JP3828541B2 - Production method of crude copper - Google Patents
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- JP3828541B2 JP3828541B2 JP2003530006A JP2003530006A JP3828541B2 JP 3828541 B2 JP3828541 B2 JP 3828541B2 JP 2003530006 A JP2003530006 A JP 2003530006A JP 2003530006 A JP2003530006 A JP 2003530006A JP 3828541 B2 JP3828541 B2 JP 3828541B2
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/0047—Smelting or converting flash smelting or converting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0054—Slag, slime, speiss, or dross treating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Description
本発明は、懸濁融解炉などの融解反応炉において粗銅を、粗銅の硫化物精鉱および／または微細粉砕銅マットから直接製造する乾式冶金方法に関するものである。 The present invention relates to a dry metallurgy method in which crude copper is directly produced from a crude copper sulfide concentrate and / or finely pulverized copper mat in a melting reactor such as a suspension melting furnace.
公知の従来技術の方法は、未精製銅もしくは粗銅を硫化物精鉱からいくつかの段階によって製造し、それによると精鉱を懸濁融解炉などの懸濁反応炉で空気もしくは酸素富化空気によって融解し、これにより50〜75重量% の銅およびスラグを含有する銅濃厚含有マットができる。この種の方法は、例えば米国特許第2,506,557号に開示されている。懸濁融解炉で生成された銅マットは、例えばPierce-Smith型の転炉もしくは自溶転炉で粗銅に変換し、さらに陽極炉で精製する。 Known prior art methods produce unrefined copper or crude copper from sulfide concentrate in several stages, whereby the concentrate is air or oxygen-enriched air in a suspension reactor such as a suspension melting furnace. Which results in a copper-rich mat containing 50-75% by weight copper and slag. Such a method is disclosed, for example, in US Pat. No. 2,506,557. The copper mat produced in the suspension melting furnace is converted into crude copper by, for example, a Pierce-Smith type converter or a self-melting converter, and further refined in an anode furnace.
懸濁反応炉において１つの処理段階で直接、硫化物精鉱から粗銅を製造することは一定の境界条件内では経済的に実行可能である。粗銅の直接製造に関する最大の問題には、銅のスラグに対する反応や大量のスラグ形成が含まれている。大量のスラグは銅の回収のための更なる処理工程を必要とするが、これがその工程の経済的実行可能性を左右する。 It is economically feasible to produce crude copper from sulfide concentrate directly in one process step in a suspension reactor within certain boundary conditions. The biggest problems with the direct production of crude copper include the reaction to copper slag and the formation of large amounts of slag. Large amounts of slag require additional processing steps for copper recovery, which affects the economic viability of the process.
精鉱の銅含有量が十分に大きく、例えば精鉱の銅含有量が通常40重量% を越えるオ−ストラリアのOlympic Dam 製錬所におけるように、典型的には少なくとも銅37重量% である場合、１つの段階で直接粗銅を生成することが経済的に可能である。上述の精鉱を用いる場合、スラグの量は中ぐらいになるが、粗銅を製造するためには、粗銅の硫黄含有量が低く、すなわち硫黄が１重量% 以下なので、酸化条件を選択して、生成されるスラグが15〜25重量% の銅を含有するようにする必要がある。 If the copper content of the concentrate is sufficiently large, typically at least 37% copper, such as in the Olympic Dam smelter in Australia, where the copper content of the concentrate usually exceeds 40% by weight It is economically possible to produce crude copper directly in one stage. When using the above concentrate, the amount of slag is moderate, but to produce crude copper, the sulfur content of crude copper is low, ie, sulfur is 1% by weight or less, so the oxidation conditions are selected, It is necessary that the slag produced contains 15 to 25% by weight of copper.
銅含有量がより少ない精鉱は、精鉱が有利な組成である場合は、粗銅を直接製造することに適していることもある。例えば、ポーランドのGlogow 製錬所では、鉄含有量が低く、その結果生じるスラグ量はさほど大きくないので、粗銅を精鉱から一段階で製造している。通常の精鉱によって一段階で銅を製造すると、すべての鉄分および他の脈石がスラグ化する。この種の方法は米国特許4,030,915号に開示されている。 A concentrate with a lower copper content may be suitable for producing crude copper directly if the concentrate has an advantageous composition. For example, the Glogow smelter in Poland produces crude copper in one step from concentrate because the iron content is low and the resulting slag amount is not very large. When copper is produced in one step with normal concentrate, all iron and other gangues are slagged. This type of method is disclosed in US Pat. No. 4,030,915.
