FI57090B - SAETT ATT REGLERA VAERMEINNEHAOLLET OCH UTJAEMNA TEMPERATURER I OLIKA SULFIDERINGSPROCESSER - Google Patents

Description

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Patent * · och reglftentyreltan Arnttlun utl »* d och uti.ikrHtan pubiie« r * d 29.02.80 (32) (33) (31) Pyydetty etuolkeu »—Begird prlorlMt (71) Outokumpu Oy, Outokumpu, FI; Töölönkatu 1+, 00100 Helsinki 10,

Suomi-Finland (FI) (72) Simo Mäki pirtti, Nakkila, Pekka Tapio Setälä, Nakkila, Finland-Finland (Fl) (7 ^) Berggren Oy Ab (3I +) A way to regulate the amount of heat in different sulphidation processes and equalize temperatures - Sätt att reglera värmeinneh & llet This invention relates to the control of various sulfidation processes. The invention relates mainly to the control of sulphidation processes which aim, in the mainly solid state, for the sulphidation of complex minerals containing Cu, Ni, Co, Zn, Pb, Fe as the main component and, in addition, impurity metals. The purpose of sulphidation is then to decompose the original complex minerals and at the same time to convert the main metals and impurities they contain into stable independent sulphides. Such sulfidation-based conversion requires the use of high sulfur vapor partial pressures to provide sufficient reaction rates as well as stable sulfides, usually of high sulfur content. On the other hand, many complex minerals melt at relatively low temperatures, so sulfidation must be performed under conditions where the melting temperatures of the mineral matrices are not exceeded and / or where the use of high sulfur pressures raises the melting temperature ranges of the decomposing and regenerating mineral matrices. Such sulfidation processes are usually carried out in the temperature range of 700-1200 ° K (427-927 ° C) and in the sulfur vapor partial pressure range of 0.1-1.0 atm.

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When high sulfur pressures are used, the amount of heat required for processing must be introduced into the system indirectly, because e.g. the use of fossil fuel in the reaction space leads to a decrease in the partial pressure of sulfur and also to sulfur losses due to flue gas reactions. Indirect heating of sulfidation systems, in turn, easily causes melting and sintering of complex minerals, because due to the poor heat transfer properties of the mineral powders, a large temperature gradient must be used in the transfer.

The method according to the invention eliminates the need for external heat transfer and internal fossil fuel in sulphidation plants.

The process according to the invention can also be used for high-temperature sulfidation processes, melt-refining, etc.

Likewise, the method according to the invention is quite independent of the equipment and other technology used in the processes. Because of the new method, elemental sulfur vapor is easily recycled, no pollutants are present, and both solid and gaseous product phases are condensed into powders or sulfur polymers, the new process is almost irreplaceable in many sulfidation processes not only for energy savings but also for labor and nature protection.

The process of U.S. Pat. No. 3,459,535 improves the solubility of copper in Cu-Fe-S minerals in acidic, oxidative autoclave leaching. This is done by treating said minerals in a temperature range of 300-600 ° C in contact with elemental sulfur and this steam. The treatment takes place in an externally heated retort. It can be shown that below 501 ° C chalcopyrite and bornite are sulphidated to idite (Cu ^ FeSg) as well as pyrite. Above 50i ° C, the bornite becomes stable again, and above 508 ° C, in addition to the bornite, chalcopyrite becomes stable.

Analogous to the above is the process according to USP 3,817,743, in which chalcopyrite is sulfided at a temperature in the range of 460-500 ° C to X-bornite (Cu3FeS2 phase with an excess of sulfur of about 0.5% by weight) and idite at sulfur pressure P <200 mmHg .

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Among the above-mentioned older processes, mention may be made of the process according to U.S. Pat. No. 1,523,980 (Colcord or Hulst process), in which molten lead is sulfided with elemental sulfur (solid or vapor) to separate copper as an impurity as solid digenite. In the process according to DE 497 312, sulfur or sulfur donors are added to a molten metal or alloy (Pb, Sn, Sb and the like) to remove copper as sulphide. Pitch, tar, etc. are used as reducing agents in the process. In the process according to DE 431 984, the impurity metals, Zn, Pb, Cu and the like are removed from the crude antimony as sulphides by adding and melting. The use of elemental sulfur vapor to determine phase equilibria is a commonly used, albeit difficult, method. A view of various method applications can be found in the publications: H.E.

Maxwin, R.H. Lombard: Econ. Geol., 32, 1937, 203-284 and T. Rosenqvist, T. Harvlg: Meddeledse Nr. 12 fra Metallurgisk kornit ^, Trondheim, Norway, May 1958, 21-52.

Reduction-sulphidation processes aim at the reduction of oxide ores at low temperatures and at the recovery of precious metals present in these low concentrations, either as an alloy or as a sulphide rock. The group includes quite a number of methods for refining Ni, Co and Cu-containing limonite and / or serpentite laterite ores. Precious metals are reduced and sulphidated from the ores, and the product obtained is separated from the side rock by conventional methods (dissolution, magnetic separation, smelting, etc.). The reduction and sulfidation take place in the temperature range of 700-1100 ° C in a tube furnace or fluidized bed reactor (e.g. patents: USP 3,004,846; 3,030,201; 3,272,616), and the sulfidation means is usually a reducing gas (H2S, COS, etc.). . Many sulfur-donating substances, pyrites, sulfur injection into flue gases, SO 2 feed to reduction zones, S-containing crude oil, etc. can be used for sulfidation (e.g. patents: USP 3,388,870; 3,535,105; 3,772,423; 3,819,801).

Common to said sulfidation processes is that when attempting to produce metallized or conventional sulfide rock as a solid or molten phase, the sulfur pressure required for sulfidation is generally very low. Examples are nickel sulphidation reactions: NiO - + Ni ♦ Ni + Ni ^ Sj + x:

700 ° C: Ps, ^ 10 “10-3.7x10” 10 atm. stone: 20.6-21.8% by weight S

900 ° C: Ps2 1.5x10 -10 atm. stone: 19.2-30.3 weight- * S.

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The group of methods in which the impurities of concentrates and ores are to be evaporated or converted into an easily separable form, as in the previous one, has a large number of patented and / or otherwise disclosed methods. In the process according to USP 1 762 867, the distillation of the impurity components of mainly copper complex concentrates and technical intermediates is carried out by evaporating the sulphides of the metals Hg, As, Sb, Sn, Cd and finally the zinc sulphide in the temperature range 600-1200 ° C, leaving the remaining product phase C -Fe-Sulfide matte. When applying the method, for example in a tube furnace, sulfur or sulfur-releasing compounds, iron and limestone are added to the charge in addition to coke, if necessary (to avoid the effects of the low melting point of sulphides). The charge is heated by counter-current flue gases, which allow the volatile sulfides to be oxidized before they leave the furnace space.

Quite known is the method according to patent DRP 504 487 (Skappel) for the treatment of complex ores. In one embodiment of the process, the impure concentrates or industrial intermediates are melted or sintered together with sodium sulfide (Na 2 S, Na 2 SO 4 + C, etc.) to form suitable eutectic gums and Na 2 S-MeS double salts in the system. The product obtained is decomposed with water into a powder-slurry mixture containing separate sulphides, from which the separate sulphide phases can be separated by conventional means. When the charge is heated or melted, some of the impurities evaporate and some are removed in the water washing step (e.g. As). The temperature range for the application of the method is between 600 and 1600 °, depending on the raw material.

