CA1107515A - Continuous smelting and refining of cement copper - Google Patents

Continuous smelting and refining of cement copper

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Publication number
CA1107515A
CA1107515A CA281,396A CA281396A CA1107515A CA 1107515 A CA1107515 A CA 1107515A CA 281396 A CA281396 A CA 281396A CA 1107515 A CA1107515 A CA 1107515A
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CA
Canada
Prior art keywords
copper
metal
kiln
gas
oxidizing
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
Application number
CA281,396A
Other languages
French (fr)
Inventor
Douglas Pollock
Omar Sobarzo
Rolando Urquiza
Carlos Vilches
Jamie Bolanos
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
De Acero Del Pacifico Sa Cia
Original Assignee
De Acero Del Pacifico Sa Cia
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by De Acero Del Pacifico Sa Cia filed Critical De Acero Del Pacifico Sa Cia
Priority to CA365,051A priority Critical patent/CA1115515A/en
Application granted granted Critical
Publication of CA1107515A publication Critical patent/CA1107515A/en
Expired legal-status Critical Current

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Classifications

    • 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
    • C22B15/006Pyrometallurgy working up of molten copper, e.g. refining
    • 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
    • C22B15/003Bath smelting or converting
    • C22B15/0032Bath smelting or converting in shaft furnaces, e.g. blast furnaces

Landscapes

  • 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)
  • Vertical, Hearth, Or Arc Furnaces (AREA)

Abstract

Abstract of the Disclosure Use of a shaft kiln in continuous smelting and refining of cement copper is made possible with a mix preheater, a re-fined gas preheater, an air preheater, an air feeder and forehearths for cement oxidation and reduction, and wherein oxidation is achieved by injecting oxidant gases and reduction by injecting preheated petroleum gas, subsequent to having placed a layer of charcoal on the smelt.

Description

I' 11~7515 The present invention relates to a novel shaft kiln and a method of continously smelting and refining cement copper therein and in related equipment.
The shaft kiln has an upper gas chamber, and inter- -mediate stack zone including coke charging means, a lower hearth zone including tuyeres for air injection, means for preheating charge with sensible heat from the upper gas chamber, pneumatic charge injectors to inject preheated charge into the intermediate zone, a gas off-take on the upper gas chamber including a heat exchanger for air pre-heating.
In operation, cement copper is mixed with fluxes and preheated in the preheater, and then injected with a ~ heated gas into the shaft kiln containing hot coke at the - 15 level of highest temperature, to effect rapid melting with-out dusting losses and formation of metal and slag phases, oxidizing the copper to puri~y it, and then treating the metal with a reducing agent, to produce high purity copper.
The present invention is directed to a method for obtaining metallic copper with a purity of 99.9% by direct fire smelting and refining of cement copper in a specially designed shaft kiln in a single,continuous operation. The present invention is advantageously employed in conjunction with the cont~ucus, high-purity process for producing granu-lar cement copper described in U.S. Patent No. 3,874,940, assigned to the same assignee as the instant application.
The shaft ~iln is a vertical furnace traditionally used for smelting iron, scrap iron or pig iron, and which is provided with nozzles or tuyeres at its lower end. It ~2751S

