Calcium sulfide decomposition process

Abstract

The present invention relates to a process for decomposing calcium sulfide (CaS) into calcium oxide (CaO) and sulfur dioxide (SO.sub.2), comprising:—providing a reactor containing calcium sulfide and a source of carbon,—oxidizing the source of carbon so as to generate carbon dioxide (CO.sub.2),—reacting the calcium sulfide with said carbon dioxide so as to produce carbon oxide (CaO), sulfur dioxide (SO.sub.2) and carbon monoxide (CO) according to the following reaction: CaS+3CO.sub.2˜CaO+SO.sub.2+3CO wherein the oxygen and carbon contents in the oxidation step are chosen such that: (i) the mass ratio C/CaS is comprised between 0.15 and 0.35 and (ii) the mass ratio O.sub.2/C is comprised between 5 and 25.

Claims

1. A process for decomposing calcium sulfide (CaS) into calcium oxide (CaO) and sulfur dioxide (SO.sub.2), comprising: providing a reactor containing calcium sulfide and a source of carbon, oxidizing the source of carbon so as to generate carbon dioxide (CO.sub.2), reacting the calcium sulfide with said carbon dioxide so as to produce calcium oxide (CaO), sulfur dioxide (SO.sub.2) and carbon monoxide (CO) according to the following reaction:
CaS+3CO.sub.2.fwdarw.CaO+SO.sub.2+3CO wherein the oxygen (O.sub.2) and carbon (C) contents in the oxidation step are chosen such that: (i) the mass ratio C/CaS is comprised between 0.15 and 0.35 and (ii) the mass ratio O.sub.2/C is comprised between 5 and 25.

2. The process of claim 1, wherein the ratio C/CaS is equal to 0.25.

3. The process of claim 1, wherein the ratio O.sub.2/C is equal to 8.

4. The process of claim 1, wherein in the oxidation step the reactor is heated to a temperature comprised between 900° C. and 1200° C.

5. The process of claim 4, wherein the reactor is heated by induction.

6. The process of claim 1, wherein the source of carbon comprises at least one of: coal, coke, charcoal, and shale oil.

7. The process of claim 1, wherein the reactor is a continuous reactor comprising an inlet and an outlet for flowing O.sub.2 through the calcium sulfide and the source of carbon.

8. The process of claim 1, wherein the reactor is a fluidized bed reactor or a rotary kiln.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Further features and advantages of the invention will be apparent from the detailed description that follows, based on the appended drawings wherein:

(2) FIG. 1 relates to calcium sulfide decomposition using CO.sub.2: (a) dimensionless outlet quantities per unit of CaS—and (b) energy requirement for the mass unit of CaS. The dashed line in (b) shows the required CO.sub.2/CaS when CaS conversion is complete. The data are obtained by equilibrium calculation using FactSage™ simulations.

(3) FIG. 2 illustrates an induced heated fluidized bed reactor scheme for gypsum decomposition experiments by carbon oxidation;

(4) FIG. 3 relates to calcium sulfide decomposition using carbon combustion when C/CaS≈0.2: (a) dimensionless outlet quantities and (b) energy requirement for the mass unit of CaS. The dashed line in (b) shows the optimum O.sub.2/C when CaO and SO.sub.2 yields are maximum. The data are obtained by equilibrium calculation using FactSage™ simulations.

(5) FIG. 4 shows the production of SO.sub.2 from CaS decomposition by carbon oxidation in the induction fluidized bed reactor at 1100° C. with a total sample amount of 6 g, for various C/CaS and O.sub.2/CaS ratios.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

(6) The invention relates to CaS decomposition by carbon (e.g., coal, coke, charcoal, or any other source of carbon) oxidation (O.sub.2 above stoichiometry conditions) to remove any undesired CaS produced from PG decomposition reactions or any other processes and convert it to CaO and SO.sub.2.

(7) Calcium sulfide decomposition can be performed in an oxidative environment at 1100° C. as mentioned in reactions (1) and (2):
CaS+1.5O.sub.2.fwdarw.CaO+SO.sub.2  (1)
CaS+2O.sub.2.fwdarw.CaSO.sub.4  (2)

(8) However, it could lead to CaSO.sub.4 formation requiring further treatment of the solid.