フィンランド特許第104838号は、懸濁反応炉において粗銅を硫化銅精鉱から直接製造する方法を開示しており、それによると、精鉱と、フラックスと、酸素富化空気を反応炉に供給する。精鉱から放出される熱を結びつけて、スラグ量を比較的少なくするために、懸濁反応炉へ精鉱とともに、冷却された微細粉砕銅マットを供給し、それによって反応炉へ供給する空気の酸素富化の程度は少なくとも酸素50% になる。 Finnish patent 104838 discloses a method for producing crude copper directly from copper sulfide concentrate in a suspension reactor, according to which concentrate, flux and oxygen-enriched air are fed to the reactor. . In order to combine the heat released from the concentrate and reduce the amount of slag, a cooled finely pulverized copper mat is supplied to the suspension reactor along with the concentrate and thereby the air supplied to the reactor. The degree of oxygen enrichment is at least 50% oxygen.
しかし、このフィンランド特許第104838号はその工程を、酸素富化量が酸素50% より大きく、他方精鉱品質を、精鉱内の銅が31% より多い範囲に限定している。この特許は精鉱の品質によっては、珪酸鉄（実質的にカルシアを含まない）および鉄酸石灰塩スラグ（実質的に珪酸塩を含まない）の両方を用いるように限定される。 However, this Finnish Patent 104838 limits the process to an oxygen enrichment greater than 50% oxygen, while concentrate quality is limited to a range with more than 31% copper in the concentrate. This patent is limited to use both iron silicate (substantially free of calcia) and ferrate lime salt slag (substantially free of silicate) depending on the quality of the concentrate.
PCT 特許出願第WO 00/09772号は、硫化銅精鉱を酸素精錬し、硫化銅精鉱中のほとんどの鉄分を除去してスラグにし、その中の硫黄の一部またはそのほとんどを二酸化硫黄SO2 として除去し、それによって硫化物精鉱から銅をホワイトメタルとして、すなわち、ほぼホワイトメタルのマットもしくは粗銅として得ることにより硫化銅精鉱を精錬する方法を開示している。この方法によれば、SiO2材およびCaO材をフラックスとしてその硫化銅精鉱に対して添加することによって酸素精錬を行なって次のものを製造する；CaO/(SiO2+CaO)の重量比が0.3 〜0.6 (CaO/SiO2=0.43〜1.5)およびFe/(FeOx+SiO2+CaO)の重量比が0.2 〜0.5 のスラグと、ホワイトメタル、ほぼホワイトメタルのマットもしくは粗銅を製造する。そのPCT特許出願第WO 00/09772号の目的は、硫化銅精鉱もしくはマットを1300℃以下の温度で連続酸化してホワイトメタルもしくは粗銅を、磁鉄鉱による困難化なく製造する硫化銅精鉱精錬工程を提供することであり、これは、銅のスラグへの損失のない硫化銅精鉱もしくはSiO2含有マットの処理に適用可能であり、スラグの銅含有量を浮遊選鉱によって回収可能で、砒素とアンチモンと鉛をスラグへ除去する能力が高く、耐火物の腐食が少ない。 PCT Patent Application No. WO 00/09772 discloses that copper sulfide concentrate is subjected to oxygen refining to remove most of the iron content in the copper sulfide concentrate into slag, and a part or most of the sulfur therein is sulfur dioxide SO. A method is disclosed for refining a copper sulfide concentrate by removing it as 2 and thereby obtaining copper from the sulfide concentrate as white metal, ie, approximately as white metal mat or crude copper. According to this method, SiO 2 material and CaO material are added as flux to the copper sulfide concentrate to produce oxygen by refining; weight ratio of CaO / (SiO 2 + CaO) 0.3 to 0.6 (CaO / SiO 2 = 0.43 to 1.5) and Fe / (FeOx + SiO 2 + CaO) with a weight ratio of 0.2 to 0.5 and white metal, almost white metal mat or crude copper. The purpose of the PCT patent application No. WO 00/09772 is a copper sulfide concentrate refining process in which copper sulfide concentrate or mat is continuously oxidized at a temperature of 1300 ° C or less to produce white metal or crude copper without difficulty by magnetite. This is applicable to the treatment of copper sulfide concentrate or SiO 2 containing mats without loss of copper to the slag, and the copper content of the slag can be recovered by flotation, and arsenic and High ability to remove antimony and lead to slag, and less refractory corrosion.