In the process according to Finnish patent 49 186, reduction sulphidation is carried out on serpentine barrels at low temperature. The metallized sulfide obtained by sulfidation is filter-melted using the melt solubility opening of the Me-MeS system into sufficiently large granules (while the oxidizer remains solid). The metals of the Me-MeS system are divided by continuous annealing from the area of the solubility orifice at a decreasing temperature so that Ni, Co, Pt metals, (Fe), etc. are enriched in the metal phase and metals Cu, Cr, Mn, etc. are separated into the sulfide layer surrounding the phase. -MeS system from the oxide matrix as well as the Me phase from the MeS phase by conventional means.

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In the above-mentioned methods, the amount of heat required for processing is fed to the feed by means of fossil fuel in the reaction space. The sulfur potential of the system then remains low.

In the method according to Finnish patent application No. 1912/74, the components of complex concentrates are disassembled from their complex compounds and re-stacked into stable independent sulphides corresponding to the new conditions for both main metals (Cu, Ni, Co, Pb, Zn) and impurities (As, Sb, Bi, Se, Te, Ga , In, Te, Hg, Ge, Sn, etc.). Some of the impurities evaporate quantitatively under the treatment conditions (600-800 ° C, Pg = 0.25-1.00 atm) and some can be separated after processing by conventional means. The method does not usually require additional heat. feed to the sulfidation furnace. Among the methods that work with additional external technology, the method that has been extensively studied today should be mentioned, where e.g. arsenic is evaporated from its compounds by heating these (Fe, Cu, Ni, Co-based sulfides or arsenides) with pyrite. However, the amounts of pyrite required are large. The decomposition of pyrite to obtain sulfur in reactions also requires very large amounts of energy (e.g. HW. Loose: Chemismus der Entfernung von Arsen aus senen Verblndungen mit Eisen, Kupfer, Nickel und Kobalt dure Erhitzen in Anwesenheit von Pyrit, Dissertation Arbeit, Breslau 1931, 1-73) .

It is therefore an object of the present invention to provide a method for controlling the amount of heat and for stabilizing the temperatures of various sulphidation processes carried out in a sulfur vapor atmosphere, and the main features of the invention appear from the appended claim 1.

The control method according to the invention utilizes very high dissociation-recombination energies associated with changes in atomic number as a molecule of sulfur vapor in the temperature and pressure range mentioned below. These amounts of energy released or bound are functions of both sulfur vapor temperature and partial pressure.

The amounts of dissociation-recombination energy are so large that they are sufficient in many low temperature sulfidation processes to cover the amounts of energy required for sulfidation reactions, impurity evaporation, and heat loss from equipment. In this case, the sulphation processes are made economically self-sufficient, by controlling only the temperature and / or the partial pressure of the sulfur vapor fed to the sulphification plant.

The new method of regulating and controlling sulphidation processes operates in the temperature range of 400-900 ° C and in the elemental sulfur vapor partial pressure range of 0.1-1.00 atm.

The invention is mainly directed to the treatment of predominantly sulfide complex ores containing copper, zinc, lead, nickel, cobalt and iron as the main metal, which ores have been formed as a result of low temperature and pressure penumatolytic and especially hydroternic mineralization. These ores are usually stacked with a large amount of heavy elements as an impurity, which effectively prevents the technical exploitation of these ores. Common to these complex minerals is e.g. the fact that they both form and decompose and / or melt at quite low temperatures. The sulphidation of these minerals, in order to separate the sulphides of both the impurities and the main components into their own phases, must be controlled in terms of the order of events, the rate, the amount of sulphidation and other factors so that no melt phases are formed.

The process according to the invention makes it possible to carry out the sulfidation process with respect to heat. In this case, the amount of heat provided by the actual exothermic mineral sulfidation event should be sufficient to cover the heat loss of the processing device, the evaporation enthalpies, and the amount of heat required to heat the sulfidation medium and concentrate from the preheating temperature to the reaction temperature. Thus, no additional heat is supplied to the sulfidation system by fossil fuel in the reaction space or by externally heating the processing equipment. In most cases, such an additional heat supply would be very difficult to achieve due to the low melting temperature range of the material to be processed or the high sulfur potential required.

In the new method under consideration, the temperature balance of the sulphidation system is controlled by preheating the ore to a temperature where no chemical or physical changes harmful to processing occur in the matrix of complex minerals. recombination-thermal quantities. These heat amounts are utilized by adjusting the sulfur vapor feed temperature and partial pressure, as well as the central feed point for the sulfur vapor and other feed components.

By means of the method according to the invention, in addition to the system temperature balance, the melting temperature ranges of complex minerals, the rate of sulfidation reactions, the structure of the product rice, the structure of impurity sulphides remaining in the matrix as well as impurity compounds volatile under process conditions can be controlled. The use of this method enables the use of sulphidation technology, which is even more versatile and at the same time simpler, quite economical and independent of the most frequently used technical equipment. Using the method, it is also possible to carry out sulfidation processes requiring high sulfur potentials which were not possible before.

The process according to the invention thus regulates the course of the various sulphide processes, taking advantage of the large changes in the heat content of the gas phase associated with the dissociation and recombination of the sulfur vapor molecules. As an example of the ratio of heat amounts: At one atmosphere pressure, temperature, T = 700 ° K is the average atomic number of sulfur vapor molecules, V = 6.97 and enthalpy values (kcal / kg S): gas enthalpy, ΔΗ700_2 ^ ρ = 62.82 and heat of formation,

Allege = 170.36. At temperature, T = 1100 ° K are the corresponding values: V = 2.07, ΔΗ ^ 100_298 = 96.58 and ΔΗ ° 29β = 575.14. The amount of heat available for process control is thus in the temperature range A (AHe + f) = 404.78 kcal / kg S. Of this amount, conventional thermal gas enthalpy then accounts for only 8.3% and dissociation-recombination energy for 91.7%. As a function of temperature, this dissociation energy is also a function of the partial pressure of sulfur vapor and such that the energy change corresponding to the change in the atomic number of molecules occurs at different partial pressures in different temperature ranges. The suitability of sulfur vapor for the control of sulfidation processes is thus quite wide in its field of application and specifically in methods where the partial pressure of sulfur vapor varies between, Ps = 0.1-1.00 atm and in the temperature range, T = 70-1-1200 ° K. In addition to the temperature control of the processes, the final states of the reaction products, the assembly, cooling, the order of sulfidation events, ignition, etc. can be controlled by the peculiar behavior of the sulfur vapor.

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The method according to the invention is particularly suitable for carrying out sulfidoin processes which require even high element partial pressures. Indirect transfer of external heat is in processes usually difficult due to the low heat conductivity of concentrate and ore powders as well as the melting of complexes. On the other hand, direct heating of the reaction space, e.g. with flue gases, is not suitable. As a result, the partial pressure of sulfur decreases and the formation of harmful, sulfur-consuming gas components (COS, HjS, etc.). The use of combustion gases would also lead to harmful dust problems in the processes, in addition to gas pollutants that pollute the environment and are technically difficult to deal with. It is clear that the method is also suitable for use in many high temperature sulfidation processes.

