JPH0429730B2 - - Google Patents
Info
- Publication number
- JPH0429730B2 JPH0429730B2 JP13938084A JP13938084A JPH0429730B2 JP H0429730 B2 JPH0429730 B2 JP H0429730B2 JP 13938084 A JP13938084 A JP 13938084A JP 13938084 A JP13938084 A JP 13938084A JP H0429730 B2 JPH0429730 B2 JP H0429730B2
- Authority
- JP
- Japan
- Prior art keywords
- slag
- chromium
- carbon
- furnace
- weight
- 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.)
- Expired
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- 239000002893 slag Substances 0.000 claims description 71
- 239000011651 chromium Substances 0.000 claims description 45
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 42
- 229910052804 chromium Inorganic materials 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 22
- 229910000604 Ferrochrome Inorganic materials 0.000 claims description 21
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 20
- 239000000571 coke Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 239000000292 calcium oxide Substances 0.000 claims description 10
- 235000012255 calcium oxide Nutrition 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 239000012768 molten material Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical group [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、クロム鉱滓を還元溶融させ、溶融物
を、フエロクロム金属と、６価クロムを含有しな
いか又は６価クロムを溶出しないスラグに分けて
回収する方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention involves reducing and melting chromium slag and separating the melt into ferrochrome metal and slag that does not contain hexavalent chromium or does not elute hexavalent chromium. Regarding the method of collection.
従来、クロム鉱滓を還元溶融して、フエロクロ
ムの有価属を回収すると共に無害化スラグを得る
に、クロム鉱滓の融点が極めて高い（1650℃以
上）ために電気炉を利用していた（例えば特開昭
58−1053号公報、特開昭58−1054号公報、特開昭
58−11761号公報、特開昭58−25455号公報）。
Conventionally, electric furnaces have been used to reduce and melt chromium slag to recover the valuable metals of ferrochrome and to obtain harmless slag because the melting point of chromium slag is extremely high (1650℃ or higher) (for example, Akira
Publication No. 58-1053, Japanese Patent Publication No. 58-1054, Japanese Patent Publication No. 1983
58-11761, JP-A-58-25455).
しかし、クロム鉱滓は副産物であるためにクロ
ムや鉄等の有価金属成分の含有率が低く、フエロ
クロム金属を製造するに熱エネルギーの消費が膨
大となり、高価な電力を利用することは経済面か
ら実用化しにくい欠点があつた。
However, since chromium slag is a by-product, it has a low content of valuable metal components such as chromium and iron, and producing ferrochrome metal consumes a huge amount of thermal energy, making it economically impractical to use expensive electricity. There were some drawbacks that were difficult to overcome.
本発明の目的は、クロム鉱滓から有価物である
フエロクロム金属を回収すると共に、廃棄物を無
害化されたスラグにするに、経済的に実用化可能
な低コストで処理できるようにする点にある。 An object of the present invention is to recover ferrochrome metal, which is a valuable material, from chromium slag, and to process the waste into harmless slag at an economically practicable low cost. .
本発明の特徴手段は、炭素可燃物質の燃焼によ
り高温炉床を竪形炉内に形成すると共に、その高
温炉床を、炭素系可燃物質を燃焼させる酸素量を
制御することにより、又は、他より還元性ガスを
導入することにより還元雰囲気に維持し、スラグ
形成剤は少くともシリカ及びカルシヤ源を含み、
クロム鉱滓とスラグ形成剤中のシリカ（SiO2）
とカルシヤ（CaO）を、夫々15％（重量）以上の
割合で、前記高温炉床に供給して溶融させ、得ら
れた溶融物を前記高温炉床の下部から炉外に取出
すことにある。
The characteristic means of the present invention is to form a high-temperature hearth in a vertical furnace by burning a carbon-based combustible material, and to form the high-temperature hearth by controlling the amount of oxygen for burning the carbon-based combustible material; A reducing atmosphere is maintained by introducing a more reducing gas, the slag forming agent contains at least a silica and calcia source,
Silica (SiO 2 ) in chromium slag and slag formers
and calcia (CaO), each at a ratio of 15% (weight) or more, are supplied to the high-temperature hearth and melted, and the obtained molten material is taken out of the furnace from the lower part of the high-temperature hearth.