しかし、PCT特許出願第WO 00/09772号は、適切なスラグの組成範囲を、スラグ中のCaO/SiO2比が1.5 よりも低くなり、スラグ中のシリカ含有量が比較的大きく、最低でも純粋なCaO-SiO2-FeOx 系 (CaO=18.8%)においてSiO2が約12.4% になる一定の領域に限定している。スラグ中の石灰含有量が増えるにしたがって、スラグのシリカ含有量も増す必要があり、スラグ総量はしたがって増大する。例えば、CaO/(CaO+SiO2)比が0.6 であり、Fe/(CaO+SiO2+FeOx)比が0.5 から0.2 まで減少した場合、スラグ量は２倍以上になる。CaO/SiO2の最大比は1.5 である。 However, PCT Patent Application No. WO 00/09772 describes a suitable slag composition range with a CaO / SiO 2 ratio in the slag of less than 1.5, a relatively high silica content in the slag, and at least pure In a CaO—SiO 2 —FeO x system (CaO = 18.8%), the SiO 2 content is limited to a certain range of about 12.4%. As the lime content in the slag increases, the silica content of the slag needs to increase, and the total amount of slag therefore increases. For example, when the CaO / (CaO + SiO 2 ) ratio is 0.6 and the Fe / (CaO + SiO 2 + FeO x ) ratio is decreased from 0.5 to 0.2, the amount of slag is more than doubled. The maximum ratio of CaO / SiO 2 is 1.5.
本発明の目的は、従来技術の欠点を解消し、改善された方法を完成して、懸濁反応炉において、粗銅もしくは高品位のマットを硫化物精鉱および／または微細粉砕銅マットから直接製造し、この方法では、スラグを生成するためにシリカ(SiO2) および石灰(CaO) 含有材料の両方も投入し、スラグは、1250〜1350℃の温度範囲で流動性である。本発明の主たる新規構成要件は上記の特許請求の範囲から明らかである。 The object of the present invention is to eliminate the disadvantages of the prior art, complete an improved process, and produce crude copper or high quality mats directly from sulfide concentrate and / or finely ground copper mats in a suspension reactor. However, in this method, both silica (SiO 2 ) and lime (CaO) containing materials are also input to produce slag, and the slag is fluid in the temperature range of 1250-1350 ° C. The main novel features of the invention are apparent from the appended claims.
本方法によれば、酸素含有気体とともに硫化銅精鉱および／または銅マットを懸濁融解炉などの融解反応炉の中へ投入し、その中へシリカ(SiO2) および石灰(CaO) 含有材料の両方も投入し、スラグを生成して、スラグ中のCaO/SiO2比が1.5 よりも大きくなるようにする。そのスラグは1250〜1350℃の温度範囲で流動性である。このスラグの流動性に関して重要なことは、スラグも、酸化形状の銅を少なくとも６重量% 含有することである。 According to this method, a copper sulfide concentrate and / or copper mat together with an oxygen-containing gas is introduced into a melting reaction furnace such as a suspension melting furnace, and silica (SiO 2 ) and lime (CaO) -containing material therein. Both are added to produce slag so that the CaO / SiO 2 ratio in the slag is greater than 1.5. The slag is fluid in the temperature range of 1250-1350 ° C. What is important with regard to the fluidity of this slag is that it also contains at least 6% by weight of oxidized copper.
本発明の方法は、スラグ中の酸化銅が磁鉄鉱ばかりでなく、ケイ酸二カルシウムをも効果的に溶かすという事実に基づいており、このことがCaO-SiO2-FeOx スラグの銅精錬への適用性を限定している。銅の硫黄含有量が0.8重量% よりも低くなっている酸化条件において、精鉱および／または微細粉砕マット中の銅の一部が酸化して溶解作用が生じ、それによって運用範囲を広げることができる。すなわち、前記PCT特許出願第WO 00/09772号の方法に設定されているようなそれぞれの限定CaO/(CaO+SiO2) = 0.3〜0.6 およびFe/(CaO+SiO2+FeOx) = 0.2〜0.5 が解消される。 The method of the present invention is based on the fact that the copper oxide in the slag effectively dissolves not only magnetite but also dicalcium silicate, which is the reason for the copper refining of CaO-SiO 2 -FeO x slag. Limited applicability. Under oxidizing conditions where the sulfur content of copper is lower than 0.8% by weight, some of the copper in the concentrate and / or finely pulverized mat may be oxidized to cause a dissolving action, thereby expanding the operating range. it can. That is, the respective limits CaO / (CaO + SiO 2 ) = 0.3 to 0.6 and Fe / (CaO + SiO 2 + FeO x ) = 0.2 as set in the method of the PCT patent application WO 00/09772. ~ 0.5 is eliminated.
本発明の方法は融解反応炉において、銅精鉱および／またはマットばかりでなく、珪酸塩含有材料および石灰含有材料の混合物質から粗銅もしくは高品位のマットを製造する。1.0重量% より少ない硫黄を有する粗銅と比較的少ない量のスラグを製造するために、冷却された微細粉砕銅マットを融解反応炉へ投入し、その場合、砒素およびアンチモンのスラグ形成を増進させるために石灰の活動度は大きいが、粗銅から鉛を除去するためにシリカの活動度が大きい。 The method of the present invention produces crude copper or high quality mats in a melting reactor from a mixture of silicate-containing material and lime-containing material as well as copper concentrate and / or mat. To produce crude copper with less than 1.0 wt% sulfur and a relatively small amount of slag, a cooled finely ground copper matte is introduced into the melting reactor, in which case slag formation of arsenic and antimony is enhanced. Although the activity of lime is large, the activity of silica is large in order to remove lead from crude copper.