uses metallurgical coke as fuel and its interior carries a lining of refractory material. Such a kiln has three main parts:
(a) The lower section or hearth of the kiln, where the smelt metal descending from the charge in the shaft is collected. This part is provided with a lower outlet or tap to allow outflow of the melt.
(b) The intermediate section, situated immediately above the hearth is the area of the kiln exhibiting the highest temperature, and at its lower end are the tuyeres and wind boxes, through which air is blown in.
(c) The highest section of the kiln, above the mid-section, is where the loading gates or chutes are situated to receive the ore, coke, and flux.
In order to smelt metal, the shaft kiln uses the heat irradiated by an incandescent coke column that is ^ permeable to gases. It is provlded with combustion igni-tion and maintaining systems, and air is blown in through the tuyeres. Coke and iron scrap or whatever are loaded ~0 through the charging gates in alternate layers that descend progressively to the intermediate section to the extent that the fuel is consumed, and the metal completes smelting -- at this area of higher temperature. The smelt metal drips through the incandescent coke and deposits itself on the hearth.
It is impossible to smelt cement copper in a conven-tional shaft kiln, because on loading the cement through the upper gates, it is drawn by the gas current originating in the combustion zone and blown out of the furnace. Nor is it possible to load intermittently significant amounts 75~5 of cement, because its fine granulation obstructs the permeability of the incandescent column, causing the kiln to extinguish. Although in theory bri~uetted cement copper could be loaded alternatively with the coke, in practice this is not practical because the added cost of manufac-turing briquettes raises costs to non-commercial levels.
The present invention provides for loading the ce-ment mixed with flux directly to the intermediate section of the shaft kiln, avoiding the indicated inconveniences of loading through the upper gates, and without obstruc- ¦
ting the normal operation of the kiln. To this effect, specific improvements on the conventional shaft kiln have been designed, enabling cement copper smelting and refi ning to be carried out in a continuous process.
A general object of the present invention is to provide an improved shaft kiln for smelting and refining of cement copper.
Another object of the present invention is to pro-vide an improved method for smelting and refining of ce-ment copper.
A still further object of the present invention isto provide a method fox the cont~nous fire refining of cement copper.
The present invention provides a me~x~ of refi~u~
5 cement copper comprising:
mixing cement copper with desired fluxes and preheating the mixture;
injecting the mixture with a heated gas into an oxidizing shaft kiln at the level of highest temperature, to efféct rapid melting of said mixture without significant dust-ing losses and the formation of molten metal and slag phases;

:, 1~ 1'751S

oxidizing said metal phase to drive impurities into said slag;
removing said slag and covering said metal with a - reductant;
treating said metal with a reducing agent to pro-duce a copper of high purity; and recovering said copper.
miS invention ~her provides the metho~ of substantiallY
continuously refining ~t copper comprising:
maintaining a column of incandescent coke in an oxidizing shaft kiln;
continuously charging a preheated mixture of cement copper and desired fluxes into the hottest portion of said column by injection with a heated gas;
collecting molten metal and slag phases in a hearth of said kiln and transferring said phases to a forehearth;
oxidizing said metal to drive impurities into said s~g;
replacing said slag with a reductant;
treating said metal with a heated hydrocarbon gas to produce a copper of high purity; and recovering said copper.
Various other objects and advantages of the inven~
tion will become clear from the following description of embodiments, and the novel features will be particularly pointed out in connection with the appended claims.
Reference will hereinafter be made to the accompany-ing drawings, wherein:

-3a-7~;315 FIGURE 1 is a side elevation view, partly in section, of a shaft kiln in accordance with the invention;
FIGURE 2 is a side elevation view, partly in section, of the forehearth used in conjunction with the shaft kiln of FIGURE l; and FIGURE 3 is an end elevation of FIGURE 2.

As shown in FIG. 1, the ïnvention contemplates supp-lementing a conventional kiln ~.10 with a mix preheater 12 having a metal tray 14 that is placed in the upper part and over the kiln 10. This tray is indirectly heated by the as-cending stream of hot gases produced by combustion inside the kiln. Combustion gases flow through an oblique lateral shaft 16 protruding out the side of the kiln, immediately under the base of tray 14~ Coke is loaded.through a gate 1~ 18 situated on the side of the kiln, immediately under the upper gas chamber 20, from where the oblique shaft 16 ori-ginates.
Cement copper and fluxes are loaded onto the tray 14 through hopper 13. The mix is homogenized by means of a mixing pallet or rabble 22 propelled by a conventional motor located in the box 24. Tests have shown that the mix reaches a suitable temperature in the preheater for the purpose of this invention as described hereinbelowO The mix is unloaded continuously thxough the down pipe 26 into the hopper of an air feeder 30 upon being pushed therein by the mixing pallet 22.
Air mix feeder 30 comprises the receiving hopper 28 in~o which the mix drops from the tray 14 through the down pipe 26, and has a conical base connected to the pipe 32 ~751S

