003913 materials processing Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical class O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- OWTFKEBRIAXSMO-UHFFFAOYSA-N arsenite(3-) Chemical compound [O-][As]([O-])[O-] OWTFKEBRIAXSMO-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
本発明は、鉛やヒ素といった成分の溶出が抑制されたスラグおよびその製造方法に関する。 The present invention relates to a slag in which elution of components such as lead and arsenic is suppressed, and a method for producing the slag.
銅などの非鉄金属の乾式製錬において、スラグの安定的なリサイクルが、事業の継続の観点から重要になっている。特に、スラグのリサイクルのためには、製錬炉から排出されるスラグを資源化することが求められ、用途に応じて環境的見地から基準が設けられている。 In the dry smelting of non-ferrous metals such as copper, stable recycling of slag is important from the viewpoint of business continuity. In particular, in order to recycle slag, it is required to recycle slag discharged from the smelting furnace, and standards are set from an environmental point of view according to the application.
その中でも、平成１５年環境省告示第１９号に規定される有害物質の含有量試験（ＪＩＳ Ｋ ００５８−２：２００５）、および平成３年環境庁告示第４６号に規定される有害物質の溶出量試験（ＪＩＳ Ｋ ００５８−１：２００５）の結果に基づく、土壌汚染に関する基準を満たすことが求められる。当該基準で規制されている元素の中でも、特にＡｓ（砒素）、Ｐｂ（鉛）の溶出量を可能な限り低減させることが求められている。 Among them, content testing of hazardous substances specified in the Ministry of the Environment Notification No. 19 (JIS K 0058-2: 2005) and elution of hazardous substances specified in the Environment Agency Notification No. 46 in 1991 It is required to satisfy the criteria for soil contamination based on the results of a quantity test (JIS K 0058-1: 2005). Among the elements regulated by the standards, it is particularly required to reduce the amount of As (arsenic) and Pb (lead) as much as possible.
特許文献１には、平成３年環境庁告示第４６号に規定される含有量試験にてＡｓの溶出量を低減させる技術が開示されている。これによれば、溶融スラグを水砕してスラグを製造するに際して、水砕水の中の浮遊物を沈降分離して、再び水砕処理に供することにより、浮遊物に含まれるＡｓを除去することが可能になり、結果的に平成３年環境庁告示第４６号に規定される溶出量試験にてＡｓの溶出量を低減させることができる。 Patent Document 1 discloses a technique for reducing the amount of As eluted in a content test specified in Environment Agency Notification No. 46 of 1991. According to this, when the molten slag is granulated to produce slag, the suspended matter in the granulated water is settled and separated, and again subjected to the granulation treatment, thereby removing As contained in the suspended matter. As a result, the elution amount of As can be reduced in the elution amount test specified in Notification No. 46 of the Environment Agency in 1991.
非特許文献１、２には、大気中で加熱したスラグについて、それぞれ平成３年環境庁告示第４６号に規定される溶出量試験、および平成１５年環境省告示第１９号に規定される含有量試験を行う技術が開示されている。非特許文献１においては、６００℃以上の温度でスラグを加熱処理することで、平成３年環境庁告示第４６号の含有量試験においてスラグからのＰｂの溶出量が抑えられたことが示されている。また、非特許文献２においては、５００℃〜９００℃程度の温度でスラグを加熱することで、平成１５年環境省告示第１９号の溶出量試験においてスラグからＡｓおよびＰｂの溶出量が抑えられたことが示されている。 In Non-Patent Documents 1 and 2, slag heated in the atmosphere contains the elution amount test stipulated in 1991 Environment Agency Notification No. 46 and the 2003 Ministry of the Environment Notification No. 19 A technique for performing a quantity test is disclosed. In Non-Patent Document 1, it is shown that the amount of Pb elution from slag was suppressed in the content test of Environment Agency Notification No. 46 in 1991 by heat-treating slag at a temperature of 600 ° C. or higher. ing. Further, in Non-Patent Document 2, by heating slag at a temperature of about 500 ° C. to 900 ° C., the elution amount of As and Pb from the slag can be suppressed in the elution amount test of Ministry of the Environment Notification No. 19 in 2003. It has been shown.
