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AU2002325965B2 - Method for the production of blister copper - Google Patents
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AU2002325965B2 - Method for the production of blister copper - Google Patents

Method for the production of blister copper Download PDF

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Publication number
AU2002325965B2
AU2002325965B2 AU2002325965A AU2002325965A AU2002325965B2 AU 2002325965 B2 AU2002325965 B2 AU 2002325965B2 AU 2002325965 A AU2002325965 A AU 2002325965A AU 2002325965 A AU2002325965 A AU 2002325965A AU 2002325965 B2 AU2002325965 B2 AU 2002325965B2
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Australia
Prior art keywords
copper
slag
cao
blister
sio
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Expired
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AU2002325965A
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AU2002325965A1 (en
Inventor
Cesar Acuna Rojas
Carlos Caballero Deramond
Pekka Hanniala
Ilkka Kojo
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Metso Corp
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Outotec Oyj
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0026Pyrometallurgy
    • C22B15/0028Smelting or converting
    • C22B15/0047Smelting or converting flash smelting or converting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0026Pyrometallurgy
    • C22B15/0054Slag, slime, speiss, or dross treating
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)

Description

WO 03/025236 PCT/FI02/00748 1 METHOD FOR THE PRODUCTION OF BLISTER COPPER This invention relates to a pyrometallurgical method of producing blister copper in a smelting reactor, such as a suspension smelting furnace, directly from its sulfidic concentrate and/or finely ground copper matte.
A well-known method of the prior art is to produce raw copper or blister copper from a sulfidic concentrate in several stages, whereby the concentrate is smelted in a suspension reactor, such as a suspension smelting furnace, with air or oxygen-enriched air, which results in copper-rich matte containing 50 weight-% copper and slag. This kind of method is described in e.g. US patent 2,506,557. Copper matte formed in a suspension smelting furnace is converted in for example a Pierce-Smith type converter or a flash converter into blister copper and refined further in an anode furnace.
The production of blister copper from sulfidic concentrate directly in one process step in a suspension reactor is economically viable within certain boundary conditions. The greatest problems involved in the direct production of blister include copper deportment to slag and the large amount of slag formed.
The large amount of slag requires further treatment process step for copper recovery, which affects the economic feasibility of the process.
If the copper content of the concentrate is high enough, typically at least 37 weight-% copper, as for example at the Olympic Dam smelter in Australia, where the copper content of the concentrate normally exceeds 40 weight-%, it is possible economically to produce blister directly in one stage. When using the previously described concentrate the slag amount is moderate, but in order to produce blister, which has low sulphur content, less than 1 weight-% sulphur, the oxidation conditions must be selected so that the produced slag contains -25 weight-% copper.
Concentrate with a lower copper content can also be suitable for direct blister WO 03/025236 PCT/FI02/00748 2 production, if it has an advantageous composition. For example, at the Glogow smelter in Poland, blister copper is produced from concentrate in one stage, since the iron content is low and the resulting amount of slag is not significantly high. The production of copper in one stage with the normal concentrates causes slagging of all the iron and other gangues. This type of method is described in the US patent 4,030,915.
The Fl patent 104838 describes a method to produce blister copper in a suspension reactor directly from a sulfidic copper concentrate, whereby the concentrate, flux and oxygen-enriched air are fed into the reactor. The cooled and finely-ground copper matte is fed into the suspension reactor along with the concentrate in order to bind the heat released from the concentrate and to decrease the amount of slag relatively, whereby the degree of oxygen enrichment of the air fed to the reactor is at least 50 oxygen.
This Fl patent 104838 is however, limiting the process to areas, where the oxygen enrichment is higher than 50 oxygen and on the other hand the concentrate quality is limited to above 31 copper in a concentrate. The patent is limited to use both iron silicate slag (essentially free from calcia) and calcium ferrite slag (essentially free from silicate) depending on the concentrate quality.
The PCT patent application WO 00/09772 describes a method of smelting copper sulphide concentrate by oxygen-smelting the copper sulphide concentrate, and removing most of the iron in the copper sulphide concentrate into slag as well as removing part or most of the sulphur therein as sulphur dioxide S0 2 thereby obtaining copper from sulphide concentrate as white metal, nearly white metal matte or blister copper. According to the method the oxygen-smelting is carried out to produce; slag in which a weight ratio of CaO/(SiO 2 +CaO) is 0.3 to 0.6 (CaO/SiO 2 0.43 to 1.5) and a weight ratio of Fe/(FeOx+SiO 2 +CaO) is 0.2 to 0.5, and a white metal, nearly white metal matte, or blister copper, by adding SiO 2 material and CaO material to the copper WO 03/025236 PCT/FI02/00748 3 sulphide concentrate as flux. The object of that PCT patent application WO 00/09772 is to provide a copper sulphide concentrate smelting process for producing white metal or blister copper with continuous oxidation of copper sulphide concentrate or matte at the temperature of 1300 °C or less, without magnetite complications, which is applicable for the treatment of copper sulphide concentrate or matte containing SiO 2 with less loss of copper to slag, capable of recovering copper content of slag by flotation, with high removability of arsenic, antimony and lead into slag, and with less erosion of refractories.