that penetrates into the inside of kiln 10. Hot air is carried by the pipe 32 and carries the mix that falls into the same tube from hopper 28. The location of feeder 30 v is important, and should be about 45-50% of the shaft height.
If the mix is fed too high, cement will be blown out; if the feeder is too low, unmelted cement will reach the hearth. The mix is dispersed in the column of incandescent coke and it smelts rapidly and drops in a liquid state in-to the kiln hearth, from which it continuously descends down the outlet 34 to the forehearth 36 situated directly under it.
Oblique lateral shaft 16 carries the outflow of com-bustion gases from the gas chamber 20 placed immediately under the metal tray 14. The shaft dimensions are conven-tionally established in relation to the characteristics of the kiln and it has an inclination of between 30 and 45, to facilitate collection of any fines therein and their return to the shaft by gravity, or removal through - gate 17.
To effect the heating of air blown into the air feeder through the tube 32, a coil 38 is set up inside the shaft 16, the dimensions of which are determined conventio-nally under the specifications for the desired operation.
Air is blown in by means of a conventional compressor (not shown) through a pipe 40, heated in the coil 38 by the latent heat of gases leaving through the shaft 16, and carried hot by pipe 32 to air feeder 30. A second coil 42 - is placed inside shaft 16 to heat the previously-gasified liquified petroleum gas supplied under pressure through pipe 44. The dimensions of the coil are determined con-~75~S

ventionally under the speci~ications of the desired opera-tion. The hot natural gas leaves under pressure through pipe 46 and is carried by conventi~nal means to the fore-hearth 36 for use in reducing the metal. The gas is heated in order to secure a more effective reduction in the fore-hearth.
As shown in FIGURE 2, forehearth 36 comprises conven-tional dumping containers, intern~lly lined with refractory material 47 and provided with conventional displacement means. A conventional burner 48 is provided on one of the walls to maintain the bath temperature. A lid S0 internally lined with refractory material is provided with a conven-tional gas outlet 52. The forehearth is provided with a drop hole 54, through which the smelted metal coming down the slag tap 34 of the furnace~ drops, and a tapping hole 56.
Forehearths 36 are dumpable or dumping the already refined copper into molds, and are displaceable so that they may be alternated among each other to receive smelted metal from the kiln and likewise in the refi~ingprocess that is carried out in the forehearth itself. FIG. 2 also depicts the other common elements of displaceable dumping containers, such as burner hoses, chassis, wheels, dumping shaft, handle and so forth. FIG. 3 is an end view of the forehearth ~hat best illustrates the foregoing.
In accordance with the invention, contin~us smel-ting and refining are carried out as follows: The kiln is ignited by conventional methods until it reaches operating temperature, coke being loaded via the loading gate 18.
Loading of cement and flux is started on the tray 14 to preheat them. The mixing pallet 22 homogenizes the mix, ~7~15 that drops down the pipe 26 to reach the air feeder 30.
Air is compressed by the compressor, carried by pipe 40 and preheated in the coil 38, wherefrom it reaches the air feeder through pipe 32 to enter into injector 30, that simul- .
taneously receives the mix from the hopper 28. The cement and flux mix is in-blown under pressure-together with air through the tube in the intermediate section of the $ur-nace, that is the one having the highest temperature in the incandescent coke column that drops inside the fur-nace. Experiments carried out indicate that intimate con-tact of the copper cement with the încandescent coke ef-fects the first reducing phase that eliminates the super-ficial oxide from the cement, thereby enabling easy smel-ting of the metal and minimum loss of fines caused by the furnace gas current. In the event of very fine or very old cements, which implies excess oxide, a reducing agent (fine coal, for instance) is added ta the mix at the tray 14.
The cement drops in the incandescent coke column, smelts and falls as liquid metal onto the'hearth of the kiln. Experience indicates that on passing in front of tuyeres 58 of the furnace, the metal undergoes its $irst oxidation, the'refore the refining process commences in the same furnace in a primary way. The'smelted copper reaches the bottom of the hear~h, where t~pping is carried out continuously with an open tap hole. On leaving the tap hole, contact of liquid copper with the'atmosphere con-tinues, and the oxidation reaction started in passing in front of the tuyeres continues.