ブリスタ炉へ投入する微細粉砕マットを、公知のいずれかの種類の融解炉で製造した60〜78重量% の銅含有量を有するマットとすることができる。入手可能な精鉱の銅含有量およびその組成に応じて、および微細粉砕マットの量に応じて、一台の懸濁精錬装置をブリスタ精錬装置として直接設計することができる。 The finely pulverized mat charged into the blister furnace can be a mat having a copper content of 60 to 78% by weight produced in any known type of melting furnace. Depending on the copper content of the concentrate available and its composition, and depending on the amount of finely pulverized mat, a suspension refining unit can be designed directly as a blister refining unit.
スラグは一段階もしくは望ましくは二段階のスラグ精選でさらに処理される。この二段階精選方法は２つの電気炉か、または１つの電気炉および１つのスラグ濃縮設備のいずれかを含んでいる。スラグをスラグ濃縮設備で処理する場合、スラグ精鉱を融解反応炉へ戻して投入することができる。粗銅は、通常の精錬のために陽極炉へ行く。 The slag is further processed in one stage or preferably in two stages of slag selection. This two-stage screening method includes either two electric furnaces or one electric furnace and one slag concentration facility. When processing slag with a slag concentration facility, the slag concentrate can be returned to the melting reactor and charged. The crude copper goes to the anode furnace for normal refining.
高品位マットの製造を自溶炉において行なう場合、ブリスタ精錬段階において製造されるスラグを望ましくは粒状化して、銅回収用の一次融解炉へ投入することができる。これの経済性は、原料混合物中の精鉱の量および製造されるスラグの量によって左右される。一次融解炉からのスラグはその後通常の一段階のスラグ精選へ行くか、または、スラグの銅含有量によっては直接処理（電気炉、スラグ精選炉、もしくはスラグ浮遊選鉱）される。 When the high-grade mat is produced in a flash furnace, the slag produced in the blister refining stage can be desirably granulated and put into a primary melting furnace for copper recovery. The economics of this depend on the amount of concentrate in the raw material mixture and the amount of slag produced. The slag from the primary melting furnace then goes to the usual one-stage slag selection or directly processed (electric furnace, slag selection furnace, or slag flotation) depending on the copper content of the slag.
以下の実施例および添付の図面を参照して、本発明をさらに詳細に説明する。 The invention will now be described in more detail with reference to the following examples and the accompanying drawings.
実施例１
粗銅を小型懸濁試験融解炉において一連の試験で製造し、その場合、銅含有原料は、微細粉砕銅マット（Cu 72.3重量%、Fe 3.4重量%、S 20.3重量%）と、銅精鉱（Cu 29.2重量%、S 33.7重量%、Fe 21.0重量%）であった。銅マットと精鉱の混合物（kgマット）／（kgマット+ kg精鉱）*100は50〜100% の間の範囲にした。原料投入量は毎時100〜200kg にした。製造する粗銅の酸化度を酸素係数（原料トン当りNm3 O2 ）により調整し、スラグの組成（スラグ中のCaO/SiO2およびFe/SiO2 ）は珪砂および石灰を原料へ添加して調整した。工程パラメータが一定に保たれている各期間の後、スラグおよび粗銅を小型試験炉の沈降機から取り出して、生成された粗銅およびスラグを分析した。粗銅の平均硫黄含有量は硫黄0.2重量% （硫黄0.01〜0.89%）であった。
Example 1
Crude copper is produced in a series of tests in a small suspension test melting furnace, in which case the copper-containing raw material is a finely pulverized copper mat (Cu 72.3 wt%, Fe 3.4 wt%, S 20.3 wt%) and copper concentrate ( Cu 29.2 wt%, S 33.7 wt%, Fe 21.0 wt%). Copper mat and concentrate mixture (kg mat) / (kg mat + kg concentrate) * 100 was in the range between 50-100%. The raw material input was 100 to 200 kg per hour. The degree of oxidation of the crude copper produced is adjusted by the oxygen coefficient (Nm 3 O 2 per ton of raw material), and the slag composition (CaO / SiO 2 and Fe / SiO 2 in the slag) is adjusted by adding silica sand and lime to the raw material did. After each period when the process parameters were kept constant, slag and crude copper were removed from the settling machine of the small test furnace and the produced crude copper and slag were analyzed. The average sulfur content of the crude copper was 0.2% by weight sulfur (0.01 to 0.89% sulfur).