The PCT patent application WO 00/09772, however, limits the suitable slag composition area to a window, where the CaO/SiO 2 ratio in the slag is lower than 1.5 and where the silica content in the slag is relatively high, minimum being about 12.4 SiO 2 in the pure CaO-SiO 2 -FeOx system (CaO 18.6 As the lime content in the slag is increasing the silica content of the slag has to be increased, too, and the total slag amount increases accordingly. For example when the CaO/(CaO+SiO 2 ratio is 0.6 and the ratio Fe/(CaO+SiO 2 +FeOx) decreases from 0.5 to 0.2 the slag amount is more than doubled. The highest CaO/SiO 2 ratio is The object of the invention is to eliminate drawbacks of the prior art and to achieve an improved method to produce blister copper or high grade matte in a suspension reactor directly from a sulfidic concentrate and/or finely ground copper matte wherein both silica (SiO 2 and lime (CaO) bearing materials are also fed in order to form a slag, which is fluid at the temperature range of 1250 1350 OC. The essential novel features of the invention are apparent from the appended claims.
According to the method a copper sulphide concentrate and/or copper matte with oxygen-containing gas is fed into a smelting reactor, such as a suspension smelting furnace, into which both silica (SiO 2 and lime (CaO) bearing materials are also fed in order to form a slag so that the CaO/SiO 2 ratio in the slag is higher than 1.5, and which slag is fluid at the temperature range of 1250 1350 WO 03/025236 PCT/FI02/00748 4 Essential to the slag fluidity is that the slag also contains copper in oxidized form at least 6 weight percent.
The method of the invention is based on the fact that oxidized copper in slag fluxes effectively both magnetite and dicalcium silicate, which limits the applicability of the CaO-SiO 2 -FeOx slag in the copper smelting. In the oxidation conditions, where the sulphur content in copper is below 0.8 weight-%, part of the copper in the concentrate and/or in the finely ground matte is oxidized causing the fluxing effect, which allows the widening of the operation window, i.e. eliminates the limitations CaO/(CaO+SiO 2 0.3 to 0.6 and Fe/(CaO+SiO 2 +FeOx) 0.2 to 0.5 as set in the method of the PCT patent application WO 00/09772.
The method of the invention produces blister copper or high grade matte in a smelting reactor from a mixture of copper concentrate and/or matte as well as silicate containing material and lime containing material. The cooled and finely ground copper matte is fed into the smelting reactor in order to produce blister copper with lower than 1.0 weight-% sulphur and a relatively low amount of slag, in which the activity of lime is high in order to increase the slagging of arsenic and antimony, but in which the activity of silica is high in order to eliminate lead from the blister copper.
The finely ground matte fed into the blister furnace may be matte produced in any kind of known smelting furnace having a copper content of 60 78 weight- A single suspension smelting unit may be designed directly as a blister smelter depending on the copper content and composition of the available concentrates and on the amount of the finely ground matte.
The slag is treated further in a single-stage or preferably two-stage slag cleaning. The two-stage cleaning method includes either two electric furnaces or an electric furnace and a slag concentrating plant. If the slag is treated in a WO 03/025236 PCT/FI02/00748 slag concentrating plant, the slag concentrate can be fed back into the smelting reactor. Blister copper goes for normal refining in an anode furnace.
If the production of the high-grade matte is carried out in a flash smelting furnace, the slag produced in the blister smelting stage can be preferably granulated and fed into the primary smelting furnace for copper recovery. The economy of this depends on the amount of the concentrate in the feed mixture and on the slag amount produced. The slag from the primary smelting furnace goes then to a normal single-stage slag cleaning or directly disposed (an electric furnace, a slag cleaning furnace or slag flotation) depending on the copper content of the slag.
The invention is further described in more detail with reference to following examples and to the appended drawings, where Fig. 1 shows copper content of different slag types as a function of normalized oxygen partial pressure (T=1300 in blister copper according to the example 1, Fig. 2 shows the distribution coefficient of arsenic between slag and blister copper in different slag types as a function of the normalized oxygen partial pressure in blister copper according to the example 1, Fig. 3 shows the distribution coefficient of lead between slag and blister copper in different slag types as a function of the normalized oxygen partial pressure in blister copper according to the example 1, Fig. 4 shows the copper content of slag given in FeO, CaO Si0 2 100 diagram according to the example 1, Fig. 5 shows the distribution coefficient of arsenic between slag and blister shown in FeOx CaO Si0 2 100 diagram normalized to Cu) in slag according to the example 1, Fig. 6 shows the distribution coefficient of lead between slag and blister shown in FeO× CaO Si0 2 100 diagram normalized to Cu) in slag 20 according to the example 1, and WO 03/025236 PCT/FI02/00748 6 Fig. 7 shows the 200 cP viscosity temperature of the slag given in FeOx CaO SiO 2 100 diagram normalized to Cu) in slag 15 according to the example 1.
Example 1 Blister copper was produced in a suspension mini pilot smelting furnace in a series of tests, where the copper containing raw materials were finely grained copper matte (72.3 weight-% Cu, 3.4 weight-% Fe, 20.3 weight-% S) and copper concentrate (29.2 weight-% Cu, 33.7 weight-% S, 21.0 weight-% Fe).