The liquid metal and the slag fall in the forehearth through the drop hole 34, The bath temperature at the fore-hearth is maintained by activating the burner 48. Once copper has been accumulated to the extent of l/4 of the total capacity of the forehearth, oxidation of the copper begins. To effect this, the in~ection nozzle 60 is connec-ted to a hose blowing in air, oxygen, or conventional mix-ture of the two, thereby originating direct oxidation, con-trolled under conventional techniques, of the remaining impurities of the metal. The main impurity is iron, and this is captured in the oxidation process by the slag tp form silicates. Progress of the oxidation process is deter-mined by sample fracture, according to tec'hniques known to experts, and by conducting periodic flushing to elimi-nate impurities. In the bath, the'liquid copper and theslag are separated by the difference of specific gravity, as known in the art.
Once ~he forehearth has been filled, it is with-drawn from the furnace and replaced by another that con-tinues to receive the'liquid metal from the kiln. All of the slag is removed from the oxidized bath in the fore-hearth, and a charcoal layer is added. Subsequently, a conventional injection nozzle is introduced, connected to the pipe 46 through which the reduction gas flows under pressure. This is cracked at 800C. in the coil 42.
Partial cracking of the gas is featured by the short and brilliant flame it reflects, as known to the experts in the art, and which is necessary for the reduc-tion phase that is carried out in the forehearth. This is the finaI phase of the process according to the invention, ' .

1~i';~75~ s and its duration is controlled by conventional sample fractures.

Once the reduction phase is completed, the copper is refined and it is then cast on molds in the ordinary fashion.
The forehearth is then free to return the kiln and, there-fore, start a new cycle.

EXAMPLES
During a first phase, tests are carried out to obtain an experimental verification of the smelting process of copper in a shaft kiln, adjust the operation and optimize operating parameters. Only limited loads of copper cement were used, because only one forehearth to receive the smel-ted copper was available. The following are typical values of this sequence:
Loads: 200 kg cement copper, 68 to 80% Cu and 8 to 12% Fe 26 kg SiO2 (13% of the cement load~ as flux 13 kg Na2CO3 (6.5% of the cement load) as flux The furnace operates at a conventional temperature of about 1300~C., which is also maintained in ; 20 the forehearth by burner 48. The charge preheater was ef~ec-tive to heat the Gharge to about 100-120C., which was satisfactory. Alr from coil 38 was preheated to about 600 -700C.
Flows used were as follows;
cement injector air : 19 to 20 ft3/min pressure 2 kgr/cm2 oxidation air : 8 ft3/min liquified gas (L.P.G.) : 0.33 kg/min 75~5 preheating coke : 35 to 40 kg smelting coke : 50 to 60 kg granulation of coke used : 100% between 2" + 3"
Times for phases carried out were:
loading smelting in kiln : 50 to 60 min oxidation in forehearth : 15 to 20 min In the series of tests carried out, reduction was accomplished with poling and gas, with and without pre~
heating.
Times employed in each case are as follows:
- Poles = 35 to 45 min - Unheated gas = 30 to 45 min - ~eated gas = 4 to lO min It was possible to appreciate that on reducing with poles and unheated gas, the endothermic nature of the reac-tion rapidly cooled the bathO The case was different on reducing with preheated natural gas at approximately 800C, when it was observed that the bath did not cool off, but in fact increased its temperature. Those skilled in the art will appreciate that the gas system must be purged of air before start-up to avoid explosion hazards.
Pilot experiences showed the following results;
Smelting speed was 260 kg/hour of total load. With fresh, hi~h purity cement copper, this smelting speed may repre-sent 220 kg/hour or more of fine copper. Coke rate was 22 to 25% of the total load.
This figure is for the pilot equipment, and a lower - coke rate would be expected in an industrial facility. This consumption figure does not include preheating coke for the bed, as this is a fixed quantity.