本発明において、クロム鉱滓というのは、クロ
ム鉱石よりクロム酸塩を製造する際に副生する残
滓をいうが、主としてクロム酸アルカリを製造す
る際に副生する残渣をいう。 In the present invention, chromium slag refers to the residue produced as a by-product when producing chromate from chromium ore, but mainly refers to the residue produced as a by-product during the production of alkali chromate.
また、他の残滓としてクロムメツキ工程からの
メツキ廃液の処理物であつてもよい。 Further, other residue may be a treated plating waste liquid from the chrome plating process.
クロム鉱滓はその性質上組成は大幅に異なるけ
れも、通常、クロムおよび鉄分はCr2O3＋Fe2O3
として10〜58重量％の範囲で含有しており、その
うち、数千ppmの六価クロムを含有する。 Although the composition of chromium slag varies greatly due to its nature, the chromium and iron content is usually Cr 2 O 3 + Fe 2 O 3
The content ranges from 10 to 58% by weight, including several thousand ppm of hexavalent chromium.
本発明におけるフエロクロム源としてのクロム
鉱滓は、直接それ自体使用できることは勿論であ
るが、必要に応じて該鉱滓の中和処理あるいは六
価クロムの還元処理を施したものであつてもよ
い。 It goes without saying that the chromium slag as a ferrochrome source in the present invention can be used directly as such, but if necessary, the chromium slag may be subjected to a neutralization treatment or a hexavalent chromium reduction treatment.
また、クロム鉱滓というのは、上記の意味での
鉱滓は勿論、必要に応じてクロム鉱石、あるい
は、製鉄又は非鉄金属工場から副生する鉄−クロ
ム系残滓も含んだ場合であつてもよい。 Further, the chromium slag is not only slag in the above sense, but may also include chromium ore or iron-chromium residue produced as a by-product from a steel manufacturing or non-ferrous metal factory, if necessary.
次に、スラグ形成剤というのは、上記鉱滓より
フエロクロムを回収する場合に他の成分を無害化
したスラグとして回収するための添加剤であり、
これはシリカ源およびカルシウム源をいう。 Next, the slag forming agent is an additive for recovering ferrochrome from the slag as slag with other components rendered harmless.
This refers to a source of silica and a source of calcium.
シリカ源としては、珪石、珪砂、珪華、酸性白
土、石炭灰、その他適当なものを単独で又は組合
せて利用でき、、また、カルシウム源としては、
石灰石、生石灰、消石灰、珪酸カルシウム系の精
錬スラグ、その他適当なものを単独で又は組合わ
せて利用できる。 As a silica source, silica stone, silica sand, silica, acid clay, coal ash, and other suitable materials can be used alone or in combination, and as a calcium source,
Limestone, quicklime, slaked lime, calcium silicate-based refined slag, and other suitable materials can be used alone or in combination.
炭素系可燃物質としては、コークスが望ましい
が、例えば無煙炭等の練炭、黒鉛電極屑、その他
各種のものを単独又は混合使用できる。 As the carbon-based combustible material, coke is desirable, but for example, briquettes such as anthracite, graphite electrode scraps, and various other materials can be used alone or in combination.