(9) Another process at 1100° C. that can be used for CaS decomposition employs CO.sub.2 according to:
CaS+3CO.sub.2.fwdarw.CaO+3CO+SO.sub.2  (4)

(10) Note that this requires CO.sub.2/CO≈30 for a complete CaS conversion (see FIG. 1(a)). A complete CaS removal by high CO.sub.2 flow in the inlet of the reactor can cause particle entrainment. When using a fluidized bed reactor, high CO.sub.2 flow can cause the particle discharge, which not only affects the reaction kinetics but also requires massive filtration. About 95% of the injected CO.sub.2 is discharged from the reactor, which can yield serious environmental impacts. Moreover, the process of using CO.sub.2 requires considerable amounts of energy (≈42 kJ/g CaS, FIG. 1(b)). As a result, this method is not recommended for a complete CaS conversion.

(11) Carbon as the source of energy under oxidizing conditions undergoes the two following reactions:
C+0.5O.sub.2.fwdarw.CO  (5)
C+O.sub.2.fwdarw.CO.sub.2  (6)

(12) where these reactions are exothermic. Calcium sulfide does not directly react with carbon. However, CaS can be converted to CaO and SO.sub.2 according to
CaS+3CO.sub.2.fwdarw.CaO+SO.sub.2+3CO  (7)

(13) Among the products of reaction (7), CaO and CO do not react with CaS while SO.sub.2 can react with CaS and produce CaSO.sub.4:
CaS+2SO.sub.2.fwdarw.CaSO.sub.4+2S  (8)

(14) Then, various reactions can occur between CaS and CaSO.sub.4, thereby leading to desired solid and gas products:
3CaSO.sub.4+CaS.fwdarw.4CaO+4SO.sub.2  (9)
CaSO.sub.4+3CaS.fwdarw.4CaO+4S  (10)
CaS+3CaSO.sub.4+4CO.sub.2.fwdarw.4CaCO.sub.3+4SO.sub.2  (11)
CaS+3SO.sub.3.fwdarw.CaO+4SO.sub.2  (12)

(15) With sufficient amounts of carbon and controlled amounts of oxygen, carbon can produce the required amounts of energy and, simultaneously, the required amount of CO.sub.2 to initiate the CaS decomposition process. Therefore, in continuous streams of CaS and carbon, while oxygen is injected, all reactions occur with the heat provided by carbon combustion.

(16) The present invention is illustrated in further detail below by non-limiting examples and embodiments.

(17) Pure CaS (%99.99, particle diameter 20<d.sub.p<60 μm, ρ≈2.6 g/cm.sup.3) was provided by Sigma-Aldrich, USA, and coal (particle diameter 20<d.sub.p<60 μm) as a source of carbon was provided by Recommunity Inc., Canada, with the heating value of 28,280 kJ/Kg and characterized by CHNS (determination of the mass fractions of carbon (C), hydrogen (H), nitrogen (N) and sulfur (S)) and NAA (Neutron Activation Analysis) presented in tables 5 and 6 below, respectively.

(18) CaS decomposition experiments by carbon oxidation were performed in a novel, heat-induced fluidized bed reactor that was able to be heated up to 1100° C. at 200° C./s.

(19) The scheme of a reaction device 100 comprising this reactor 10 is illustrated in FIG. 2.

(20) The reactor 10 comprises a gas inlet 20 from which oxygen O.sub.2 (reacting gas) is supplied to the reactor. An oxygen source 21 in communication with a digital flow controller 22 powered by a power supply 23 allows to control the flow of oxygen O.sub.2 being introduced into the reactor 10.

(21) Similarly, the reactor 10 comprises a gas inlet 30 from which nitrogen N.sub.2 (carrier gas) is supplied to the reactor. A nitrogen source 31 in communication with a digital flow controller 32 powered by a power supply 33 allows to control the flow of nitrogen being introduced into the reactor 10.

(22) The gases leave the reactor via the gas outlet 40 which comprises a thermal and/or electrical insulation 41.

(23) An analysis device 50, such as an FTIR spectrometer (Fourier Transform InfraRed) can be used to analyze the gases leaving the reactor, in order to collect data from which infrared spectrum, emission spectrum or absorption spectrum, for example, are obtained. A nitrogen source 51 in communication with a digital flow controller 52 powered by a power supply 53 are provided for this purpose.

