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6.1.2. Sulphur disposal in a gas phase.

sulphur transition in a gas phase occurs basically in oxidising area barbotazhnoj zones, and also everywhere in the course of coking of coal loaded into the oven. Laboratory experiments and practice koksohimicheskogo manufactures testify, that at coking in a gas phase passes from 15 to 40 % of sulphur of coal [125].
In industrial conditions from all quantity of the sulphur containing in mix material koksovoj the ovens, passes in coke of 64,3 %, in H2S - 30,1 %, in pitch and nadsmolnuju water - 5,6 % [126].
In the conditions of process ROMELT coking proceeds at very high speeds of heating that can influence both degree of disposal of sulphur, and on makeup of gaseous products. Laboratory experiments on a coal-to-coke conversion both in a gas phase, and on a surface and in volume of slag melt have shown, that speeds of heating reach 500 °/minutes Real speeds of heating, possibly, still above. In work [127] where for gauging of temperature of a coal particle on a surface of slag melt optical pyrometers were used, the particle in weight of 3,5 mg (diameter of 1,5 mm) got temperature 1000 °s during an order of 1 second.
Experiences on high-speed pyrolysis of various coals in inert atmosphere are resulted in table 25. Here results of an estimation of disposal of sulphur are yielded at pyrolysis anzherskogo coal in the course of a regenerative fusion on a pilot plant by results of the assaying taken of the oven koksovogo the rest. It is visible, that a fraction of the sulphur deleted in flying has made 16,7-44 %. Laboratory experiment yields the result which is keeping within these breaking points. Antratsitovyj shtyb and especially a brown coal had the big degree of disposal of sulphur. Remaining in koksovom the rest sulphur is in a kind of sulphides, in particular, FeS to what testify given [128] and the explorations carried out by us (coincidence of spectra JAGR koksovogo the rest and iron sulphide).
The sulphur contents in used coals to (numerator) and after heating (denominator)
Table 25 Coal the Contents of sulphur the Fraction of the sulphur deleted with summer-chimi (in recalculation on firm carbon), % In coal, % In recalculation on 100 g firm carbon, g Kuznetsk pool, Anzher - sknj coal of the brand of OS 0,34/0,31 0,46/0,35 23,9 Kansko-Achinsk pools, the Irsha-Borodino coal of brand Б2 of 0,58/0,29 1,97/0,38 80,7 Donetsk pool, the brand And 0,86/0,62 1,22/0,77 36,9 Regenerative fusion, Anzhersky coal of the brand of OS (0,33-0,39) / (0,26-0,32 (0,43-0,53) / (0,29-0,36 16,7-44,0 Transition of this part of sulphur koksovogo the rest (burning down in a tuyere region in the presence of free oxygen) in a gas phase in the form of S02 with the subsequent partial conversion in COS and S2 on type reactions:
S02 +2C - COS + CO Kp = 6,74* 104 (6.1)
S02 + 2C = 2CO + 0,5S2 Kp—7,5* 10s (6.2) in a zone of conversion C02 on coal) can provide two processes: burning koksovogo the rest and burning out from slag of a part of the sulphur which have passed with ashes koksovogo of the rest in slag in the form of sulphide gland.
In slag all sulphur containing in a ferriferous part of raw materials and fljusujushchih (except for sulphur directly containing in metal iron, for example, to a steel shaving) also in the form of sulphides passes also. This part of sulphur also can to leave in oxidising area barbotazhnoj zones in the form of S02 with the subsequent partial conversion in COS and S2.
The assaying of the gas seeded over a bathroom in a smelting process of slurry, has shown, that it contains, % (it is volume.): S02 - (1,05 - 1,4) *10 "2; WITH - 61,2 - 70,2; SOg - 5,9 - 9,8; Н2-8,1 - 13,5.
Thus the runout of sulphur in the form of S02 made of a bosh 0,13 - 0,21 kg/ch*m3 or 5... 10 % from the sulphur deleted in a gas phase (1,93-2,57 kg/ch).
Accepting, that all sulphur deleted from a bosh, is in a kind of gaseous bridgings, for average makeup of gas at temperatures 1450 - 1550 °s have calculated equilibrium partsialnye pressure serosoderzhashchih gases, the Pas: Рзо2 = 0,17-.0,21; Pso-3,8 - 4,7; (Ps+PCOS+Ps+PHS+PCS+PCS2+PH2S) = 136 "172 Thus, actual Pso2 - 10,5 - 14,0 it is considerable above equilibrium, i.e. Answers higher values Ро2. neravnovesnost a waste gas specifies in formation S02 in zones with high oxidising potential. In a bosh of oven ROMELT those are zones close barbotazhnyh furm.
For check of this assumption have spent a gas sampling directly from a gas cavity in slag volume on various distance from a sawn-off shotgun furm. Samples seeded special cooled otbornikom, entered into melt through dutevoj the channel furmy (fig. 67 see,).
Contents S02 in gas increases on a course of a gas stream (fig. 67 see,). On distance 0,3... From a nozzle gas contained 0,4 m, % (it is volume.): WITH - 2; С02 - 6,5; 02 - 57,5; Н2 - 0,25.
The calculated values partsialnyh pressure serosoderzhashchih the gases which are in a tuyere region at temperature 1500 °s in balance with actual with-derzhaniem S02 (Pso2=38,5 the Pas), make, the Pas: Р30=1*Ю "3; PH2S-1,6*T0" 3;
(Ps+Phs+Pcs+Pcos+Pcs25+Ps2) = 8,34* JU "5. It shows, that in nearby tuyere region practically all sulphur in gas should be in kind S02.
Weight S02, formed in nearby tuyere region (0,14... 0,17 kg/ch), approximately same, as well as in gas on a runout from a bosh. As end of oxidising of sulphur from slag on distance 0,3... 0,4 m from a nozzle are improbable, it is possible to assume, that formed then S02. (And also С02;) it is recovered by carbon in the top courses of bubbled slag with the high contents of coal. However to balance with gas phase SO2. To be recovered its contents considerably above the equilibrium is not in time and consequently on a runout from a bosh.