次に試験期間のうちの１つの結果を一例として示す。 Next, the result of one of the test periods is shown as an example.
マット投入率 89.7kg/h
マット品質（Fe 3.4%、S 18.2%、As 0.26%、Pb 0.2%） Cu 72.3 %
精鉱投入率 59.9kg/h
精鉱品質（Fe 20.9%、S 30.7%、SiO2 5.1%、
As 1.3%、Pb 0.11%） Cu 30.2%
珪砂投入率 0.5kg/h
石灰投入率 10.3kg/h
精鉱燃焼器への技術的酸素供給率 29.0Nm3/h
精鉱燃焼器への空気供給率 31.0Nm3/h
酸素富化 59.2%
酸素係数 254.4Nm3O2/t
熱損失を均衡させるための反応シャフト
および沈降機へのブタン投入 3.03kg/h
試験期間（原料供給状態） ３時間10分
取出し温度 1300℃
製造された粗銅の品質：
硫黄含有量 S 0.08%
砒素含有量 As 0.077%
鉛含有量 Pb 0.035%
生成スラグの品質：
銅含有量 Cu18.3%
石灰含有量 CaO 19.3%
シリカ含有量 SiO2 7.6%
鉄含有量 Fe 28.2%
砒素含有量 As 0.68%
鉛含有量 Pb 0.28%
CaO/SiO2(重量%/重量%) 2.54
Fe/SiO2(重量%/重量%) 3.71
CaO/(CaO+SiO2)(重量%/重量%) 0.72
スラグと粗銅の間の砒素分配係数 8.8
スラグと粗銅の間の鉛分配係数 8.0
Mat loading rate 89.7kg / h
Matt quality (Fe 3.4%, S 18.2%, As 0.26%, Pb 0.2%) Cu 72.3%
Concentrate input rate 59.9kg / h
Concentrate quality (Fe 20.9%, S 30.7%, SiO 2 5.1%,
As 1.3%, Pb 0.11%) Cu 30.2%
Silica sand input rate 0.5kg / h
Lime input rate 10.3kg / h
Technical oxygen supply rate to concentrate combustor 29.0Nm 3 / h
Air supply rate to concentrate combustor 31.0Nm 3 / h
Oxygen enrichment 59.2%
Coefficient of oxygen 254.4Nm 3 O 2 / t
Butane input to reaction shaft and settling machine to balance heat loss 3.03kg / h
Test period (raw material supply state) 3
Quality of crude copper produced:
Sulfur content S 0.08%
Arsenic content As 0.077%
Lead content Pb 0.035%
Generated slag quality:
Copper content Cu18.3%
Lime content CaO 19.3%
Silica content SiO 2 7.6%
Iron content Fe 28.2%
Arsenic content As 0.68%
Lead content Pb 0.28%
CaO / SiO 2 (wt% / wt%) 2.54
Fe / SiO 2 (wt% / wt%) 3.71
CaO / (CaO + SiO 2 ) (wt% / wt%) 0.72
Arsenic partition coefficient between slag and crude copper 8.8
Lead partition coefficient between slag and crude copper 8.0
本方法の適用可能性を、試験運転の結果および図１〜図７に基づいてさらに説明する。 The applicability of this method will be further described based on the results of the test operation and FIGS.
図１は、粗銅中の正規化した酸素分圧（T=1300℃）の関数としてさまざまなスラグの種類の銅含有量を示す。スラグのCaO/SiO2比（所定のFe/SiO2 比における）が大きくなると、スラグの銅含有量が減少することが分かる。比較するため、鉄かんらん石（珪酸鉄）スラグの銅含有量も図１に示す。鉄かんらん石スラグと比較して、同じ酸素ポテンシャルにおける銅含有量はかなり低い。 FIG. 1 shows the copper content of various slag types as a function of normalized oxygen partial pressure (T = 1300 ° C.) in crude copper. It can be seen that as the CaO / SiO 2 ratio of slag (at a given Fe / SiO 2 ratio) increases, the copper content of the slag decreases. For comparison, the copper content of iron olivine (iron silicate) slag is also shown in FIG. Compared to iron olivine slag, the copper content at the same oxygen potential is much lower.