(24) The reactor 10 is formed of a tube, preferably made of alumina, loaded with sand 11, and phosphogypsum 12 and coal 13, prior to the reaction. Within the reactor 10, stainless steel vertical rods 14 are fixed to a plate. A metal coil 15, preferably a copper coil, is wrapped around the tube of the reactor 10 and supplied with energy by an induction heating power supply 60. The temperature is the reactor is controlled by a temperature controller 70. The reaction device 100 is advantageously provided with a Data Acquisition System 80 (DAS or DAQ) for sampling signals of various experimental parameters and converting them into computer processable values.

(25) The flow of nitrogen N.sub.2 and oxygen O.sub.2 with predetermined rates fluidize the material inside the tube so that it provides the minimum fluidization conditions, which is achieved by synchronizing the flow rates and the temperature inside the reactor 10 measured by thermocouples. However, the ratio between nitrogen N.sub.2 and oxygen O.sub.2 is kept constant by the digital flow controller 22

(26) The current flow (which changes direction with a very high frequency) in the metal coil 15 induces a magnetic field so that the direction of said magnetic field also changes with a very high frequency. The stainless steel rods 14 act as conductors where the current is induced by the magnetic field. As a consequence, heat is released by Joule effect inside the tube of the reactor 10 surrounded by the metal coil 15.

Example—Optimum carbon and O.SUB.2 .for CaS decomposition to SO.SUB.2 .and CaO

(27) The CO.sub.2 required to react with CaS and produce SO.sub.2 and CaO is provided by carbon combustion. Therefore, oxygen should be above stoichiometry to assure enough amounts of CO.sub.2 production. Low oxygen content yields CO formation, which does not react with CaS. As a result, the oxygen amount injected into the reactor should at least fulfill energy requirements for all decomposition reactions. Then, the produced CO.sub.2 can initiate CaS initial conversion to SO.sub.2 and CaO as follows:
CaS+3CO.sub.2.fwdarw.CaO+SO.sub.2+3CO  (7)

(28) On the other hand, if the injected oxygen is too high, although the released energy would be higher, it yields large amounts of CO.sub.2 production, which can lead to CaSO.sub.4 formation instead of CaO and SO.sub.2 according to the following reaction:
CaS+2O.sub.2.fwdarw.CaSO.sub.4  (13)

(29) Therefore, oxygen should be optimized for this process. FactSage™ simulation results provided in FIG. 3(a) and (b) show that the heat provided by carbon combustion when C/CaS≈0.2 and O.sub.2/C≈6 provides ample heat (≈10.5 kJ/g CaS), which also can be used for preheating the solid feed and the oxidizing gas before the decomposition reactor.

(30) In general, the following four series of reactions take place in order as the process starts. Step one includes carbon combustion and CaS oxidation in the presence of oxygen:
C+0.5O.sub.2.fwdarw.CO  (5)
C+O.sub.2.fwdarw.CO.sub.2  (6)
CaS+1.5O.sub.2.fwdarw.CaO+SO.sub.2  (14)
CaS+2O.sub.2.fwdarw.CaSO.sub.4  (13)

(31) in which reaction (6) with respect to reaction (5) is the most probable phenomenon due to the high concentration of oxygen in the reactor. Although the oxygen is under control, the side reaction (13) occurs unfavorably compared to reaction (14). In step two after CaSO.sub.4 production, however negligible, the following series of reactions occur not only between CaSO.sub.4 and CaS, but also with carbon, which ultimately helps the favorable production of CaO and SO.sub.2:
CaSO.sub.4+CO.fwdarw.CaO+SO.sub.2+CO.sub.2  (15)
CaSO.sub.4+4CO.fwdarw.CaS+CO.sub.2  (16)
2CaSO.sub.4+C.fwdarw.2CaO+2SO.sub.2+CO.sub.2  (17)
CaSO.sub.4+4C.fwdarw.CaS+4CO  (18)

(32) and also
3CaSO.sub.4+CaS.fwdarw.4CaO+4SO.sub.2  (19)
CaSO.sub.4+3CaS.fwdarw.4CaO+4S  (20)
CaS+3CaSO.sub.4+4CO.sub.2.fwdarw.4CaCO.sub.3+4SO.sub.2  (21)
CaS+3SO.sub.3.fwdarw.CaO+4SO.sub.2  (22)