クロム鉱滓、スラグ形成剤及び炭素系可燃物質
からなる原料混合物はクロム鉱滓の物性によつて
一様ではないが、クロム鉱滓とスラグ形成剤中の
SiO2及びCaO濃度は夫々15％（重量）以上にす
ることが必要である。この理由は、六価クロムの
還元を完全にすると共に、スルグ中にわずかに残
留するクロム成分の再酸化が起らないように、実
質的に無害のスラグを回収するという観点から求
められた理由と炉操業の観点から低融点で分離し
易いスラグを得るために設定されるものである。 The raw material mixture consisting of chromium slag, slag forming agent, and carbon-based combustible material varies depending on the physical properties of chromium slag, but the
It is necessary that the SiO 2 and CaO concentrations are each 15% (by weight) or more. The reason for this was to complete the reduction of hexavalent chromium and to recover essentially harmless slag to prevent re-oxidation of the chromium components remaining in the slag. From the viewpoint of furnace operation, this is designed to obtain a slag with a low melting point and easy separation.
本発明において、後述の竪形炉へ供給する原料
混合物の投入形態は、諸原料、主としてクロム鉱
滓の物理化学的特性によつて、幾つかの態様があ
る。 In the present invention, there are several modes of charging the raw material mixture to the vertical furnace described below, depending on the physicochemical characteristics of the various raw materials, mainly the chromium slag.
例えば、クロム鉱滓、シリカ源およびカルシウ
ム源を予め混合造粒してペレツト化したものと、
炭素系可燃物質とからなる場合、上記において、
該ペレツト化に際し例えば微細コークスを添加配
合したものである場合、又は、特にペレツト化す
ることなく、原料形態に応じて混合又は別個に投
入する場合などがある。 For example, chromium slag, a silica source and a calcium source are mixed and granulated into pellets,
When consisting of carbon-based combustible substances, in the above,
When pelletizing, for example, fine coke may be added to the coke, or the coke may not be pelletized, but may be mixed or added separately depending on the form of the raw materials.
なお、操作上の問題および、炉内の速やかな還
元反応を生起するためには、予めペレツト化した
ものが好ましく、また、炭素系可燃物質の炉内投
入に際しては、他の原料と一緒に又は別々に行つ
てもよく、その投入方式は問わない。 In addition, in order to avoid operational problems and to cause a rapid reduction reaction in the furnace, it is preferable to pelletize the carbon-based combustible material in advance, and when introducing the carbon-based combustible material into the furnace, it should not be mixed with other raw materials or They may be done separately, and the method of inputting them does not matter.
ペレツトは、例えば、パルプ廃液、CM6、タ
ール等の歴青物質、ペントナイト、セメントなど
の結合剤にて通常は最低10mm以上の大きさの造粒
物とするのがよい。 The pellets are preferably made into granules with a size of at least 10 mm using, for example, pulp waste liquid, CM6, a bituminous substance such as tar, and a binder such as pentonite or cement.
かかる原料混合物を竪形炉へ投入すると炉内に
おいて還元溶融が生じ、フエロクロムの金属成分
と無害化されたスラグ成分とになり、それぞれ比
重差によつて分離回収されるが、その作用効果は
次の如くである。 When such a raw material mixture is put into a vertical furnace, reductive melting occurs in the furnace, and it becomes the metal component of ferrochrome and the harmless slag component, which are separated and recovered based on the difference in specific gravity, but the effects are as follows. It's like this.
本発明は実験の結果、竪形炉を用い、スラグ形
成剤としてのシリカ源及びカルシウム源の両方を
上述のように適当量添加すると、コークス等の炭
素系可燃物質による高温炉床によつても得られる
1200℃以上程度の温において、炭素系可燃物質の
還元作用によりクロムを金属溶融物にでき、また
鉄分も金属溶融物にでき、クロムと鉄の合金であ
るフエロクロム金属が生成されるところにその特
徴があり、平炉では、クロム鉱滓に該反応を効率
的に行なわせることは難しい。竪形炉として、例
えばキユポラ炉が一般的であるが、これに限定さ
れるものでない。
As a result of experiments, the present invention has found that when a vertical furnace is used and appropriate amounts of both a silica source and a calcium source as slag forming agents are added as described above, even a high-temperature hearth made of carbon-based combustible materials such as coke can be used. can get
At temperatures above 1200℃, chromium can be made into a metal melt by the reduction action of carbon-based combustible substances, and iron can also be made into a metal melt, producing ferrochrome metal, which is an alloy of chromium and iron. Therefore, in an open hearth furnace, it is difficult to make the chromium slag perform this reaction efficiently. A typical vertical furnace is, for example, a cupola furnace, but is not limited thereto.