図２は、粗銅中の正規化した酸素分圧の関数としてさまざまなスラグの種類におけるスラグと粗銅との間の砒素の分配係数LAs (slag/Cu)=(スラグ中のAsの% ）／（粗銅中のAsの% ）を示す。スラグのCaO/SiO2比（所定のFe/SiO2 比における）が大きくなると、砒素の分配係数LAs (slag/Cu)が大きくなることが分かる。比較するため、珪酸鉄スラグと粗銅との間の砒素の分配係数も図２に示す。砒素の鉄かんらん石スラグの分配係数LAs (slag/Cu)と比較して、同じ酸素ポテンシャルにおいてCaO/SiO2スラグのものの方が大きく、粗銅から砒素を除去する能力がかなり大きいことを示している。 Figure 2 shows the distribution coefficient of arsenic between slag and crude copper, L As (slag / Cu) = (% of As in slag ) / various slag types as a function of normalized oxygen partial pressure in crude copper. (% Of As in crude copper). It can be seen that the arsenic distribution coefficient L As (slag / Cu) increases as the CaO / SiO 2 ratio of slag (at a predetermined Fe / SiO 2 ratio) increases. For comparison, the distribution coefficient of arsenic between iron silicate slag and crude copper is also shown in FIG. Compared to the distribution coefficient L As (slag / Cu) of arsenic iron olivine slag, CaO / SiO 2 slag is larger at the same oxygen potential, indicating a much greater ability to remove arsenic from crude copper. ing.
図３は、粗銅中の正規化した酸素分圧の関数としてさまざまなスラグの種類におけるスラグと粗銅との間の鉛の分配係数LPb (slag/Cu)=(スラグ中のPb % ）／（粗銅中のPb % ）を示す。スラグのCaO/SiO2比（所定のFe/SiO2 比における）が大きくなると、鉛の分配係数LPb (slag/Cu)がわずかに減少することが分かる。比較するため、鉄酸石灰塩スラグと粗銅との間の鉛の分配係数も図３に示す。鉛の鉄酸石灰塩スラグの分配係数LPb (slag/Cu)と比較して、同じ酸素ポテンシャルにおいてCaO/SiO2スラグのものの方が大きく、粗銅から砒素を除去する能力がもっと高いことを示している。 FIG. 3 shows the distribution coefficient L Pb (slag / Cu) = (Pb% in slag) / (lead slag between slag and crude copper in various slag types as a function of normalized oxygen partial pressure in crude copper. Pb% in crude copper). It can be seen that the lead distribution coefficient L Pb (slag / Cu) slightly decreases as the slag CaO / SiO 2 ratio (at a given Fe / SiO 2 ratio) increases. For comparison, the distribution coefficient of lead between iron lime salt slag and crude copper is also shown in FIG. Compared to the partition coefficient L Pb (slag / Cu) of lead ferrate lime salt slag, CaO / SiO 2 slag is larger at the same oxygen potential, indicating more ability to remove arsenic from crude copper ing.
図４は、FeOx+CaO+SiO2=100 の図に記載したスラグの銅含有量を示す。結果を1300℃の温度、およびlog Po2= -4.5 の酸素分圧に正規化している。定酸素分圧でFeOx+CaO+SiO2 ＋酸化銅スラグによって運転した場合、CaO/SiO2比が1.5 よりも大きくかつCaO+SiO2+FeOx 系のCaO 含有量が20% よりも大きい時、スラグの銅含有量は10〜20%の間にあることがわかる。 FIG. 4 shows the copper content of the slag described in the diagram FeO x + CaO + SiO 2 = 100. The results are normalized to a temperature of 1300 ° C and an oxygen partial pressure of log Po 2 = -4.5. When operated with FeO x + CaO + SiO 2 + copper oxide slag at constant oxygen partial pressure, when the CaO / SiO 2 ratio is greater than 1.5 and the CaO + SiO2 + FeO x system has a CaO content greater than 20% It can be seen that the copper content of the slag is between 10-20%.
図５は、スラグ中のCuの%=20% に正規化したFeOx+CaO+SiO2=100 の図に示すスラグと粗銅との間の砒素の分配係数を示す。試験結果に基づく等分布線も示す。CaO/SiO2比が1.5 よりも大きい場合、その系のCaO が増えると、分配係数は大きくなる。 FIG. 5 shows the distribution coefficient of arsenic between slag and crude copper shown in the figure of FeO x + CaO + SiO 2 = 100 normalized to% = 20% of Cu in the slag. An isodistribution line based on the test results is also shown. If the CaO / SiO 2 ratio is greater than 1.5, the partition coefficient increases as the CaO in the system increases.
図６は、スラグ中のCuの%=20% に正規化したFeOx+CaO+SiO2=100 の図に示すスラグと粗銅との間の鉛の分配係数を示す。CaO/SiO2比が1.5 よりも大きい場合、その系のCaO 含有量が減ると、鉛の分配係数が大きくなる。 FIG. 6 shows the distribution coefficient of lead between the slag and the crude copper shown in the diagram of FeO x + CaO + SiO 2 = 100 normalized to% of Cu in the slag = 20%. When the CaO / SiO 2 ratio is greater than 1.5, the lead partition coefficient increases as the CaO content of the system decreases.