ところで、特許文献１の技術では、平成３年環境庁告示第４６号に規定される溶出量試験においてはＡｓの溶出量を抑えることができたが、Ｐｂについては溶出量を抑えることが難しいことがあることがわかった。 By the way, in the technique of Patent Document 1, the elution amount of As was able to be suppressed in the elution amount test prescribed in the Environment Agency Notification No. 46 of 1991, but it is difficult to suppress the elution amount of Pb. I found out that
また、非特許文献１、２の技術では、追試をしても再現性が低く、特に平成３年環境庁告示第４６号の溶出量試験において、ＰｂとＡｓとの溶出量が上昇することがあることが、本発明者等により確認された。 In addition, in the techniques of Non-Patent Documents 1 and 2, reproducibility is low even if a supplementary test is performed, and in particular, in the dissolution test of Environment Agency Notification No. 46 in 1991, the dissolution amount of Pb and As may increase. It has been confirmed by the present inventors.
そこで、本発明は、非鉄製錬スラグまたは廃棄物溶融スラグから、平成３年環境庁告示第４６号（溶出量試験）で、ＰｂおよびＡｓの両方の溶出量を抑えたスラグを提供することを目的としている。 Therefore, the present invention provides a slag that suppresses the elution amount of both Pb and As from non-ferrous smelting slag or waste molten slag in 1991 Environment Agency Notification No. 46 (elution test). It is aimed.
本発明者らが鋭意検討した結果、一般的なスラグの表面に成長する鉄酸化物の枝状結晶を抑制し、その表面の平均突起高さが２μｍ未満に制御されているスラグは鉛とヒ素の溶出性が抑制されることを見出した。 As a result of intensive studies by the present inventors, iron oxide branch crystals growing on the surface of a general slag are suppressed, and the slag whose average protrusion height on the surface is controlled to be less than 2 μm is composed of lead and arsenic. It was found that the elution property of was suppressed.
また、本発明者らは、前項のスラグ表面の鉄酸化物はマグネタイトであり、鉄酸化物が枝状成長しないことからスラグ表面を緻密に被覆することになり、その為、スラグ内部の元素成分の溶出が抑制されることを見出した。 In addition, the present inventors, the iron oxide on the surface of the slag in the previous paragraph is magnetite, the iron oxide does not grow in a branch shape, so that the surface of the slag will be densely coated, so that the element component in the slag It has been found that elution of is suppressed.
本発明者らは、さらに前項に記載されるスラグは一般的な水砕スラグを、酸素分圧を１０-8以上、０．２未満に設定し、５００〜９００℃で熱処理することにより得ることができること、および炉内雰囲気は不活性ガスとして窒素もしくは二酸化炭素を含んでいれば表面にマグネタイト層を形成しやすいことを見出した。 The present inventors further obtain the slag described in the preceding paragraph by subjecting a general granulated slag to a heat treatment at 500 to 900 ° C. with an oxygen partial pressure set to 10 −8 or more and less than 0.2. It has been found that if the atmosphere in the furnace contains nitrogen or carbon dioxide as an inert gas, it is easy to form a magnetite layer on the surface.
すなわち本発明は以下の発明を含有する。
（１）非鉄製錬スラグを加熱することにより生じさせた鉄酸化物を表面に有し、その鉄酸化物凸部の平均高さが２μｍ未満であることを特徴とするスラグ。
（２）前記非鉄製錬スラグ表面に成長した鉄酸化物はマグネタイトであることを特徴とする、（１）記載のスラグ。
（３）非鉄製錬スラグを温度５００〜９００℃および酸素分圧１０-8以上、０．１５以下の雰囲気下にて加熱処理すること、を特徴とするスラグの製造方法。
（４）前記非鉄製錬スラグを加熱する温度が７００℃を超える場合は雰囲気の酸素分圧を０．０５未満とすること、を特徴とする（３）記載のスラグの製造方法。
That is, the present invention includes the following inventions.
(1) A slag characterized by having iron oxide produced by heating non-ferrous smelting slag on the surface, and the average height of the iron oxide protrusions being less than 2 μm.
(2) The slag according to (1), wherein the iron oxide grown on the surface of the non-ferrous smelting slag is magnetite.
(3) A method for producing slag, characterized by heat-treating non-ferrous smelted slag in an atmosphere having a temperature of 500 to 900 ° C. and an oxygen partial pressure of 10 −8 or more and 0.15 or less.