Briefly mention some of the sulfidation processes within the scope of the process according to the invention:

Disintegration of impure complex marriages and re-stacking of the matrix (eg Finnish patent application no. 1912/74).

Sulphidation of impurities into their own non-volatile minerals (partial melt processes) and multi-stage sulphidation processes (pre- '^ r-kits 4 and 5).

- Low temperature sulfidation processes in which the pre-heating, ignition and quenching processes of the concentrate are performed using elemental sulfur (Examples 1-3).

Colcord and similar processes (USP 1,523,980).

Refining of antimony and tin alloys (DRP 431 984, British Patent No. 1,348,278).

Constant temperature sulfidation processes - Matrix changes of copper concentrates for dissolution as continuous processes (USP 3,459,535).

- High temperature zone reduction sulfidation processes in zone temperature control (USP 3,754,891; 3,900,310).

The process according to the invention is well suited for the treatment of predominantly sulfide complex ores containing the metals Cu, Zn, Pb, Ni, Co, Fe and the like as the main metal, which have been formed in part by pegmatite pneumatolytic and especially hydrothermal mineral formation. The mineral-forming "solutions" (temperature 400-450 ° C, pressure 225-250 kg / cm 2) are then enriched with 9 57050 high-order elements of the periodic table, which are easily mobile in the operating range of the process and have a high vapor pressure (but harmful to the parent metals). considered as impurities). The structure of such ore minerals can be altered by a suitable sulfidation treatment so that the impurities and parent metals form their own independent sulfides, which can be separated from each other by conventional methods.

In this context, on the basis of the Coalition Party, some mineral groups should be mentioned:

Pyritic and arsenic, antimony-rich groups: (Fe, Co, Ni) (S, Se, Te, As) ,, (Fe, Co, Ni) (As, Sb) S> Cu (Fe, Ga, In) S, 2 2

Cu3 (Ge, Fe, As, Sb) S4 and others.

Lead, zinc and silver groups: (Cu, Ag) 20 (Fe, Zn, Hg, Ge, Sn) 4 (As, Sb, Bi) 0S2g, (Zn, Cd, Hg) (S, Se, Te),

Pb ($, Se, Te).

Tin, zinc and silver groups:

Cu3 (As, Sb, Fe, Ge, V) S4, Cu2 (Ag, Fe, Zn, Sn) S4.

Cobalt, nickel, silver, bismuth, uranium groups: (Co, Ni, Ag, U) (As, Bi) 3.

Arsenic, amtimonj, bismuth complex minerals:

Ag3 (As, Sb) S3, Cu3BiS3, Cu (Sb, Bi) S2 »Ag (As.Bi) S2, (Pb, Cu) (As, jb, Bi) S3 and others.

In addition to natural minerals, many technical high temperature intermediates containing similar impurities, but not complex, are within the scope of the process according to the invention.

The control method according to the invention is thus based on the utilization of the dissociation energy of the molecules associated with the change in the atomic number of the sulfur vapor molecules as a function of partial pressure and temperature.

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It is known that sulfur vapor has a very complex structure. The fine structure of the individual vapor molecules is almost unknown. The quantitative role of different vapor molecules in the gas phase is also controversial. The heat of formation of the molecular species as well as the specific heat are already known, at least technically, with sufficient accuracy, so that the total enthalpies of the individual components of the gas phase can be calculated relatively accurately.

The invention will be described in more detail below with reference to the accompanying drawings, in which Figures IA and IB show concentrations and enthalpy of sulfur vapor molecules as a function of temperature, Figure 2 shows total sulfur vapor pressure as an average atomic number and temperature of the entire apparatus and Figure 5 shows a stability plot of minerals as a function of sulfur activity and temperature.

Appendix IA shows the concentrations of sulfur vapor molecules Sy (v * 2-8) as a function of temperature. Of particular note is the almost complete absence of the sulfur molecule used in conventional calculations from the gas phase. The total alpha of sulfur vapor (referenced to solid rhombic sulfur) has been calculated in Figure IB corresponding to vapor pressures Ps = 1.0 and 0.1 atm. The figure also shows the change in the average atomic number of the gas phase molecules as a function of temperature. Figure 2 calculates the total pressure of sulfur vapor as a function of the average atomic number and temperature of its vapor molecules. The change in the total vapor pressure to the atomic number of the molecule at two partial pressures of the dissociated vapor is marked as a parameter in the figure.

The dissociation energy used to control sulfidation is seen qualitatively in Figure IB. At a temperature of 1100 ° K (827 ° C) there is a total heat content of sulfur vapor at one atmospheric pressure, AHe + f 575.1 kcal / kg. The average atomic number of vapor molecules at t 1 is v «2.07.

As the gas phase cools to 700 ° K (427 ° C), 404.7 kcal / kg of heat is released by the recombination of sulfur molecules while the sulfur remains vaporous (700 ° K, AHe + f * 170.4 kcal / kg, 11 57090 v = 6, 97). The amount of heat released is thus 240% of the amount of heat required to melt and evaporate the sulfur to a temperature of 700 ° K. It can be seen from Figure IB that the partial pressure of sulfur vapor in the gas phase has a fairly large effect on the dissociation-recombination energy temperature range.

The amount of energy released or bound over a wide range of sulfur vapor temperatures and partial pressures allows for a versatile technical application of the phenomenon in many sulfidation processes, especially at low temperatures.

For the enthalpy change of sulfur vapor as a function of temperature, e.g. isobaric approximate equations in the following form: pg = 1.0 atm, T = B00-1000 ° K, AHe + f, kcal / kg S exp10 (~ 159'568 + 1 ^ 4'577 x - 69.002 x 10-V + 46727 / T)

Pg <0.1 atm, T = i700-900 ° K, AHe + f, kcal / kg S * exp1Q (-198.922 + 257.952 x 10 "3T - 108.538 x 1θ" 6Τ2 + 51673 / T).

Similar approximate equations can be calculated for all partial pressures by determining the gas phase composition. It should be noted that the equation is not in itself exactly in line with reality, because in processing, corresponding to the consumption of the amount of sulfur, a partial pressure change follows, which the equation itself does not take into account.

Sulfur vapor dissociation by thermal excitation:

The establishment of an equilibrium between the molecular species of sulfur vapor is a very slow process, especially at low temperatures. In equilibrium, sulfur represents an intermediate case between organic and inorganic compounds. The evaporation temperature of sulfur as well as the evaporation temperature is lower than that of other inorganic substances and on the other hand only slightly higher than that of most organic compounds (sublimation energies, & 29β 'kcal / g-at: 2.87-2.97, f 19.2 / Te, 29.0 / As, 49.3 / Sb, etc.). The vast majority of organic compounds as well as their vapors are thermodynamically metastable. The slow equilibrium is apparently also the cause of some of the many allotropies of sulfur.

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The activation energy of sulfur vapor equilibration is proportional to the energy of the s-s bond in the ring molecules in which all sulfur molecules apparently occur. All sulfur molecules have a 2-bond obvious. The dissociation energy of molecules increases only slightly with increasing atomic number: D298 'kcal / Atom; l ·; 50.85 (S2, 54.40 / Sj, 54.73 / s2, 60.56 / Sg, 61.90 / Sg, 62.31 / S2 and 63.06 / Sg). Selenium, which in many respects is analogous to sulfur, does not show imbalance conditions at low temperatures. Its binding energy as well as evaporation: temperature show lower and higher values than sulfur values, respectively.