試験調査におけるスラグの粘度は充分に低く、炉から通常の取出し口を介して取り出すことができた。スラグの粘性挙動を研究するために、試験調査において生成したスラグのいくつかに関してさらに詳細な粘度測定を行った。図７は、スラグ中のCuの%=15% に正規化したFeOx+CaO+SiO2=100 の図に記したスラグの200cP 粘度時の温度を示す。スラグのCaO 含有量が増加しつつある場合は、200cP 粘度時の温度が上昇する。理論上の計算によれば、図７に破線で示すように固形磁鉄鉱の形成がこの種のスラグの有用性を限定している。 The slag viscosity in the test study was sufficiently low and could be removed from the furnace via a normal outlet. In order to study the viscosity behavior of slag, more detailed viscosity measurements were made on some of the slag produced in the test study. FIG. 7 shows the temperature at 200 cP viscosity of the slag shown in the diagram of FeO x + CaO + SiO 2 = 100 normalized to% of Cu in the slag = 15%. If the CaO content of the slag is increasing, the temperature at 200cP viscosity will increase. According to theoretical calculations, the formation of solid magnetite limits the usefulness of this type of slag, as shown by the dashed line in FIG.
ここで、図１〜図７における結果は、スラグのCaO/SiO2比が1.5 よりも大きい場合、スラグを炉から取り出すのに十分な流動性をスラグは有することと、スラグの銅含有量がそのスラグ中でCu 8%よりも大きい場合、FeOx+CaO+SiO2=100 において計算したスラグのCaO 含有量は20% よりも大きくなることを示している。 Here, the results in FIGS. 1 to 7 show that when the CaO / SiO 2 ratio of the slag is larger than 1.5, the slag has sufficient fluidity to take out the slag from the furnace, and the copper content of the slag is It shows that when the slag is larger than Cu 8%, the CaO content of the slag calculated at FeO x + CaO + SiO 2 = 100 is larger than 20%.
Claims (6)
系において計算した石灰含有量が20% よりも大きくなるようにすることを特徴とする製造方法。 In a suspension melting reactor, crude copper or high-grade mat is produced directly from copper sulfide concentrate-containing material and / or finely pulverized copper mat, and oxygen-containing gas, copper concentrate and / or finely pulverized copper mat are supplied to the reactor. In the charging method, CaO and SiO 2 -containing flux is introduced into the melting reactor together with oxygen-containing gas, copper concentrate and / or copper mat, and a part of the copper in the concentrate and / or the mat is fed. Oxidized to produce slag, in which the CaO / SiO 2 ratio is from 1.5 to 2.54 , the copper content is in the oxidized form, CaO + SiO 2 + FeO x = 100
A production method characterized in that the lime content calculated in the system is greater than 20%.
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| FI20011859A FI115536B (en) | 2001-09-21 | 2001-09-21 | A process for producing crude copper |
| PCT/FI2002/000748 WO2003025236A1 (en) | 2001-09-21 | 2002-09-20 | Method for the production of blister copper |
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| JP3828541B2 true JP3828541B2 (en) | 2006-10-04 |
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| US (1) | US20040244534A1 (en) |
| EP (1) | EP1436434A1 (en) |
| JP (1) | JP3828541B2 (en) |
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| CN (1) | CN1295364C (en) |
| AU (1) | AU2002325965B2 (en) |
| BR (1) | BR0212651A (en) |
| CA (1) | CA2459962C (en) |
| EA (1) | EA005386B1 (en) |
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| PL (1) | PL197523B1 (en) |
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| KR101844707B1 (en) | 2014-05-14 | 2018-04-02 | 오토텍 (핀랜드) 오와이 | A method of converting copper containing material |
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| US7164200B2 (en) | 2004-02-27 | 2007-01-16 | Agere Systems Inc. | Techniques for reducing bowing in power transistor devices |
| FI120157B (en) * | 2007-12-17 | 2009-07-15 | Outotec Oyj | Process for processing copper copper |
| KR101005848B1 (en) * | 2008-02-01 | 2011-01-05 | 장광식 | Women's Shoe Heels |
| JP4908456B2 (en) * | 2008-06-02 | 2012-04-04 | パンパシフィック・カッパー株式会社 | Copper smelting method |
| JP4949342B2 (en) * | 2008-09-04 | 2012-06-06 | パンパシフィック・カッパー株式会社 | Copper smelting method |
| SE533677C2 (en) * | 2009-04-05 | 2010-11-30 | Boliden Mineral Ab | Method for refining copper bullion containing antimony and / or arsenic |