Fig. 67 Scheme of a gas sampling from a tuyere region () and change partsialnogo pressure SO2 in gas depending on distance I between a point of selection of sample and a nozzle cut furmy ()
1 zone of a blowing through; 2-otbornik samples, 3 - analyzed gas; 4 water cooled wall, 5 - a water cooled nozzle furmy; 6 - blow
Thus, in oven ROMELT the basic quantity of sulphur leaves in a gas phase, and only a part in the form of SO2 which is formed as a result of oxidising of sulphur of slag by blow oxygen.
Some part of sulphur can leave in a gas phase in the course of restoration as a result of course of reactions:
2FeS (S) +C=2 [Fe] +CS2 Кр=2,8+10 ' 4 (6.3)
And
FeS (5K) +CO = [Fe] +COS Кр=2,3*10-4 (6.4)
In the course of ROMELT disposal of sulphur from slag is described by the equation of reaction of the first order. As the slag tank is close to a condition of an open reactor
Full melting pot, stationary concentration of sulphur in slag for irreversible reaction of the first order is defined by the equation:
-K*Cs + ZOiCoi, - OiCs=0 (6.5)
Then,
Cs=ZC0lai / (K+ai) (6.6)
Where: and, = m/M, ch "1; To - a constant of speed, ч*1; Cs-stationary concentration of sulphur in slag, weights, a fraction; C„ j; - concentration of sulphur in a submitted burden constituent, weights, a fraction, a] =h/M, ch "1; h - speed of formation of slag, t/ch; p ^ - a burden constituent feed speed, t/ch; M - weight of a bubbled course of slag, t.
The formula (6.6) gives linear linkage between stationary concentration and a charging rate of sulphur and can be applied only to that is frequent sulfurs which passes directly in slag. It is all sulphur of raw materials and a part of sulphur of coal.
At wasps. = {(^ + - (Z^m + ^ SHCH} ^ 01 h m m} at m of m and
In our case:
1 PC0D PC vcs (e] mCS (M) c = (1) {(SL + _ (—?
Or 3FeS+502=Fe304+3S02 it is possible only at the first stage and, hence, only half of sulphur koksovogo the rest which is burning down at furm, should pass neposred-stvenno in a gas phase, as proves to be true experimentally.
About same also data by definition of makeup of gas in a tuyere region indirectly testify. The relation of weights of carbon and sulphur on distance 0,38м from a sawn-off shotgun furmy is equal in gas 85 while this relation is equal in the used coal 340, i.e. the quantity of the sulphur which have passed in a gas phase for the account of burning koksovogo of the rest makes only—25 % from total of the sulphur which have passed in a gas phase in nearby tuyere regions, the others of 75 % have come from slag. As arrival of sulphur to the oven with raw materials (slurry) makes about half from blanket arrival (arrival with coal is considered minus sulphur leaving at pyrolysis) and all it passes in slag, the fraction of sulphur of the coal passing in slag, will make-25 % that gives percent sgo-revshej the sulphur which have passed in slag from coal-50 of %, 52 % practically coinciding with the above-stated value for transition of sulphur of coal in slag.
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A source: Usachyov Alexander Borisovich. Development of theoretical and technological foundations of iron production by the POMEJIT liquid phase reduction process. DISSENTATION for the degree of Doctor of Technical Sciences.. 2003

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