Due to the behavior of the sulfur vapor, it is preferable to prepare it under reduced pressure and using a suitable catalyst. In the method under consideration, a carrier gas is used for the production of sulfur vapor, which is impregnated with molten sulfur and fed to a preheating device.

The vapor pressure of molten sulfur is of the form:

Log (P / atm) = -6109.6411 / T + 16.64157 -17.05358 X 1θ "3Τ + 7.9769 x 10_6T2

The partial pressure of the resulting sulfur vapor is adjusted by adjusting the temperature of the molten sulfur bath. When, for example, a sulfur bath temperature of 427 ° C is used, the partial pressure of the steam obtained is Pg = 0.767 atm and the average atomic number of its molecules corresponds to v = 6.62. The preheating device then gives a gas phase at 600 ° C: Pg = 0.845 atm, v = 4.05 and at 700 ° C a gas phase: Pc = 0.01 atm,

A thermally resistant general sulfur catalyst is suitable as the equilibrium catalyst for sulfur vapor. Particularly suitable for this purpose is a chromite catalyst which, in addition to excellent catalytic capacity, has good thermal conductivity, thermal resistance and also a small but effective surface area per unit weight compared to other catalysts (the space requirement of the catalyst is small due to the high density).

Figure 3 shows a sulfur vapor production device used in the new method. The device operates at atmospheric pressure. The evaporator 2 consists of two nested electrically heated tanks.

S 7 O 9 O

The temperature of the outer tank 15 is well below the evaporation point of the sulfur, so that the elemental sulfur can be fed to the tank in a solid state. The inner tank 16 is an externally thermally insulated electric evaporator which forms an integral container with the outer tank 15. The sulfur vapor is lifted from the tank by means of preheated nitrogen 4. From the evaporator, the sulfur vapor and the carrier gas flow to an electric ethno heater 3 filled with chromite catalyst, where the sulfur vapor is given the desired temperature and the corresponding equilibrium state. From the preheater, steam flows through an electrically heated pipe to the reaction space 1 of the sulfidizer, where the preheated concentrate is also fed.

Figure 4 shows an apparatus arrangement for performing sulfidation processes. The apparatus comprises a concentrate preheating device 6 with feed and heating devices 7, a sulphidation device 1 with feed and discharge devices (sulphidated product concentrate 8, gas phase 9, sulfur polymer 10), an evaporator device 2 corresponding to Figure 3, a steam dissociation device 3 and a nitrogen evaporator.

Utilization of thermal dissociation-recombination energy of sulfur vapor in process control of sulfidation processes:

The new control method is mainly applicable to sulphidation processes carried out at high sulfur vapor partial pressure and often at low temperature. These processes are usually quite complex in terms of the mechanism and thus the technological operation required. For this reason, the examples considered also contain essential parts of the theoretical foundations of the control method. The examples include only part of the scope of the new method.

It should also be noted that some of the high sulfur partial pressure sulfidation processes in the present field of application cannot currently be performed in any other way, so the importance of the control method as the only process control method is completely crucial.

In order to determine the sulfidation processes under consideration, the stability ranges of the starting and product minerals of the application examples as well as the gas phases as a function of temperature and sulfur activity have been calculated in Figure 5. From the temperature and sulfur pressure values given in the examples, the reality of the sulfidation processes can be stated.

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Example 1

The example contemplates the processing of a sulfide cobalt arsenide concentrate in which the complex mineral contained in the concentrate is decomposed and sulfided to a more stable compound. The arsenic contained in the concentrate is removed from the system together with the sulfur vapor. In this case, the partial pressure of sulfur in the vapor phase must be sufficient both to keep the volatile arsenic sulphide stable and also to maintain the mineral composition of the sulphide concentrate obtained as a product approximately equal to the mineral balance: (Co, Fe) S2 + FeyoS12. According to the stability drawing of Figure 5, at 1000 ° K (727 ° C), the partial pressure of sulfur vapor must be above 0.1 atm before and after sulfidation (stability range CoSj-FeS ^ ^; As ^ Sg (g) boils at 980 ° K).

The heat and mass balance calculations corresponding to Example 1 with the calculation bases and explanations used are summarized in Table 1.

The partial pressure of sulfur vapor in the feed gas phase was Pg = 0.50 atm and in the product gas phase P_ = 0.255 atm, respectively, so that it is in the correct operating range both before and after sulfidation (product gas phase, atm: Pc = 0.255, P. e = 0.064 and

bm AE

P = 0.681). 2

The temperature of the sulfur bath in the evaporation of sulfur was 630 ° K and the average atomic number of molecules in the steam was v = 6.88. The total cheap of the sulfur vapor at the evaporation temperature was 160.1 kcal / kg S. The saturation pressure of the sulfur vapor was Pg = 0.233 atm, i.e. the S ~ pressure of the stability plot calculated P ^ = 0.50 atm.

^ b2

The heat of formation of the concentrate corresponding to Example 2 was = -259.8 Mcal / t and that of the sulfated concentrate was ΔΗ298 = -337.3 Mcal / t, respectively. The decomposition and re-stacking of the complex concentrate is thus a strongly exothermic process in the present case. The heat consuming factors of the process are the heating of the concentrate and sulfur vapor (and carrier gas) from the feed temperature to the reaction temperature, as well as the heat losses of the processing device. From the balance sheets in Table 1, it can be stated that when supplying the concentrate to the system at a temperature T ^ = 473 ° K (200 ° C), the gas phase supply temperature must be T2 = 950OK (677? C). When raising the preheating temperature of the concentrate to T. = 773 ° K (500 ° C), the gas phase must be fed at a temperature Tj B 869 K (596 ° C). In both cases, the total enthalpy of sulfur vapor is still well below the value corresponding to the reaction temperature (1000 ° K). The exothermic heat amount obtained in the sulfidation is then used for the dissociation heat required by the sulfur vapor (between T2-1000 ° K) and for the implementation of the temperature balance in other respects. The temperature of the feed phases of the sulfidation can thus be varied within quite wide limits, which is crucial both in controlling the rate of sulfidation, the melting of the complexes and the like.

In order to obtain an illustrative picture of the change in heat amounts associated with the control method, the heating of the feed concentrate mentioned in Example 1 by recombination (polymerization) heat from the drying temperature of the concentrate to the ignition temperature of the sulfidation reactions is further considered.

The enthalpy of the feed concentrate corresponds to the following equation (01): (01) ΔΗ = 110,263 x 1θ “1Τ + 22,857 x 10_6T2 - 26,820 Mcal / t rich tea

Take the amount of elemental sulfur corresponding to the example, ie 291.2 kg. The total alpha of this amount of sulfur (ΔΗ € + £, Meal) corresponds to Equation (02)

(02) logAHe + f = -160.1033 + 184.5768 x 10_3T - 62.0020 x 1θ'6Τ2 + 46726.5 / T

The temperature of the concentrate fed to the sulphidation system is taken to be 400 ° K (127 ° C), which corresponds to the product temperature obtained from a conventional dryer. Elemental sulfur is evaporated to a temperature of 1000 ° K (727 ° C), whereby the average atomic number of its vapor molecules is v = 2.17 and the enthalpy AHe + f = 157.7 Mcal.