| WO2012033454A1 (en) * | 2010-09-10 | 2012-03-15 | Jernkontoret | Production of nano sized ferrite |
| RU2520292C1 (en) * | 2012-12-06 | 2014-06-20 | Общество С Ограниченной Ответственностью "Медногорский Медно-Серный Комбинат" | Processing of sulphide copper-lead-zinc materials |
| JP5612145B2 (en) * | 2013-03-07 | 2014-10-22 | パンパシフィック・カッパー株式会社 | Method for producing electrolytic copper |
| JP6665443B2 (en) * | 2015-08-18 | 2020-03-13 | 住友金属鉱山株式会社 | Operating method of flash smelting furnace |
| CN106521183A (en) * | 2016-11-02 | 2017-03-22 | 阳谷祥光铜业有限公司 | Method for smelting high-arsenic copper sulfide ore |
| RU2639195C1 (en) * | 2016-12-02 | 2017-12-20 | Федеральное государственное автономное образовательное учреждение высшего образования "Сибирский федеральный университет" | Method of processing of nickel-containing sulfide copper concentrates |
| BE1025769B1 (en) * | 2017-12-14 | 2019-07-08 | Metallo Belgium | Improved pyrometallurgical process |
| RU2734613C2 (en) * | 2019-02-08 | 2020-10-21 | Открытое акционерное общество "Научно-исследовательский и проектный институт обогащения и механической обработки полезных ископаемых "Уралмеханобр" | Horizontal converter and combined melting-converting method |
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| US1312115A (en) * | 1919-08-05 | Hoisting mechanism | ||
| CA1107080A (en) * | 1977-05-09 | 1981-08-18 | John M. Floyd | Submerged injection of gas into liquid pyro- metallurgical bath |
| SU1312115A1 (en) * | 1982-07-22 | 1987-05-23 | Всесоюзный научно-исследовательский горно-металлургический институт цветных металлов | Method of treating copper and copper-zinc sulfide concentrates |
| FI78125C (en) * | 1983-11-14 | 1989-06-12 | Vni Gorno Metall I Tsvet Met | FOERFARANDE FOER BEHANDLING AV JAERNHALTIGA KOPPAR- ELLER KOPPAR / ZINKSULFIDKONCENTRAT. |
| CA1234696A (en) * | 1985-03-20 | 1988-04-05 | Grigori S. Victorovich | Metallurgical process iii |
| AUPM657794A0 (en) * | 1994-06-30 | 1994-07-21 | Commonwealth Scientific And Industrial Research Organisation | Copper converting |
| US6231641B1 (en) * | 1998-02-12 | 2001-05-15 | Kennecott Utah Copper Corporation | Enhanced phase interaction at the interface of molten slag and blister copper, and an apparatus for promoting same |
| JP3682166B2 (en) * | 1998-08-14 | 2005-08-10 | 住友金属鉱山株式会社 | Method for smelting copper sulfide concentrate |
| AU6792300A (en) | 1999-08-23 | 2001-03-19 | 3Com Corporation | Architecture for a network management service which identifies and locates usersand/or devices within an enterprise network |
| BR0016890A (en) * | 2000-01-04 | 2002-10-08 | Outokumpu Oy | Method for the production of blister copper in a suspended reactor |
| JP3702764B2 (en) * | 2000-08-22 | 2005-10-05 | 住友金属鉱山株式会社 | Method for smelting copper sulfide concentrate |
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| KR101844707B1 (en) | 2014-05-14 | 2018-04-02 | 오토텍 (핀랜드) 오와이 | A method of converting copper containing material |
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| JP2005503481A (en) | 2005-02-03 |
| AU2002325965B2 (en) | 2008-01-24 |
| WO2003025236A1 (en) | 2003-03-27 |
| FI115536B (en) | 2005-05-31 |
| CN1556867A (en) | 2004-12-22 |
| EA200400266A1 (en) | 2004-10-28 |
| EP1436434A1 (en) | 2004-07-14 |
| PL368532A1 (en) | 2005-04-04 |
| BR0212651A (en) | 2004-08-24 |
| KR100929520B1 (en) | 2009-12-03 |
| PE20030425A1 (en) | 2003-06-13 |
| CA2459962A1 (en) | 2003-03-27 |
| YU24704A (en) | 2006-08-17 |
| ZA200401902B (en) | 2004-09-08 |
| FI20011859L (en) | 2003-03-22 |
| CA2459962C (en) | 2011-01-04 |
| KR20040029183A (en) | 2004-04-03 |
| CN1295364C (en) | 2007-01-17 |
| MXPA04002601A (en) | 2004-06-07 |
| FI20011859A0 (en) | 2001-09-21 |
| EA005386B1 (en) | 2005-02-24 |
| RO122640B1 (en) | 2009-10-30 |
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| US20040244534A1 (en) | 2004-12-09 |
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