(4) The method for producing slag according to (3), wherein when the temperature at which the non-ferrous smelting slag is heated exceeds 700 ° C., the oxygen partial pressure of the atmosphere is less than 0.05.
本発明によれば、非鉄製錬スラグまたは廃棄物溶融スラグから、平成３年環境庁告示第４６号（溶出量試験）で、ＰｂおよびＡｓの両方の溶出量を抑えたスラグを提供することを目的としている。 According to the present invention, from non-ferrous smelting slag or waste molten slag, it is possible to provide a slag that suppresses both the Pb and As elution amounts in 1991 Environment Agency Notification No. 46 (elution amount test). It is aimed.
以下、本発明の実施形態について説明する。
本発明は、非鉄製錬スラグを加熱することにより生じさせた鉄酸化物を表面に有し、その鉄酸化物凸部の平均高さが２μｍ未満であることを特徴とするスラグである。
Hereinafter, embodiments of the present invention will be described.
This invention has the iron oxide produced by heating nonferrous smelting slag on the surface, The average height of the iron oxide convex part is less than 2 micrometers, It is a slag characterized by the above-mentioned.
本発明のスラグは後述するように一定の条件下で加熱することで得られるものであるが、その加熱対象となるスラグは、非鉄金属の製錬時に排出されるスラグであってもよいし、また廃棄物を焼却処理する際に排出されるスラグであってもよく、いずれであっても本形状、すなわち加熱により表面に生じた鉄酸化物についての性状を満たせば鉛とヒ素の溶出を抑制することができる。 The slag of the present invention is obtained by heating under certain conditions as described later, but the slag to be heated may be slag discharged during non-ferrous metal smelting, In addition, it may be slag discharged when incinerating waste, and in any case, the elution of lead and arsenic will be suppressed if the shape of the iron oxide formed on the surface by heating is satisfied. can do.
このようなスラグは通常熔体として排出されるが、大量の水と接触、冷却することにより水砕しておいてもよいし、徐冷して得られるスラグを用いてもよい。このスラグが環境庁告示第４６号試験による基準を満たせば、後述するように建築資材等の資源となる。一方で、これらの試験による基準を満たさない場合は有害物として取り扱われることになる。 Such slag is usually discharged as a melt, but may be crushed by contact with a large amount of water and cooled, or slag obtained by slow cooling may be used. If this slag meets the criteria of the Environment Agency Notification No. 46 test, it becomes a resource for building materials and the like as will be described later. On the other hand, if the criteria from these tests are not met, it will be treated as a hazardous substance.
水砕の方法としては、スラグに加圧水を噴射させて、粒状化する方法、スラグを水槽に注入して急冷させて、粒状化する方法などが挙げられる。通常スラグは、非鉄製錬などから得られるものであり、水砕することにより、冷却を兼ねることができ、大気中で徐冷するのに比べると、冷却に要する時間を短くすることができるとともに、急冷させることによりスラグ組成が均一になりやすい。さらに、販売、運搬しやすい粒度にするためには、冷却後のスラリーを凝固させるための鋳型や、適切な破砕装置が必要になる。そこで、例えば炉から取り出したスラグを使用する場合、スラグを水砕することにより、スラグを短時間で製品用途に対して適切で、かつ、運搬しやすい粒度に調整しやすくなる。 Examples of the granulation method include a method in which pressurized water is injected into slag and granulated, and a method in which slag is poured into a water tank and rapidly cooled to granulate. Normally slag is obtained from non-ferrous smelting, etc., and can be used for cooling by water granulation, and it can shorten the time required for cooling compared to slow cooling in the atmosphere. The slag composition tends to be uniform by rapid cooling. Furthermore, in order to make the particle size easy to sell and transport, a mold for solidifying the cooled slurry and an appropriate crushing device are required. Therefore, for example, when using slag taken out from a furnace, it is easy to adjust the slag to a particle size that is suitable for product use and easy to transport in a short time by granulating the slag.
スラグの水砕を行う、行わないに関係なく、廃棄に際してＰｂ、Ａｓの溶出の問題を解消する必要がある。その方法の一つが、必要に応じて水砕しておいたスラグを再度溶解しない程度に加熱処理して表面性状を変化させることで溶出基準内に抑えることである。 Regardless of whether or not slag is granulated, it is necessary to solve the problem of elution of Pb and As upon disposal. One of the methods is to suppress the slag, which has been crushed as necessary, to within the elution standard by changing the surface properties by heat treatment so as not to dissolve again.