かくして、炉内に投入された、投入物は高温炉
床において速やかにかつ円滑に還元溶融され、比
重選別等により、重いフエロクロム金属と軽い溶
融スラグを分離回収でき、溶融スラグを固化させ
ると、カドミウム、鉛、六価クロム、ヒ素、全水
銀等の有害成分を溶出しないように封じ込めた、
ガラス質の固化物が得られる。 In this way, the materials put into the furnace are quickly and smoothly reduced and melted in the high-temperature hearth, and heavy ferrochrome metal and light molten slag can be separated and recovered by gravity sorting, etc., and when the molten slag is solidified, cadmium , containment of harmful components such as lead, hexavalent chromium, arsenic, and total mercury to prevent them from leaching out.
A glassy solidified product is obtained.
副生スラグは、有害成分を溶出しないため、こ
れれを配管用埋戻し材、軟弱地盤改良用ドレーン
材、道路材等として利用できる無害の固化スラグ
として処理できるばかりでなく、ステンレス原料
等の金属材料として利用できるフエロクロム金属
を得られ、省資源で極めて有利にクロム鉱滓処理
を行えるようになつた。
Since the by-product slag does not elute harmful components, it can not only be processed as harmless solidified slag that can be used as backfill material for piping, drain material for improving soft ground, road material, etc., but also as a material for metals such as stainless steel raw materials. It has become possible to obtain ferrochrome metal that can be used as a material, and it has become possible to process chromium slag very advantageously and with less resources.
その上、炭素系可燃物質を熱エネルギー源にす
るから、例えば電気炉等に比してランニングコス
トを大巾に節減できると共に、有価物回収により
経費回収を図れるから、全体として、処理コスト
を実用化に十分な程度に低くできるようになつ
た。 Furthermore, since carbon-based combustible materials are used as a thermal energy source, running costs can be significantly reduced compared to, for example, electric furnaces, and costs can be recovered by recovering valuables, so overall processing costs can be reduced to practical use. It is now possible to reduce the temperature to a level low enough to
次に、図面により実施例を示す。 Next, examples will be shown with reference to drawings.
コークス、クロム鉱滓、シリカ源及びカルシウ
ム源を、造粒し又はそのまゝ交互にあるいは同時
に二重ダンパー１ａ，１ｂの開閉により、ホツパ
ー２から竪形炉３内に供給し、炉３下部に充填さ
れたコークス層を一次羽口から供給される空気に
より燃焼させて、高温炉床５を形成する。 Coke, chromium slag, silica source, and calcium source are granulated or fed into the vertical furnace 3 from the hopper 2 by alternately or simultaneously opening and closing the double dampers 1a and 1b, and are filled into the lower part of the furnace 3. The resulting coke layer is combusted by air supplied from the primary tuyere to form a high-temperature hearth 5.
クロム鉱滓、及び、スラグ形成剤としてのシリ
カ源とカルシウム源を投入するに、これらの中の
SiO2およびCaOを夫々15％（重量）以上、望ま
しくは夫々35％（重量）以下になるように、供給
量を調整する。 Among them, chromium slag and silica source and calcium source as slag forming agents are added.
The supply amounts are adjusted so that SiO 2 and CaO are each 15% (by weight) or more, preferably 35% (by weight) or less each.