As the concentrate and sulfur vapor meet, the vapor temperature and enthalpy decrease as the atomic number of the vapor molecules increases, and the concentrate temperature and enthalpy, respectively, increase with the amount of heat released in the sulfur vapor polymerization. The heat balance of the system then corresponds to the following equation (03) 205,523 = 110,263 x 1θ “1Τ + 22,857 x 1θ“ 6Τ2 + explQ4He + f, Sv_? 57090

Equation (03) gives a value for the equilibrium temperature T = 872 ° K (599 ° C). The average atomic size of the sulfur vapor molecules increases from the initial value, v = 2.17, v = 4.18 as the volume of the gas volume decreases from 94 Nm3 to 49 Nm3, respectively.

For the thermal enthalpy of sulfur vapor (Δη, heat of formation not included) equation (04) is obtained, Kcal / kg S: (04) aHe = -161.567 + 470.813 x 10 ~ 3T - 214.667 x 10 ~ 6T2

Equations (02) and (04) give the values in the following table for the change in sulfur vapor enthalpy (McaJ / 291.2 kg S): ΔΗ 1000 ° K 872 ° K Difference Difference,% AHfi 27.54 24.97 2.57 3.91 ΔΗ £ 130.19 67.31 62.88 96.07 ^ e + f 157.73 92.28 65.45 100.00

It can be seen from the table that for heating the concentrate from 400 ° K to 872 ° K, sulfur vapor releases 62.88 Mcal as recombination energy when cooled from 1000 ° K to 872 ° K. The share of sulfur gas thermal gas enthalpy in the total heat transfer of the gas phase is only 3.93% / Δ (ΔΗ) = 3.93 Mcal /. When the evaporation point of sulfur _ - c (717.8 K) is taken as the reference state, sulfur vapor has given up only 64.9% of its recombination energy in the case under consideration. It should be noted that the final temperature reached by the concentrate and sulfur vapor, 872 ° K, is well enough to ignite exothermic sulfidation reactions. If, as a result of these reactions, the temperature of the system tends to rise too much, the sulfur vapor begins to dissociate again, causing the temperature to buffer.

It can be seen from the calculations that the amounts of heat generated by changes in the atomic number of sulfur vapor molecules are very large, and on the other hand the control of these amounts of heat is very easy, which makes the control method technologically very advantageous.

Example 2

Example 2 considers the events of structural changes, ersene sulfide formation and evaporation of the cobalt concentrate corresponding to Example 1 when some of the sulfur required by the process is added to the system as pyrite.

17 57090

Decomposition of pyrite corresponds to the reaction (equilibrium as in Example 1) FeS2 - *> Fe10S12 + (1 / 1.25 X) Sx (g)

The amount of sulfur required for the restructuring of the concentrate and for the generation of evaporative sulphide is 182.12 kg S (851.80 kg FeS2) per tonne of concentrate. The amount of free elemental sulfur of the arsenic polymer is added to the system by means of the feed gas phase, whereby the sulfur pressure of the gas phase corresponds to Example 1, i.e. Pg = 0.50 atm. If only a fraction Z of the above-mentioned amount of py is fed into the system, the required additional sulfur is fed in gaseous form (Pc = 0.50 atm).

b2

Example 2 with its material and temperature balances is detailed in Table 2.

Table 2 shows that when the amount of sulfur required for structural changes in the concentrate (65.24% of the total amount of sulfur) is fed entirely as pyrite sulfur, the temperature of the feed gas phase rises above the technical control (5616 ° C). In reality, this temperature is somewhat lower because some of the Sj-Mole used in the calculations has dissociated into the S1 molecule, resulting in a higher polymerization temperature than calculated (however, the monoatomic sulfur-vapor pressure is only 10- ^ atm at 2500 ° K).

When sulfur vapor is fed to the system at 1000 ° K (727 ° C), the amount of sulfur from pyrite is only 45.95 kg, which, however, corresponds to only 15.8% of the amount of sulfur fed.

From the results, it can be concluded that the use of pyritic sulfur to bring about structural changes in a process in which heat is introduced into the system only by means of the concentrate and the gas phase leading edge is non-existent. In particular, it should be noted that the introduction of heat into the system by means of fuel gases (i.e. the use of fossil fuel) lowers the partial pressure of the elemental sulfur so low that the process does not take place.

The result obtained is naturally due to the fact that the decomposition of pyrite is quite an endothermic process (as well as requiring a high excitation temperature). The following table has been used to calculate the base heat of formation (AH2gg) using the heat of formation of feeds and products (Mcal) per feed cost in the cases considered above: 18 57090 0uS SFrS, ~ ώ Hseed '' "product Δ 2 ky Meal Meal Meal 0 0 259.8 328.3 68.6 0.252 45.95 274.3 310.6 36.4 1,000 182.12 297.5 282.3 -15.1

It can be seen from the table that in the processing of cobalt concentrate alone (Example 1), the restructuring event is strongly exothermic. The addition of pyrite to the system makes the process endothermic.

Thus, in the case of an exothermic process, the excess heat of the system as well as the temporary rise in temperature can be easily prevented by pyrite spraying into the reaction space, as this quickly binds the excess heat to endothermic reactions. Excess heat is easily generated when the preheating temperature of the feed concentrate is raised above the amount required in the process to ignite the exothermic reaction when the preheating temperature required for concentrate processing is well below the ignition temperature of the concentrate sulfidation reactions. Advantageously, it is also possible to use a conventional product which has already been processed to a high sulfur content, which then discharges its excess sulfur endothermically (the use of such a product also prevents the reaction product from precipitating with iron). For cooling purposes, the temperature of the sulfur vapor (utilization of dissociation energy) can of course also be lowered, if this is possible without condensation of the vapor.

Example 3

The feed concentrate corresponding to Example 3 is the same as in Example 1. However, the sulfidation process operates in the stability range of cobalt-iron pyrite / (C0, Fe) S2_ /. The amount of cobalt in the concentrate is sufficient to raise the dissociation pressure of the resulting Co-pyrite to the sulfidation temperature range (1000 ° to 900 ° K). The heat of formation of the product concentrate ^ ΔΗ298 'Mca ^ per tonne of feed concentrate increases from the value ΔΗ ^ «-302.4 corresponding to Example 1 to ΔΗ ^ = 332.6, i.e. the increase in the exotherm of the process is quite large (78.9 Mcal) -

The large difference in the formation temperatures of sulphidation feed and product concentrates (113.5 Mcal / t) causes very low feed temperatures for both concentrate and gas phases. In the reaction mode of the furnace, the feed components can no longer react without ignition. For this reason, it is preferable to feed some of the elemental sulfur required for the sulfide with the concentrate, whereby ka. The temperature and partial pressure of the sulfur fed to it can be kept so high that, on cooling in the reaction space to the flash point of sulphidation of the concentrate, it releases the amount of heat required for ignition after polymerization, after which the exothermic reactions take place in the process. Momentary increases in processing temperature can be corrected by periodically diluting the sulfur gas phase of the system, whereby the dissociation of sulfur vapor and the heating of the solvent liner gas rapidly cause the system temperature to drop.

The process corresponding to Example 3 with its material and temperature balances is calculated in Table 3.

It should be noted that when carrying out the sulfidation process corresponding to Example 3 instead of Example 1, it increases the need for sulfur, but on the other hand removes the concentrate preheating unit from the processing equipment.