(33) Thus, for unfavorable CaSO.sub.4 removal, it is not necessary to add an oxidizing step similar to old processes [4] because CaSO.sub.4 is converted to either CaS or desired products by the CO produced from either carbon oxidation (reaction 5) or CaSO.sub.4—C solid-solid reaction (18). Consequently, CaS can be decomposed to CaO and SO.sub.2 by a carbon oxidation process where O.sub.2/C≈6 and C/CaS≈0.2. The energy required for all the decomposition reactions is provided with carbon oxidation at 1100° C., thereby requiring no external energy.

(34) For the experiments performed in the fluidized bed reactor, initial conditions of the feed are summarized in Table 1 below. The results of all experiments are also summarized in Table 2, which is described in the next two sections.

(35) TABLE-US-00001 TABLE 1 Inlet properties of fluidized bed experiments in the heat-induced fluidized bed reactor illustrated in FIG. 2 at 1100° C. Inlet property C/CaS 0.15 0.25 0.35 CaS (g) 5.22 4.80 4.44 C (g) 0.78 1.20 1.56 O.sub.2/PG 2, 3, 4 2, 3, 4 2, 3, 4

(36) Note that coal was used as a source of carbon in all experiments.

(37) TABLE-US-00002 TABLE 2 CaS conversion, CaO yield, and CaSO.sub.4 yield (corresponding to each cell from left to right) in a fluidized bed reactor at 1100° C. with the initial conditions summarized in Table 1 and XPS analysis summarized in Tables 3 and 4. 0.sub.2/CaS C/CaS 2 3 4 0.15 0.83, 0.55, 0.22 0.25 0.85, 0.75, 0.02 0.93, 0.83, 0.08 0.96, 0.67, 0.28 0.35 0.85, 0.77, 0.03

(38) Table 3 shows the effect of C/CaS variation with constant O.sub.2/CaS (≈3, which is considered to be optimum).

(39) When C/CaS≈0.15, O.sub.2/CaS≈3 yields more CO.sub.2 production than CO according to the following reactions:
C+0.5O.sub.2.fwdarw.CO  (5)
C+O.sub.2.fwdarw.CO.sub.2  (6)

(40) Moreover, according to the O.sub.2 abundance, the two following reactions also occur:
CaS+1.5O.sub.2.fwdarw.CaO+SO.sub.2  (14)
CaS+2O.sub.2.fwdarw.CaSO.sub.4  (13)

(41) which result in CaSO.sub.4 formation undergoing reactions (15) to (22) afterwards. As a result, CaS conversion is not high enough when C/CaS≈0.15 since CaS is reproduced at some stages or does not fully react with CO.sub.2 because of a carbon shortage.

(42) The remarkable feature of this series of reactions is that CO is produced from two reactions under any circumstances:
CaS+3CO.sub.2.fwdarw.CaO+SO.sub.2+3CO  (7)
C+0.5O.sub.2.fwdarw.CO  (5)

(43) or even from
CaSO.sub.4+4C.fwdarw.CaS+4CO  (18)

(44) providing the formation of CaSO.sub.4. The CO formation plays a significant role in obtaining high CaS conversion, because when CaS reacts with oxygen, CaSO.sub.4 formation is inevitable as a layer around CaS particles. The CO production according to the above mentioned reactions, in this case, reacts with CaSO.sub.4 and converts it to CaO and SO.sub.2. Therefore, CaS particles would again find the opportunity to be in contact with CO.sub.2 and O.sub.2 molecules and undergo decomposition reactions.

(45) By increasing the carbon in the feed from C/CaS≈0.15 to 0.25 and since oxygen is at the optimum value required to produce a sufficient amount of CO.sub.2 to react with CaS, the conversion of CaS increases while CaSO.sub.4 formation is almost halted by the fast reaction of carbon and oxygen. The CO.sub.2 formation at this stage would favor the following reaction to its maximum extent:
CaS+3CO.sub.2.fwdarw.CaO+SO.sub.2+3CO  (7)

(46) However, when carbon in the feed increases to C/CaS≈0.35, the injected O.sub.2/C would be under the optimum value, thereby producing more CO instead of CO.sub.2. Under these circumstances, the oxygen partially reacts with CaS and produces CaO and SO.sub.2 along with CaSO.sub.4. According to the higher CO formation compared to that of C/CaS≈0.25, CaSO.sub.4 yield is lowest in this case because a high amount of CO formation favors CaSO.sub.4 conversion to the other products.