加熱により表面性状を変化させることで鉛、ヒ素の溶出基準を満たす理由としては、以下の推察によるものであると考えられる。ただし、本発明は、以下の推察により制限されるものでない。
まず、環境庁告示試験で対象となっている有害成分の溶出は表面積に依存することは容易に推察される。一般に表面積の増加は、含有成分が液体中で固液界面に接触して溶解する効率を上昇させる。しかしながら鉛が単体の場合、溶出はほとんどしない。これは、酸化物であったとしても不動態化している、もしくは溶液中の炭酸イオンや硫酸イオンと不溶性塩を作ると考えられるからである。
The reason for satisfying the elution standard of lead and arsenic by changing the surface properties by heating is thought to be due to the following inference. However, the present invention is not limited by the following inference.
First, it is easily guessed that the leaching of harmful components that are the subject of the Environmental Agency Notification Test depends on the surface area. In general, an increase in surface area increases the efficiency with which a component is dissolved in contact with a solid-liquid interface in a liquid. However, when lead is a simple substance, there is almost no elution. This is because even if it is an oxide, it is considered to be passivated or to form an insoluble salt with carbonate ion or sulfate ion in the solution.
この現象を理解するには熱処理後のスラグから溶解する時の鉛の形態を知ることが必要である。本発明者らは鋭意検討した結果、鉛はイオンとして溶出するわけではなく直径０．１μｍ〜０．４５μｍ微細粒子として水溶液中に分散−懸濁することを解明した。 In order to understand this phenomenon, it is necessary to know the form of lead when dissolved from the slag after heat treatment. As a result of intensive studies, the present inventors have clarified that lead is not eluted as ions but dispersed and suspended in an aqueous solution as fine particles having a diameter of 0.1 μm to 0.45 μm.
さらにこの微粒子は、熱処理により表面に成長した枝状の酸化鉄結晶が振とうにより破砕されて生成することが分かった。したがってこの結晶が過度に成長すると、酸化鉄結晶が破砕されやすくなり、前述のように破砕されて液中に放出される微粒子濃度が上昇することになる。表面に成長する枝状結晶には、スラグ本体に比べてより多くの鉛が含まれており、その枝状結晶から放出される微粒子濃度が上昇することは、環境庁告示試験で定義される鉛溶出量の上昇を意味する。しかし枝状結晶長が表面から２μｍ未満であれば、容易に粉砕されず前述の鉛溶出量に影響を及ぼさないことが本発明者らにより見出されている。 Furthermore, it was found that the fine particles were formed by crushing the branch-like iron oxide crystals grown on the surface by heat treatment. Therefore, when this crystal grows excessively, the iron oxide crystal is easily crushed, and the concentration of fine particles that are crushed and released into the liquid as described above increases. The branch crystals growing on the surface contain more lead than the slag body, and the concentration of fine particles released from the branch crystals increases. This is the lead defined by the Environmental Agency Notification Test. This means an increase in the amount of elution. However, it has been found by the present inventors that if the branch crystal length is less than 2 μm from the surface, it is not easily pulverized and does not affect the aforementioned lead elution amount.
また、ヒ素の溶出に関してはその形態はヒ酸イオンもしくは亜ヒ酸イオンとして溶出すると考えられる。したがって、上述のように表面積を抑制すればヒ素酸物と液体中での固液界面との接触が減り溶出は改善されると考えられる。 Moreover, regarding the elution of arsenic, the form is considered to elute as arsenate ions or arsenite ions. Therefore, if the surface area is suppressed as described above, it is considered that the contact between the arsenic acid salt and the solid-liquid interface in the liquid is reduced and the elution is improved.
スラグの熱処理により表面に枝状の酸化鉄結晶が成長すると表面積の増加を引き起こす。そのため表面の枝状結晶の成長を抑える必要があり、ヒ素の溶出に関しても鉛の場合と同様に高さ２μｍ未満の成長であれば溶出試験基準を満たすことがわかった。 When branch-like iron oxide crystals grow on the surface by heat treatment of slag, the surface area is increased. Therefore, it is necessary to suppress the growth of branch crystals on the surface, and it was found that elution of arsenic satisfies the elution test standard if the growth is less than 2 μm in height as in the case of lead.