1~i{D7515 Copper of 99.9~ purity was obtained in a consistent fashion.
Through mass balances, it has been determined that the highest loss was 5% of the copper loaded. This figure may be considered as maximum, inasmuch as there are frac-tions of the copper obtained that remain embedded in the lining or in splashes that are hard to detect and that, because they represent small volumes peculiar to a pilot operation, have a greater incidence than they would in an industrial operation.
Various changes in the details, steps, materials and arrangements of parts, which have been herein des-cribed and illustrated in order to explain the nature of the invention, may be made by those skilled in the art, within the principle and scope a~ the invention as defined in the appended claims.

Claims (12)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. The method of refining cement copper comprising:
mixing cement copper with desired fluxes and preheating the mixture;
injecting the mixture with a heated gas into an oxidizing shaft kiln at the level of highest temperature, to effect rapid melting of said mixture without significant dusting losses and the formation of molten metal and slag phases;
oxidizing said metal phase to drive impurities into said slag;
removing said slag and covering said metal with a reductant;
treating said metal with a reducing agent to produce a copper of high purity; and recovering said copper.
2. The method as claimed in Claim 1, wherein said mixing and preheating are carried out in a heat-exchange relation with said shaft kiln.
3. The method as claimed in Claim 1, wherein said oxidizing step is carried out with a fluid selected from the group consisting of air, oxygen-enriched air and substantially pure oxygen.
4. The method as claimed in Claim 1, wherein said fluxes are selected from the group consisting of silica, sodium carbonate, glass, and mixtures thereof.
5. The method as claimed in Claim 1, wherein said reductant is charcoal.
6. The method as claimed in Claim 1, wherein said reducing agent is a heated hydrocarbon gas.
7. The method as claimed in Claim 1, wherein said oxidizing, reducing and recovery steps are carried out in a vessel separate from said shaft kiln.
8. The method as claimed in Claim 6, wherein said hydrocarbon is natural gas at about 800°C.
9. The method of substantially continuously refining cement copper comprising:
maintaining a column of incandescent coke in an oxidizing shaft kiln;
continuously charging a preheated mixture of cement copper and desired fluxes into the hottest portion of said column by injection with a heated gas;
collecting molten metal and slag phases in a hearth of said kiln and transferring said phases to a forehearth;
oxidizing said metal to drive impurities into said slag;
replacing said slag with a reductant;
treating said metal with a heated hydrocarbon gas to produce a copper of high purity; and recovering said copper.
10. The method as claimed in Claim 9, wherein a single shaft kiln is used in conjunction with a plurality of said forehearths.
11. The method as claimed in Claim 9, wherein said oxidizing step is carried out with a free-oxygen containing gas, and said hydrocarbon is a natural gas at about 800°C.
12. The method as claimed in Claim 1, wherein said preheated mixture is charged at a point between 45 and 50%
of the height of said kiln.
CA281,396A 1976-06-28 1977-06-27 Continuous smelting and refining of cement copper Expired CA1107515A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CA365,051A CA1115515A (en) 1976-06-28 1980-11-19 Cupola furnace to enable continuous smelting and refining of cement copper and method therefor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US05/700,217 US4056262A (en) 1976-06-28 1976-06-28 Cupola furnace to enable continuous smelting and refining of cement copper and method therefor
US700,217 1976-06-28

Publications (1)