The mixture of copper matte and concentrate (kg matte)/(kg matte kg concentrate)*100 was ranging between 50 100 The feed rate was 100 200 kg/h. The oxidation degree of blister copper produced was controlled by the oxygen coefficient (Nm 3 0 2 /ton of feed), and the slag composition (CaO/SiO 2 Fe/SiO2 in slag) was controlled by adding silica sand and lime to the feed. After each period, during which the process parameters were kept constant, the slag and blister were tapped out of the settler of the mini pilot furnace and the produced blister copper and slag was analysed. The average sulphur content of the blister was 0.2 weight-% sulphur (0.01-0.89 sulphur).
As an example results of one of the test periods is given as follows: Matte feed rate Matte quality (3.4 Fe, 18.2 S, 0.26 As, 0.2 Pb) Concentrate feed rate Conc. quality (20.9 Fe, 30.7 S, 5.1 SiO 2 1.3 As, 0.11 Pb) Silica sand feed rate Lime feed rate Technical oxygen feed rate to concentrate burner Air feed rate to concentrate burner Oxygen enrichment 89.7 kg/h 72.3 Cu 59.9 kg/h 30.2 Cu 0.5 kg/h 10.3 kg/h 29.0 Nm 3 /h 31.0 Nm 3 /h 59.2 WO 03/025236 PCT/FI02/00748 Oxygen coefficient Butane feed to reaction shaft and settler in order to balance the heat losses Duration of test (feed on) Tapping temperature Quality of blister produced: Sulphur content Arsenic content Lead content 245.4 Nm 3 0 2 /t 3.03 kg/h 3h 10 min 1300 °C 0.08 S 0.077 As 0.035 Pb Quality of slag produced: Copper content Lime content Silica content Iron content Arsenic content Lead content CaO/SiO 2 Fe/SiO2 CaO/(CaO+ SiO 2 Distribution coefficient of Arsenic between slag and blister Distribution coefficient of Lead between slag and blister The applicability of the method is further described based test runs and Figures 1 7.
18.3 Cu 19.3 CaO 7.6 SiOz 28.2 Fe 0.68 As 0.28 Pb 2.54 3.71 0.72 8.8 on the results of the Figure 1 shows copper content of different slag types as a function of normalized oxygen partial pressure (T=1300 in blister copper. It can be seen that when the CaO/SiO 2 ratio (at a given Fe/SiOz ratio) of the slag increases the copper content of the slag decreases. For comparison the copper WO 03/025236 PCT/FI02/00748 8 content of fayalite (iron silicate) slag is given in Figure 1, too. Compared with fayalite slag the copper content at the same oxygen potential is much lower.
Figure 2 shows the distribution coefficient of arsenic between slag and blister copper LAs(s l ag C u) As in slag)/(% As in blister) in different slag types as a function of the normalized oxygen partial pressure in blister copper. It can be seen that when the CaO/SiO 2 ratio (at a given Fe/SiO 2 ratio) of the slag increases the distribution coefficient of arsenic, LAs(l a g C increases. For comparison the distribution coefficient of arsenic between iron silicate slag and blister copper is given in Figure 2, too. Compared with fayalite slag distribution coefficient of arsenic LAs s l ag the one of the CaO/SiO 2 slag is higher at the same oxygen potential showing the much higher ability to remove arsenic from blister.
Figure 3 shows the distribution coefficient of lead between slag and blister copper Lpb(s lag /Cu) Pb in slag)/(% Pb in blister) in different slag types as a function of normalized oxygen partial pressure in blister copper. It can be seen that when the CaO/SiO 2 ratio (at a given Fe/SiO 2 ratio) of the slag increases the distribution coefficient of lead, Lpb(s a g C slightly decreases. For comparison the distribution coefficient of lead between calcium ferrite slag and blister copper is given in Figure 3, too. Compared with calcium ferrite slag distribution coefficient of lead Lpb(s l a g the one of the CaO/SiO 2 slag is higher at the same oxygen potential showing the higher ability to remove arsenic from blister.
Figure 4 shows the copper content of slag given in FeOx CaO SiO 2 100 diagram. The results are normalized to the temperature of 1300 °C and to the oxygen partial pressure of log po2 It can be seen, that when operating with FeOx CaO Si02 copper oxide slag at a constant oxygen partial pressure the copper content of slag is between 10-20 when the CaO/SiO2 ratio is higher than 1.5 and the CaO content in CaO+SiO2+FeOx system is higher than 20 WO 03/025236 PCT/FI02/00748 9 Figure 5 shows the distribution coefficient of arsenic between slag and blister shown in FeOx CaO Si02 100 diagram normalized to Cu) in slag The isodistribution lines based on the test results are also indicated. When the CaO/SiO 2 ratio is higher than 1.5, the distribution coefficient increases when the CaO content in the system increases.
Figure 6 shows the distribution coefficient of lead between slag and blister shown in FeOx CaO Si02 100 diagram normalized to Cu) in slag When the CaO/SiO 2 ratio is higher than 1.5, the distribution coefficient of lead increases, when the CaO content in the system is decreasing.
The viscosity of the slags in the pilot tests was low enough that they could be tapped out of the furnace through a normal tapping hole. In order to study the viscosity behavior of the slags more detailed viscosity measurements were carried out for some of the slags produced in the pilot tests. Figure 7 shows the 200 cP viscosity temperature of the slag given in FeOx CaO Si02 100 diagram normalized to Cu) in slag 15 The 200 cP viscosity temperature increases when the CaO content of the slag is decreasing. Based on theoretical calculations the solid magnetite formation is limiting the usability of this kind of slag as shown with the dashed line in Figure 7.
Now, the results in the Figures 1-7 indicate that the slag is fluid enough to be tapped out of the furnace, when the CaO/SiO 2 ratio of the slag is higher than and that the CaO content of the slag calculated in FeOx CaO SiO 2 100 is higher than 20 and when the copper content of the slag is higher than 8 Cu in the slag.