そして、一次羽口４ａから供給される空気供給
量の制御によつて又は他より還元性ガスを導入す
ることによつて高温炉床５の上部を還元雰囲気で
1200℃以上に維持し、その高温炉床５上部におい
て、クロム鉱滓を加熱溶融させると共に、クロム
及び鉄分を還元溶融して金属溶融物に変え、フエ
ロクロム金属を生成させる。 The upper part of the high-temperature hearth 5 is kept in a reducing atmosphere by controlling the amount of air supplied from the primary tuyere 4a or by introducing reducing gas from elsewhere.
The temperature is maintained at 1200° C. or higher, and in the upper part of the high-temperature hearth 5, the chromium slag is heated and melted, and the chromium and iron are reductively melted and converted into a molten metal to produce ferrochrome metal.
また、溶融物を、高温炉床５の間隙を流下させ
て、比重選別により重いフエロクロム金属を炉底
に溜めると共に、軽い溶融スラグを出滓口６によ
り連続的に炉３外に取出す。 Further, the molten material is allowed to flow down through the gap in the high-temperature hearth 5, and heavy ferrochrome metal is collected at the bottom of the hearth by specific gravity sorting, while light molten slag is continuously taken out of the furnace 3 through the slag outlet 6.
さらに、取出した溶融スラグを徐冷あるいは急
冷により固化スラグにし、炉底にフエロクロム金
属が適当量溜まると、フエロクロム金属を出鉄口
７から回収する。 Furthermore, the molten slag taken out is made into solidified slag by slow cooling or rapid cooling, and when a suitable amount of ferrochrome metal accumulates at the bottom of the furnace, the ferrochrome metal is recovered from the iron outlet 7.
他方、高温炉床５から上昇する燃焼排ガスを、
二次及び三次羽口４ｂ，４ｃからの空気で完全燃
焼させた後、排ガス路８により、排ガス処理設備
９に送る。 On the other hand, the combustion exhaust gas rising from the high temperature hearth 5,
After complete combustion with the air from the secondary and tertiary tuyere 4b, 4c, it is sent to the exhaust gas treatment equipment 9 through the exhaust gas path 8.
次に、実験例を示す。 Next, an experimental example will be shown.
実験例 １
処理対象としたクロム鉱滓は、平均粒径が
175μmで、下記組成であつた。Experimental example 1 The chromium slag to be treated had an average particle size of
It was 175 μm and had the following composition.
Cr2O3 16.7wt％
（Cr+64800PPm）
Fe2O3 38.5 〃
Al2O3 13.0 〃
MgO 14.6 〃
SiO2 3.7 〃
CaO 7.6 〃
その他 5.9 〃
上記クロム鉱滓100重量部に対し、SiO250重量
部、CaCO391重量部（CaOとして51重量部）、粉
末コークス10〜20重量部を加えて、その混和物を
成型した後150℃で２時間乾燥し、成型原料を調
製した。Cr 2 O 3 16.7wt% (Cr +6 4800PPm) Fe 2 O 3 38.5 〃 Al 2 O 3 13.0 〃 MgO 14.6 〃 SiO 2 3.7 〃 CaO 7.6 〃 Others 5.9 〃 For 100 parts by weight of the above chromium slag, SiO 2 50 parts by weight, 91 parts by weight of CaCO 3 (51 parts by weight as CaO), and 10 to 20 parts by weight of powdered coke were added, and the mixture was molded and dried at 150° C. for 2 hours to prepare a molding raw material.
キユポラ炉に形成した赤熱コークスペツドに、
成型原料と塊状コークスを重量比２：１の割合で
順次投入し、クロム鉱滓を還元溶融して、下記組
成のフエロクロム金属及びスラグを得た。 In the red-hot coke space formed in the cupola furnace,
Molding raw materials and lump coke were sequentially introduced at a weight ratio of 2:1, and the chromium slag was reduced and melted to obtain ferrochrome metal and slag having the following compositions.