Publication Number Publication Date
CA1107515A true CA1107515A (en) 1981-08-25

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US (2) US4056262A (en)
JP (1) JPS5325220A (en)
AT (1) ATA461077A (en)
AU (1) AU510112B2 (en)
BE (1) BE856122A (en)
CA (1) CA1107515A (en)
DE (1) DE2729184A1 (en)
ES (2) ES460138A1 (en)
FI (1) FI771982A (en)
FR (1) FR2361470A1 (en)
GB (1) GB1532204A (en)
IL (1) IL52385A (en)
IT (1) IT1084570B (en)
NO (1) NO772227L (en)
SE (1) SE7707398L (en)
ZA (1) ZA773721B (en)
ZM (1) ZM5177A1 (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4369955A (en) * 1980-06-25 1983-01-25 Park Ki D Cupola furnace system
US6478847B1 (en) 2001-08-31 2002-11-12 Mueller Industries, Inc. Copper scrap processing system
CN100523233C (en) * 2006-09-29 2009-08-05 宁波金田铜业(集团)股份有限公司 Energy-saving and environmental-protection refining furnace
CN104388692B (en) * 2014-10-31 2016-06-08 宁波大学 A kind of low-grade copper smelts the environment protection method of high-quality positive plate
CN104342563B (en) * 2014-10-31 2016-05-11 宁波大学 A kind of energy-conservation smelting process of low cost equipment of low-grade copper raw material
CN104388693B (en) * 2014-10-31 2016-08-31 宁波大学 A kind of low-grade copper smelts the power-economizing method of high-quality positive plate
CN104313345B (en) * 2014-10-31 2016-05-11 宁波大学 A kind of low-grade copper is smelted the power-economizing method of high-quality positive plate low cost equipment
CN104388694B (en) * 2014-10-31 2016-06-08 宁波大学 A kind of low-grade copper smelts the environment protection method of high-quality positive plate low cost equipment
CN104313344B (en) * 2014-10-31 2016-05-11 宁波大学 A kind of low-grade copper draws the environment protection method of electrician's copper bar on smelting
DE102017105551A1 (en) * 2017-03-15 2018-09-20 Scholz Austria GmbH Process for the treatment of metallurgical slags

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US284384A (en) * 1883-09-04 colliatj
US234384A (en) * 1880-11-16 Thread-cutter
US711173A (en) * 1901-06-15 1902-10-14 Duncan Mckechnie Process of recovering metallic copper from copper precipitate.
US1198434A (en) * 1916-04-26 1916-09-19 Ulysses A Garred Copper-refining.
US2194454A (en) * 1936-09-03 1940-03-19 William E Greenawalt Metallurgical process and apparatus
US2746858A (en) * 1953-02-09 1956-05-22 Claude B Schneible Company Inc Cupola furnace and method of treating gases therefrom
US3490899A (en) * 1966-10-18 1970-01-20 Continental Copper & Steel Ind Refined copper and process therefor
US3892559A (en) * 1969-09-18 1975-07-01 Bechtel Int Corp Submerged smelting

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US4056262A (en) 1977-11-01
NO772227L (en) 1977-12-29
BE856122A (en) 1977-10-17
AU2641777A (en) 1979-01-04
ZM5177A1 (en) 1978-02-21
DE2729184A1 (en) 1978-01-05
GB1532204A (en) 1978-11-15
AU510112B2 (en) 1980-06-05
IT1084570B (en) 1985-05-25
ZA773721B (en) 1978-05-30
ATA461077A (en) 1981-02-15
IL52385A0 (en) 1977-08-31
SE7707398L (en) 1977-12-29
US4090870A (en) 1978-05-23
ES464256A1 (en) 1978-08-01
FR2361470A1 (en) 1978-03-10
JPS5325220A (en) 1978-03-08
FI771982A (en) 1977-12-29
IL52385A (en) 1979-10-31
ES460138A1 (en) 1978-05-01

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