Example 4

In the case of Example 4, the sulphidation of the nickel-antimony amide concentrate mineral (Ni, Sb) is carried out so that pure minerals, i.e. sulphides of nickel and antimony, are obtained as final products. The material and temperature balances describing the different processing steps of the example are detailed in Table 4.

Nickel <'; The sulfidation of the thymonine mineral is performed in the following steps.

a. The sulfidation of nickel antimony is carried out at a temperature of about 100 ° K using a sulfur vapor partial pressure Pg = 0.35 atm. The temperature of the feed concentrate is 429 ° K (156 ° C) and the temperature of the feed gas phase is 750 ° K (477 ° C), respectively. Based on the analyzes performed, solid, antimony-free nickel sulfide phase and molten, nickel-free antimony sulfide phase are obtained as reaction products.

The heat of formation of the initial concentrate (AHjgg * Mcal / t) is ΔΗ = -110.8 and the corresponding product is δΗ - -180.3 (ie per product volume 1.444 t, δΗ * -260.4). The amount of exothermic heat released in the process is used to preheat the concentrate (429 ° to 100 ° K) and to heat the sulfidation gas phase (750 ° to 1000 ° K). The sulfur vapor in the sulphidation gas phase dissociates and its enthalpy (ΔΗ ,, kcal / kg) increases from AHg + f = 208.4 to ΔΗβ + £ - 549.4. The amount of heat required for dissociation, Δ (ΔΗβ + ^) = 341.0 is taken from exothermic sulfation reactions. In sulphidation, the partial pressure of sulfur vapor in the gas phase decreases (Pg = 0.35 —► Pg = 0.10 atm), whereby the unreacted part of the sulfur vapor taxi pressure further dissociates so that the required dissociation temperature at 1000 ° K is 17.9 kcal / kg F, b. From the sulfidation process, the reaction products and the gas phase are transferred to a cooling furnace. From the stability drawing of Figure 5, it can be seen that as the product cools, the nickel pyrrole J. Ni (NiS2) moves in the stability field while the antimony sulfide remains liquid / Sb2S3 (1] _ /. The antimony sulfide contained in the gas phase condenses in the reaction space of the cooling furnace, and the heat losses in the cooling furnace are obtained from the increase in the exotherm of the reaction products (NiS -—► NiS + NiS. ,, AHe + f = -29.8 Mcal / 1.444 t of feed mixture) from the change in content (cooling: 1000 ° K—> 890 ° K) It should be noted that 1.545 tonnes of final reaction products are obtained per tonne of antimony concentrate, with a corresponding increase in exothermicity of 179.4 Mcal / t of feed concentrate.

In the refrigeration furnace, the amount of sulfur in the sulfidation product can be determined to determine whether the refrigerated product contains antimony sulfide at the bottom or surface of the vessel or whether the antimony and nickel sulfides are mechanically mixed. Because concentrates often contain iron, the above control is simple.

c. From the cooling furnace, the sulfur and antimony-poor gas phases are led to the feed end of the sulfidation unit, where the sulfur evaporator becomes elemental sulfur. When vaporizing sulfur at 700 ° K, its heat content is = 170.4 kcal / kg Sy (v = 6.97). The temperature of the feed sulfur in the sulphidation process is 750 ° K and the heat content ΔΗ6 + ^ = 208.4 kcal / kg S. The thermal energy required for the dissociation of the sulfur, 38.1 kcal / kg S, is released by the gas phase from the cooling furnace.

Example 4 illustrates well the versatile way in which the dissociation-recombination energy of sulfur carbon can be utilized in sulfidation processes.

Example 5

Let us examine in more detail the behavior of technically very important complex, high-impurity minerals belonging to the Cu-As-S basic system during sulphidation in order to bring about structural changes.

As a technically important large ore mineral group, a series of structurally analogous (elementary booth volume eight times) fahlerzies, common form (Cu, Ag) 12 (Cu, Ag, Fe, Hg, Ge, Sn) ^ 2 (As, Sb, Bi) e a series of enargites analogous to zinc sulfide, the general form Cu ^ iAs, Sb) S4 · These, with some exceptions, hydrothermal mineral groups usually occur in the same ore deposits.

The compounds of the basic system Cu-As-S are tennantite (Cu24ASgS2g) from the Fahlerzie series and enargite (Cu ^ AsS ^) from the enargite series. The system also includes the naturally rare sinnerj11-ti (CUgAs ^ Sg), luteite (CuAsS) and compound A (Cu ^ As ^ S ^), which is involved in phase reactions but is not known in nature. The sulfidation of the above compounds is hampered by the low melting ranges of both the compounds and the phase reactions between them, which is why special sulfidation conditions are usually required.

the following examples of melting conditions of compounds and reactions are taken:

- sinterite melts as an incongruent liquid and compound A

at a temperature of 489 ° C

- enargite reacts with compound A to form tennantite and liquid at 573 ° C and compound A decomposes to tennantite and liquid at 578 ° C

- the tennantite melts with Cu ^ 2 at 665 ° C

- the enargite, in turn, decomposes into about 2 at-% As poorer enargite (u3AsQ g4S4) and into a liquid at 666 ° C. The maximum melting temperature of the Enargite assemblages is unknown.

22 57090

The Cu-As-S system has never been studied under controlled sulfur pressure, so the melt phase ranges and melting temperatures corresponding to the above and other possible reactions may deviate significantly from the measured low total pressure values. It has been found in sulphidation experiments that tennantite can be converted to enargite at temperatures> 700 ° C, which in turn can be converted to digenite and / or chalcopyrite and kernite as the sulfur polymer is present, depending on the amount of iron present or added. During treatment, no sintering of the concentrate or visible presence of melt phases can be detected. Equilibrium constants (numbered) for sulfidation of tennantite argitite systems, calculated from the available thermodynamic values (inaccurate), correspond to the values in the table on the next page. The stability ranges of the most important compounds for consideration as a function of sulfur pressure and temperature are plotted in the stability plot of Figure 5.

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Reactions 1-9 in the table:

From the extrapolated equilibrium values of reaction 1, it can be seen that the enargite becomes stable at a temperature of 1000 ° K above a sulfur pressure of Pc = 3.49 x 10 atm. b2

According to Reaction 2, the enargite decomposes into digenite as well as gaseous arsenic sulfide. At a sealing temperature of 1000 °} 'is ·. · -, 2 free energy positive. When a high sulfur fraction is used, instead of chalcosite (Cu2S), a digestion phase (Cu ^ S) within the metal subtotal is formed, whereby the activity of chalcosite λ]. advantageous for the equilibrium reaction. From the known measured values, a reaction is given

U - MCu2S (ss) * <«/ 2 | S | ss) - CU2.6S

equilibrium constant, sulfur and chalcosite activities calculated in the space range 823-11023 ° K (550-750 ° C) and at δ values, δ = 0, u are both 6- and α ^ u g functions of the form

aCu2S = "26 + 1 * 3222 - 2C3.7 / T

(<5/4) log Ρ_ = 0.3335 - 460.0 / T - (1-6) log a_ c

When taking the sulfur weight corresponding to the tennantite-enargite balance <~.