(イ) フエロクロム金属組成
Ｃ− 15.23wt％
Fe 74.2 〃
Si 3.73 〃
Ｓ 0.03 〃
Ｃ 4.38 〃
(ロ) スラグ組成
Sr2O3 8.16wt％
Fe2O3 7.50 〃
Al2O3 14.35 〃
MgO 9.74 〃
CaO 34.89 〃
SiO2 25.34 〃
尚、スラグから６価クロムは検出されなかつ
た。(a) Ferrochrome metal composition C- 15.23wt% Fe 74.2 〃 Si 3.73 〃 S 0.03 〃 C 4.38 〃 (b) Slag composition Sr 2 O 3 8.16wt% Fe 2 O 3 7.50 〃 Al 2 O 3 14.35 〃 MgO 9.74 〃 CaO 34.89 〃 SiO 2 25.34 〃 No hexavalent chromium was detected in the slag.
実験例 ２
実施例−１と同組成のクロム鉱滓100重量部に
対し、CaO25重量部、SiO225重量部、粉コーク
ス10〜20重量部を加え、さらにバイダーを加え
て、造粒原料を調製した。キユポラ炉に形成した
赤熱コークスベツドに、造粒原料と塊コークスを
重量比３：１の割合で順次投入し、かつ、コーク
スベツド上にCOガスを吹込み、クロム鉱滓を還
元溶融し、実験例−１と同様の組成を有するフエ
ロクロム金属及びスラグを得た。Experimental Example 2 To 100 parts by weight of chromium slag having the same composition as in Example-1, 25 parts by weight of CaO, 25 parts by weight of SiO 2 and 10 to 20 parts by weight of coke breeze were added, and a binder was further added to prepare a granulated raw material. did. The granulated raw material and lump coke were sequentially introduced into the red-hot coke bed formed in the cupora furnace at a weight ratio of 3:1, and CO gas was blown onto the coke bed to reduce and melt the chromium slag.Experiment Example-1 Ferrochrome metal and slag having the same composition were obtained.
尚、実験例−１及び２のいずれにおいても、フ
エロクロム金属及びスラグの炉外排出を円滑に行
えた。 In addition, in both Experimental Examples 1 and 2, the ferrochrome metal and slag could be smoothly discharged from the furnace.
比較例 １
実験例−１と同組成のクロム鉱滓100重量部に
対し、SiO240重量部、粉末コークス10〜20重量
部を加え、実験例−２と同様に造粒原料を調製
し、実験例−１と同様にクロム鉱滓を還元溶融し
たところ、組成が
Cr 21wt％
Fe 62 〃
Si 14wt％
Ｃ ３ 〃
のフエロクロム金属が得られたものの、スラグの
溶融が極めて困難で、連続処理が不能であつた。Comparative Example 1 40 parts by weight of SiO 2 and 10 to 20 parts by weight of powder coke were added to 100 parts by weight of chromium slag having the same composition as in Experimental Example-1, and a granulated raw material was prepared in the same manner as in Experimental Example-2. When chromium slag was reduced and melted in the same manner as in Example 1, ferrochrome metal with a composition of Cr 21wt% Fe 62 Si 14wt% C 3 was obtained, but it was extremely difficult to melt the slag and continuous processing was impossible. It was hot.
比較例 ２
実験例−１と同組成のクロム鉱滓100量部に対
し、CaO10重量部、SiO220重量部、粉末コーク
ス10〜20重量部を加え、実験例−２と同様に造粒
原料を調製し、実験例−１と同様にしてクロム鉱
滓を溶融しようとしたが、造粒原料は、全く溶融
せずに、単に黒色に変色して焼結しただけであつ
た。Comparative Example 2 10 parts by weight of CaO, 20 parts by weight of SiO 2 and 10 to 20 parts by weight of powder coke were added to 100 parts by weight of chromium slag having the same composition as in Experimental Example-1, and granulation raw materials were added in the same manner as in Experimental Example-2. An attempt was made to prepare and melt the chromium slag in the same manner as in Experimental Example 1, but the granulated raw material did not melt at all, but merely turned black and sintered.