上記性状を持つスラグを作成するには、非鉄製錬スラグを熱処理する際に酸素分圧１０-8以上０．２未満で５００℃〜９００℃に加熱する。本熱処理においては表面の枝状酸化鉄結晶の成長が抑制されるとともにスラグ表層が安定な鉄酸化物、例えばマグネタイトで被覆される。なお、表面はマグネタイトでなくとも安定な鉄酸化物で被覆されていれば良い。 In order to produce a slag having the above properties, when heat-treating the nonferrous smelted slag, it is heated to 500 ° C. to 900 ° C. at an oxygen partial pressure of 10 −8 or more and less than 0.2. In this heat treatment, the growth of branched iron oxide crystals on the surface is suppressed, and the slag surface layer is coated with a stable iron oxide such as magnetite. In addition, the surface should just be coat | covered with the stable iron oxide even if it is not magnetite.
また、加熱処理の条件である、温度および酸素分圧は表面性状制御に関しては独立ではなく、例えば温度が高いほど酸素分圧を下げる必要が生じる。枝状結晶の高さを２μｍ未満に制御するには、例えば６００℃以下では酸素分圧は０．１５未満であれば良いが８００℃では０．０５未満、好ましくは０．０２未満の条件が必要となる。ただし温度が低いと処理に要する時間を長くする必要がある。このように、各種操業条件の持つ制約により最適な条件が選択される。 Further, the temperature and oxygen partial pressure, which are the conditions for the heat treatment, are not independent in terms of surface property control. For example, the higher the temperature, the lower the oxygen partial pressure needs to be. In order to control the height of the branch crystals to less than 2 μm, for example, the oxygen partial pressure may be less than 0.15 at 600 ° C. or less, but the condition is less than 0.05, preferably less than 0.02 at 800 ° C. Necessary. However, when the temperature is low, it is necessary to lengthen the time required for the treatment. In this way, the optimum conditions are selected due to the constraints of various operating conditions.
以下、上記実施形態に係るスラグ処理とその形態ならびに溶出性の評価結果を示す。スラグは溶出試験に不合格のスラグと同じロットのスラグを使用した。スラグの組成分析では最初に王水溶解物と未溶解残渣に分離した。未溶解残渣はさらにフッ酸処理によりその減量からケイ酸分を定量した。フッ酸処理残渣を過酸化ナトリウムを溶剤として炭酸ナトリウムとともに融解した後に、適当な酸で希釈後にＩＣＰ−ＯＥＳで決定した。鉛の分析ではＩＣＰ−ＭＳによりその濃度を決定した。各実験例で得られたスラグの表面を白金でコーティングしたのち、ＳＥＭ画像を取得して確認した。枝状結晶高さはスラグを樹脂に埋め込んで固化した後に切り出し、研磨してその断面のＳＥＭ画像から無作為に１０点を抽出してその地点の高さを物差しで測定して換算することで求めた。全ての点の平均を用いた。
スラグの溶出性は公定法に従って行った。ヒ素と鉛の濃度は適当に硝酸で希釈した後にＩＣＰ−ＯＥＳにより決定した。
Hereinafter, the slag processing according to the above-described embodiment, its form, and the evaluation results of the dissolution property are shown. The slag was the same lot as the slag that failed the dissolution test. In the composition analysis of slag, it was first separated into aqua regia dissolved product and undissolved residue. The undissolved residue was further quantified for silicic acid content from the weight loss by hydrofluoric acid treatment. The hydrofluoric acid treatment residue was melted with sodium carbonate using sodium peroxide as a solvent, and then diluted with an appropriate acid, and then determined by ICP-OES. In the analysis of lead, the concentration was determined by ICP-MS. After coating the surface of the slag obtained in each experimental example with platinum, SEM images were acquired and confirmed. The height of the branch crystal is obtained by embedding slag in the resin and solidifying it, cutting it out, polishing it, extracting 10 points randomly from the SEM image of the cross section, measuring the height of that point with a ruler, and converting it. Asked. The average of all points was used.
Slag dissolution was performed according to the official method. Arsenic and lead concentrations were determined by ICP-OES after appropriate dilution with nitric acid.