Pg = 3.49 x 10 2 (1000 ° K) is obtained from the equations of equilibrium diene \ ι corresponding to the Cu ^ g ^ S composition and the chalcosite activity n.

aCu2S = 0.81. The vapor pressure of the arsenic sulfide is then 0.56 atm, so that the reaction (2) proceeds preferably. Due to the positivity of the free energy of the reaction, the vapor pressure α '· of the arsenic sulfide increases when the partial pressure of the sulfidization sulfur vapor is increased. On the other hand, lowering the partial pressure of sulfur results in arsenic not being removed from the system, because as the amount of sulfur in the digenite decreases, the solubility of arsenic in it increases (e.g. 500 ° C, structure (Cu, As) ^ 92s * miss ~ 0.70% by weight As ^ ^). In particular, the formation of melting phases that interfere with processing should also be noted if the digestite is broken. decreases, i.e. the sulfur partial pressure of the system is reduced. The same findings apply to reaction 7 as to reaction 2. In addition, however, it should be noted that in the tennantite-digenite equilibrium, the solid solubility of digenite and arsenic is even higher than under the conditions of reaction 2. Thus, when performing evaporative sulfidation, the sulfur pressures above the tenn-m-57C90 titite-enargite conversion are effective.

Each of reactions 3, 4, 5 and 6 takes place. When iron sulphide or iron is added to the enargite, bornite and / or chalcopyrite are obtained as reaction products. However, when carrying out the sulfidation, it can be seen that the reaction 3 proceeds poorly. Reactions 4, 5, and 6 do not yield results at the calculated sulfur limit pressure because arsenic sulfide is not stable under these conditions. It should also be noted that at low sulfur pressures, reactions proceed slowly and the presence of stationary melt phases is at risk. The phenanthite-chalcopyrite reactions of Reactions 8 and 9 are subject to the above discussion.

Table 5 shows the calculated material and temperature balances for the sulfidation process of a conventional ferrous __-containing enargilt concentrate (wt%: 30.5 Cu, 11.8 As, 0.3 Sb, 35.7 S and 15.8 Fe), where both arsenic and the anti-many volatilize as sulfides and the original enargite matrix re-emerges corresponding to the chalcopyrite-bornite (digenite) equilibrium.

Technically easily achievable values for the partial pressure of sulfur vapor and the arsenic content of the arsenic-sulfur polymer, ie Pg ® X * 0.8 atm and Y <0.4 (40% by weight As), have been placed in the general solution of the balance sheets. The concentrates under consideration have an endothermic sulfidation process, so additional heat is supplied to the system by burning part of the feed sulfur. Due to the endothermicity of the process, the concentrate is fed to the system with a high degree of preheating, i.e. at this temperature 500 ° C. The importance of high sulfur potential for the quantitative and kinetic removal of arsenic and in the prevention of melt phase formation has already been discussed above (solid solubility of arsenic in the chalcopyrite-enargite equilibrium is equal to or greater than in the corresponding digenite equilibrium).

In the technical implementation of the sulfidation process, high sulfur pressure is crucial, especially for endo-thermal sulfidation reactions. Consider this question briefly in the following summary: 26 5 7 0 9 0 a. Differential-thermal analysis shows that the enargite concentrate ignites in a sulfur atmosphere for a technically sufficiently rapid reaction at 570 ° C (temperature rise rate 6 ° C min- * and the like, increasing negative temperature gradient of the endothermic reaction -1.4 ° C min- *).

b. The enthalpy (Mcal / t) of the enargite concentrate was ΔΗβ 145.989 x 10-½ - 39.323 and the enthalpy with the heat of formation was ΔΗβ + ^ = 145.989 x 10-½ - 219.898, respectively. The total enthalpy of the sulfidation products (product sulfide-arsenic sulfide) was AHe + f * = 194.570 - 10-3T -243.709.

c. From the temperature functions of the total sulfur alpha, the values of 575.1 »541.7 and 276, 1 are calculated as the enthalpy of steam (AHe + f, kcal / kg S) at 1100, 1000 and 845 ° K at the same temperatures. corresponding to 582.6 »567.3 and 492.1, respectively.

According to the material balance in Table 5, the processing feed requirement per tonne of concentrate is 33.73 kg and this and the total amount of sulfur required to provide additional heat are 95.49 kg. The amount of heat supplied to the sulfur by the polymerisation system, as the temperature of the steam decreases from the feed temperatures of 1000 ° K and 1100 ° K to the ignition temperature of the concentrate, is calculated from the given values according to the following table

Ps, atm Δ T, ° K ΔΗβ + ί 'Mcal

X _____ 33.73 kg S 95.49 kg S

0.8-1.0 1100-845 10.09 28.55 1000-845 8.96 25.36 0.1 1100-845 3.05 8.64 1000-845 2.54 7.17

It can be seen from the table that when operating at high sulfur partial pressure, the amount of heat required to heat the concentrate from the preheating temperature of 773 ° K (500 ° C) to the ignition temperature of the reactions of 845 ° K (572 ° C) is obtained as the polymerization heat of preheated sulfur vapor. This amount of heat according to b is ΔΗβ = 10.15 Meal. In this case, the heat of polymerization is still not widely used. When supplied at low pressure, the heat of polymerization is not sufficient even to heat the concentrate.

27 57090 d. In the range of the ignition temperature of the feed concentrate, arsenic antimony sulfide is formed as a molten pure phase separating from the matrix. Using the total enthalpy values of (b), the enthalpy of the concentrate at 773 ° K is ΔΗβ + ^ = -107.05 and the enthalpy of the obtained products at 845 ° K is ΔΗβ + ^ = -79.30.

The amount of heat required to satisfy the temperature demand of both the heating of the concentrate and the endothermic reactions (without heat loss in the system) is thus 27.75 Mcal. It can be seen from the table in c) that the amount of heat provided by the polymerization of high-partial sulfur is sufficient to effect approximately low-temperature sulfidation. When operating at low sulfur partial pressure, the release of steam polymerization energy does not occur in the range useful in the process, but in a lower temperature range of about 100 ° K.

e. The (As, Sb) jSj (1) phase formed in the ignition temperature range of sulphidation must be evaporated in the process. The temperature of the system must therefore be raised in order to reach the evaporation temperature.

The amount of heat required to cover both the heat loss of the furnace and the evaporation enthalpy is obtained suitable for the process by burning part of the sulfur-steam.

Utilization of the heat of polymerization of sulfur vapor as described above also allows sulfur vapor to be burned only after the onset of sulfidation reactions, whereby the at least partially re-stacked ore matrix withstands (without sintering or melting) the temperature of the flame and combustion gases.

In addition to the general case, some cases (A, B, C, and D) from different sulfidation methods are included in Table 5 for comparison.

In cases A and Aj ~ "Sulfidation of the enargite concentrate is carried out conventionally with pure sulfur vapor. In case A, the sulfur vapor feed temperature is 900 ° K and in case A ^ 1000 ° K (i.e. the same as the temperature of the products).

In case A, the change in the total enthalpy of the gas phase from the feed temperature to the product temperature ΔΗβ + £ = 163.05 kcal / kg, of which the proportion of gas enthalpy (ΔΗε) is only 4.61 *. The dissociation energy required to raise the temperature of the gas phase sulfur (95.99 kg) between 900 ° and 1000 ° K is thus = 14.85 Meal. In the case A ^, this amount of energy 28 57090 is not needed, so the amount of sulfur used for combustion is correspondingly (15.09 Mcal) lower than in case A.