(47) TABLE-US-00003 TABLE 3 Effects of C/CaS ratio on the remaining solid composition in a fluidized bed reactor at 1100° C. by XPS analysis with the initial conditions summarized in Table 1 when O.sub.2/CaS ≈ 3. CaS CaO CaSO.sub.4 CaS CaO CaS0.sub.4 conversion yield yield C/CaS (mol. %) (mol. %) (mol. %) (≈%) (≈%) (≈%) 0.15 7.2 66.2 26.5 83 55 22 0.25 2.1 89.2 8.6 93 83 8 0.35 7.8 88.7 3.3 85 77 3

(48) Table 4 shows the effects of O.sub.2/CaS variations with constant C/CaS (≈0.25, which is considered to be optimum).

(49) For C/CaS≈0.25, the optimum O.sub.2/CaS is ≈3.

(50) Any lower amounts of oxygen in the feed favor CO production rather than CO.sub.2.

(51) Note that CaS does not react with CO directly but with CO.sub.2.

(52) As a result, partial CaS reaction with CO.sub.2 favors CaO and SO.sub.2 production, however, CaSO.sub.4 is also converted to the desired products as a result of a reaction with CO.

(53) On the other hand, any other amounts of oxygen larger than that of O.sub.2/CaS≈3 would result in the partial production of CaSO.sub.4 according to CaS+2O.sub.2.fwdarw.CaSO.sub.4.

(54) However, a large oxygen presence yields CaS decomposition to desired products as well.

(55) Thus, CaS total conversion increases at this stage while CaSO.sub.4 yield also noticeably increases.

(56) In other words, at high oxygen values more than the optimum required in the feed, CaS total conversion increases, although this increase does not culminate into the formation of desired products.

(57) TABLE-US-00004 TABLE 4 Effects of O.sub.2/CaS ratio on the remaining solid composition in a fluidized bed reactor at 1100° C. by XPS analysis with the initial conditions summarized in Table 1 when C/CaS ≈ 0.25. CaS CaO CaSO.sub.4 CaS CaO CaSO.sub.4 conversion yield yield O.sub.2/CaS (mol. %) (mol. %) (mol. %) (≈%) (≈%) (≈%) 2 9.4 88.2 2.4 85 75 2 3 2.2 89.2 8.6 93 83 8 4 1.0 69.8 29.2 96 67 28

(58) The SO.sub.2 formation patterns from all the performed experiments in the fluidized bed reactor are shown in FIG. 4.

(59) As expected based on the above experiments, the maximum SO.sub.2 production occurs when O.sub.2/CaS≈3 and C/CaS≈0.25 (curve C2).

(60) Higher amounts of either carbon or oxygen hinder SO.sub.2 formation while lower amounts result in partial CaS conversion and, thus, less desired gaseous products.

(61) TABLE-US-00005 TABLE 5 Coal characterization by CHNS. These characteristics were used in simulations and fluidized bed experiments. Compound wt. % min wt. % max C 71.5 72 H 4.8 5.0 N 1.7 1.8 S 1.3 2.2 O 8.5 8.9 Cl ppm 369 407

(62) Note that in simulations, only the carbon content of coal was considered for calculations.

(63) TABLE-US-00006 TABLE 6 NAA results for pure coal. Element (ppm) Element (ppm) Element (ppm) Element (ppm) U 1.33 V 39 Cd <0.25 Ni 17.4 Ti 633 Cl 341 Au <0.0018 Ag <0.42 Sn <53 Al 13980 Hf 0.76 Sc 3.2 I <3 Ca 1379 Ba 101 Rb 14 Mn 55 S 17455 Br 3.2 Fe 12982 Mg 880 Se 3.5 As 26 An 26 Cu <64 Mo 46.4 Sb 0.61 Co 6.3 In <0.01 Hg 0.059 W 0.48 K 2326 Si <40000 Th <1 Zr 39 La 8 Na 342 Cr 18 Cs 3.1

REFERENCES

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