Claims (4)

1. A method to produce blister copper or high grade matte in a suspension smelting reactor directly from a sulfidic copper concentrate containing material and/or finely ground copper matte, whereby oxygen-containing gas, copper Sconcentrate and/or finely ground copper matte are fed into the reactor, characterized in that CaO and SiO 2 containing flux is fed into the smelting m reactor along with oxygen-containing gas, copper concentrate and/or copper 0 matte, and part of the copper in the concentrate and/or in the matte is oxidized cI 10 in order to form a slag in which the CaO/SiO 2 ratio is higher than 1.5, and in which the copper content is in oxidized form, and in which the lime content calculated in a CaO+SiO 2 +FeOx=100 system is higher than 20
2. A method according to claim 1, characterized in that the copper content in the slag in oxidized form is at least 6 weight percent.
3. A method according to claim 1 or 2, characterized in that the activity of lime in the slag formed is high in order to increase the slagging of arsenic and antimony.
4. A method according to claim 1 or 2, characterized in that the activity of silica in the slag formed is high in order to eliminate lead from the blister copper.
AU2002325965A 2001-09-21 2002-09-20 Method for the production of blister copper Expired AU2002325965B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI20011859 2001-09-21
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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AU2002325965A1 AU2002325965A1 (en) 2003-06-05
AU2002325965B2 true AU2002325965B2 (en) 2008-01-24

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US (1) US20040244534A1 (en)
EP (1) EP1436434A1 (en)
JP (1) JP3828541B2 (en)
KR (1) KR100929520B1 (en)
CN (1) CN1295364C (en)
AU (1) AU2002325965B2 (en)
BR (1) BR0212651A (en)
CA (1) CA2459962C (en)
EA (1) EA005386B1 (en)
FI (1) FI115536B (en)
MX (1) MXPA04002601A (en)
PE (1) PE20030425A1 (en)
PL (1) PL197523B1 (en)
RO (1) RO122640B1 (en)
WO (1) WO2003025236A1 (en)
YU (1) YU24704A (en)
ZA (1) ZA200401902B (en)

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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
FI125793B (en) * 2014-05-14 2016-02-15 Outotec Finland Oy Procedure for converting materials containing 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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JP2005503481A (en) 2005-02-03
WO2003025236A1 (en) 2003-03-27
JP3828541B2 (en) 2006-10-04
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
PL197523B1 (en) 2008-04-30
US20040244534A1 (en) 2004-12-09

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