In cases B and an amount of iron powder has been added to the concentrate corresponding to the previous case such that the sulphide obtained as a whole is chalcopyrite. From the corresponding material and heat balances, it can be stated that the consumption of sulfur has increased sharply compared to the previous case. However, the sulfur vapor fed at 100 ° K consumes only 15.26 kg of sulfur required for endothermic reactions as sulfur to be burned, which is 3.6 times lower than in case A. This is, of course, due to an increase in the exotherm of the system (iron sulfides). In case C, the additional heat required in case B is produced in the system by burning iron corresponding to the equilibrium state FeS ^ 2η. The quantities to be fed were 49.99 kg of iron and 36.45 kg of sulfur. The exhaust gases are then obtained free of sulfur dioxide.

In case D, the iron required to achieve the final product chalcopyrite is added to the system as pyrrotite (FeSx). In this case, the amount of sulfur to be burned to produce the amount of heat required for endothermic reactions (as well as heat losses) has increased from the value corresponding to case B from 15.26 kg to 44.37 kg. This is due to the increase in endothermicity of the process due to the lack of exothermic heat of iron phase sulfidation in the bacon.

Let us briefly consider the sulfidation of pure enargite mineral with a degree of bornite under conditions similar to the previous examples (X = 0.8; Y = 0.4):

Corresponding to the reaction 5Cu3AsS4 + 3Fe —7 3Cu5FeS4 + 5 / 4As4Sg (g) + 1 / 4S2, 85.09 kg of iron and 180.92 kg of sulfur must be fed per tonne of enargite. According to the reaction, the amount of sulfur released is 8.14 kg. 25.82 kg of sulfur must be burned from the total sulfur feed to produce sludge heat.

When iron is replaced by pyrrotite, the amount of feed sulfur is 154.55 kg, of which 48.30 kg of sulfur must be burned in order to implement the heat balance. The amount of sulfur released in the reactions is 57.00 kg of sulfur. When the required amount of iron is added, the amount of feed sulfur is 126.53 kg, of which 29 57090 sulfur is 69.13 kg. The amount of sulfur released in the reactions is then 105.85 kg.

When the additives are fed into the system at 773 ° K and the products / Cu5FeS ^ (s) + As ^ Sg (gj_7 at 1000 ° K), the following values are obtained per ton of enargite for the endotherm of the reactions using different additives: 29.99 / Fe, 59.68 / FeS and 85 , 25

Mcal / FeSj. At 1000 ° K, the formation temperatures (Mcal / t) of the product compounds and enargite are as follows: -73.06 / CuFFeS2, -117.74 / CuFeS2 and -27.40 / Cu2AsS2.

From the examples, sulfation of enargite or its concentrates to chalcopyrite or bornite by adding the missing amount of iron as iron or its sulfides is generally not preferable because the amounts of feed sulfur easily increase with increasing endothermic reactions (despite the fact that the final sulfide products are more stable The starting materials).

in summary, the utilization of sulfur vapor dissociation-recombination heat in the treatment of the endothermic process under consideration is quite crucial. It is self-evident that as the mineral composition of the ore changes, the conditions, temperatures and partial pressure of the sulfidation process must also be varied as necessary.

Example 6

In the example, chlorination of molten copper sulfide rock is performed to evaporate the impurities it contains as chlorides. The molten stone in the example corresponds to the so-called moving stone from which the iron content has already been slag.

The migration stone is in equilibrium with metallic copper (aCu ~ 0.99), and it usually already contains a large amount of metallic copper and uncharged (Cu °) dissolved unbalanced. It is assumed that this copper adheres to its environment a lot of impurities. According to the measurements, at 1250 ° C, the distribution of the impurity components (% Me in Cu 2 S /% Me in Cu) with respect to copper sulphide and copper in equilibrium with it is as follows: 0.57 / Zn, 0.12 / Pb, 0.10 / Sn, 0.06 / Sb and 0.15 / Bi. When attempting to chlorinate melts per se, copper is chlorinated well and impurities are weak. When elemental sulfur is added to such a melt before or during chlorination, the melt takes this in excess of the stoichiometric chalcite lithium 30 57090 (Cu2S), e.g. in the case under consideration: Pg = 0.8 atm, CuxS: X = 1.902. In this case, the copper activity of the sulfide melt? decreases (α ^ 'N / 10 "^) and impurities can be selectively chlorinated.

The impurity chlorides formed in chlorination are so stable that, despite the heat-binding evaporation, the overall process is strongly exothermic and the melt temperature usually rises sharply. Utilizing the large amount of energy required for the dissociation of sulfur vapor molecules, the rate and amount of melt temperature rise can be buffered to the desired values by feeding the gaseous sulfur used at the lowest possible temperature. Any excess sulfur used is recovered and returned to the process by condensing the chlorides.

Table 6 details the migration stone chlorination process described above.

Keeping the transition stone of the example unchanged during the chlorination process (1500 ° K), the amount of heat bound by the sulfur vapor is 24.2 Mcal (700 ° K — r 1500 ° K). Allowing a melt temperature rise of 50 ° K is the dissociation bound heat amount of 17.8 Mcal. These amounts of heat are very large, as they represent 33.2% and 25.3% of the potential amount of heat in the heat balance, respectively.

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Claims (5)

49 ~ Claims 57090 1. A method for adjusting the color to air temperature and the temperature of the sulphide treatment process, the color of the sulphide process being at ambient temperature between 400 and 900 ° C and the ambient temperature at 0.1 to 1 atm, and the atmosphere is regulated by dissociation and recombination energy. A method for controlling the amount of heat and equalizing the temperatures of various sulfidation processes, wherein the sulfidation is carried out in a sulfur atmosphere at a temperature of 400-900 ° C and a sulfur partial pressure of 0.1-1 atm, characterized by controlling the sulfur pressure of sulfur molecules using sulfur energy dissociation and recombination energy. 2. A method according to claim 1, which comprises the use of an inert gas and a sulfide ring for the preparation of a three-way deletion, which comprises a dissociation and a binder color in the light atmosphere. Process according to Claim 1, characterized in that the sulfur vapor is diluted with an inert gas in the sulphidation zone in order to reduce the partial pressure of the sulfur so that the sulfur molecules dissociate and bind heat to the sulfur atmosphere. 3. A patent according to claims 1 or 2, with reference number 57090, is shown as an elemental sulphide ring for binding to a color and an atmosphere. Process according to Claim 1 or 2, characterized in that the elemental sulfur is evaporated in the sulphidation zone in order to bind heat to the sulfur atmosphere. 4. The present invention relates to the use of the same patent, including the use of carbon dioxide, and to the transfer of the genome from a brandy to a sulphide ring. Process according to one of the preceding claims, characterized in that the sulfur vapor is diluted with sulfur dioxide, preferably by burning sulfur in the downstream part of the sulphidation zone. Process according to one of the preceding claims, characterized in that the sulfur vapors removed from the sulphidation zone are returned to the sulphidation zone after heating or cooling. 5. The competent authorities have entered into force on the patent and endorsement of the patent and the use of sulphide additives and after-sales accounts for the sale or refining. Viitejulkaisu.ia-Anförda publikationer Public Finnish patent applications: -Offentlica finska patentaneökningar: 1912/7 * 4 (C 22 B).