図面は、本発明方法に利用する装置例のフロー
シートである。
３…竪形炉、５…高温炉床。
The drawing is a flow sheet of an example of an apparatus used in the method of the present invention. 3...Vertical furnace, 5...High temperature hearth.
Claims (1)
せ、溶融物をフエロクロム金属と６価クロムを含
有しないか又は６価クロムを溶出しないスラグに
分けて回収する方法であつて、炭素系可燃物質の
燃焼により高温炉床５を竪形炉３内に形成すると
共に、その高温炉床５を、炭素系可燃物質を燃焼
する酸素量を制御することにより、又は他より還
元性ガスを導入することにより還元雰囲気に維持
し、スラグ形成剤として少くともシリカ源及びカ
ルシヤ源を用い、クロム鉱滓とスラグ形成剤中の
シリカ（SiO2）及びカルシヤ（CaO）が夫々15
％重量以上の割合で、前記高温炉床５に供給して
溶融させ、溶融物を前記高温炉床５の下部から炉
外に取出すクロム鉱滓からフエロクロムを製造す
る方法。 ２ 前記クロム鉱滓として、クロム鉄鉱からクロ
ム酸塩を製造する際に生成する残滓を利用する特
許請求の範囲第１項に記載の方法。 ３ クロム鉱滓、スラグ形成剤、炭素系可燃物質
の一部のうち、１又は２以上を造粒物として用い
る特許請求の範囲第１項記載の方法。 ４ 前記炭素系可燃物質としてコークスを用いる
特許請求の範囲第１項、第２項又は第３項に記載
の方法。[Claims] 1. A method of reductively melting chromium slag together with a slag forming agent and separating and recovering the melt into ferrochrome metal and slag that does not contain hexavalent chromium or does not elute hexavalent chromium, the method comprising: A high-temperature hearth 5 is formed in the vertical furnace 3 by combustion of carbon-based combustible materials, and the high-temperature hearth 5 is formed by controlling the amount of oxygen used to burn carbon-based combustible materials, or by injecting reducing gas from other sources. At least a silica source and a calcia source are used as the slag forming agent, and silica (SiO 2 ) and calcia (CaO) in the chromium slag and the slag forming agent are each 15%
A method for producing ferrochrome from chromium slag, in which chromium slag is supplied to the high-temperature hearth 5 and melted at a ratio of 1.5% or more by weight, and the molten material is taken out of the furnace from the lower part of the high-temperature hearth 5. 2. The method according to claim 1, wherein the chromite slag is a residue generated during the production of chromate from chromite. 3. The method according to claim 1, wherein one or more of chromium slag, a slag forming agent, and a part of carbon-based combustible material are used as granules. 4. The method according to claim 1, 2, or 3, in which coke is used as the carbon-based combustible material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13938084A JPS6119757A (en) | 1984-07-04 | 1984-07-04 | Preparation of ferrochrome from chromium slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13938084A JPS6119757A (en) | 1984-07-04 | 1984-07-04 | Preparation of ferrochrome from chromium slag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6119757A JPS6119757A (en) | 1986-01-28 |
| JPH0429730B2 true JPH0429730B2 (en) | 1992-05-19 |
Family
ID=15243969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13938084A Granted JPS6119757A (en) | 1984-07-04 | 1984-07-04 | Preparation of ferrochrome from chromium slag |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6119757A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2578436B2 (en) * | 1987-08-27 | 1997-02-05 | 東京瓦斯株式会社 | Melting method of incinerated ash |
| CN112063860B (en) * | 2020-08-31 | 2022-08-05 | 中国科学院过程工程研究所 | A kind of method for extracting chromium from chromium-containing material |
-
1984
- 1984-07-04 JP JP13938084A patent/JPS6119757A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6119757A (en) | 1986-01-28 |
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