（実験例１）
銅製錬自熔炉から採取した水砕スラグ（熱処理前の溶出試験結果は表１に示す）を酸素分圧１０-8〜０．２において６００℃で６時間熱処理した。酸素分圧０．２１のときは空気雰囲気とした。０．１と０．０５の時は窒素ガスと酸素ガスを混合して調整した。酸素分圧１０-8のときは二酸化炭素ガスを用いた。同様に８００℃においても同じ試験を行った。各分圧における枝状結晶の高さ平均を図１と図２に示す。
(Experimental example 1)
Granulated slag collected from a copper smelting flash furnace (the dissolution test results before heat treatment are shown in Table 1) was heat-treated at 600 ° C. for 6 hours at an oxygen partial pressure of 10 −8 to 0.2. An air atmosphere was used when the oxygen partial pressure was 0.21. In the case of 0.1 and 0.05, adjustment was made by mixing nitrogen gas and oxygen gas. Carbon dioxide gas was used when the oxygen partial pressure was 10 −8 . Similarly, the same test was conducted at 800 ° C. The average height of the branch crystals at each partial pressure is shown in FIGS.
（実験例２）
実験例１で得たスラグに対して平成３年環境庁告示第４６号（溶出量試験）に供し、その有害物の溶出性を評価した。結果を表２と表３に示す。
(Experimental example 2)
The slag obtained in Experimental Example 1 was subjected to Environmental Agency Notification No. 46 (dissolution test) in 1991, and the dissolution of harmful substances was evaluated. The results are shown in Tables 2 and 3.
表２と表３の結果から枝状結晶高さが２μｍ未満であればヒ素ならびに鉛の溶出は大きく抑えられることが分かる。また図１と図２の結果からスラグの加熱温度は５００℃〜９００℃であれば酸素分圧を調整すれば溶出を抑えたスラグになることが示唆される。表２、３によれば６００℃、８００℃の結果のみであるが、非鉄製錬スラグの軟化点を考慮すると、特に７００℃以上に加熱する場合は、酸素分圧の調節が非常に重要になり、酸素分圧は例えば０．０５未満に調整する必要がある。 From the results of Tables 2 and 3, it can be seen that the elution of arsenic and lead can be greatly suppressed if the branch crystal height is less than 2 μm. Moreover, from the results of FIGS. 1 and 2, it is suggested that if the heating temperature of the slag is 500 ° C. to 900 ° C., the elution is suppressed by adjusting the oxygen partial pressure. According to Tables 2 and 3, only the results at 600 ° C. and 800 ° C. are taken into consideration, but considering the softening point of non-ferrous smelting slag, especially when heating to 700 ° C. or higher, the adjustment of oxygen partial pressure is very important. Therefore, the oxygen partial pressure needs to be adjusted to less than 0.05, for example.
酸素分圧０．２１、温度８００℃での加熱処理スラグの表面のＳＥＭ像を図３に示し、酸素分圧１０-8、温度８００℃での加熱処理スラグの表面のＳＥＭ像を図４に示す。酸素分圧０．２１の場合は多くの枝状結晶が確認でき、比表面積が大きいことがわかる。その為ヒ素の溶出量が高いものと考えられる。鉛の溶出量については熱処理により表面が鉄酸化物でおおわれると目立って溶出量は低下する。 The SEM image of the surface of the heat-treated slag at an oxygen partial pressure of 0.21 and a temperature of 800 ° C. is shown in FIG. 3, and the SEM image of the surface of the heat-treated slag at an oxygen partial pressure of 10 −8 and a temperature of 800 ° C. is shown in FIG. Show. When the oxygen partial pressure is 0.21, many branch crystals can be confirmed, and it can be seen that the specific surface area is large. Therefore, the arsenic elution amount is considered to be high. Regarding the amount of lead elution, the amount of lead is noticeably reduced when the surface is covered with iron oxide by heat treatment.
以上、本発明の実施例について詳述したが、本発明は係る特定の実施例に限定されるものではなく、特許請求の範囲に記載された本発明の要旨の範囲内において、種々の変形・変更が可能である。 Although the embodiments of the present invention have been described in detail above, the present invention is not limited to such specific embodiments, and various modifications and changes can be made within the scope of the gist of the present invention described in the claims. It can be changed.
Claims (4)
The method for producing slag according to claim 3, wherein when the temperature at which the non-ferrous smelting slag is heated exceeds 700 ° C, the oxygen partial pressure of the atmosphere is set to less than 0.05.
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