In the following, the present invention is described on the basis of examples. A first example relates to the application of the present invention in a power plant operation, in order to reduce or even eliminate the CO2 discharge arising therein while obtaining energy.
According to the present invention, there is an array of chemical reactions running in a targeted way, in which new chemical compounds (called products) result from the starting materials (also called educts or reactants). The reactions according to the present invention of the method identified at the beginning as the main process are designed in such a way that CO2 is consumed and/or bound in significant quantities.
In a first exemplary embodiment, sand which is admixed with mineral oil or oil shales are used as starting materials, for example. These starting materials are supplied to a reaction chamber, for example, in the form of an afterburner or a combustion chamber. CO2 is blown into this chamber. In the first exemplary embodiment, this CO2 may be the CO2 exhaust gas which arises in large quantities when obtaining energy from fossil combustibles and up to now has escaped into the atmosphere in many cases. In addition, (ambient) air is supplied to the chamber. Instead of the ambient air, or in addition to the ambient air, steam or hypercritical H2O at over 407° C. may be supplied to the method.
Furthermore, nitrogen is to be blown in at another point in the method, or the combustion chamber, respectively.
In addition, a type of catalyst is used. Aluminum is especially suitable. Under suitable environmental conditions, a reduction occurs in the chamber, which may be represented greatly simplified as follows:
This means that the quartz component present in the sand or shale is converted into crystalline silicon.
The mineral oil of the sand used assumes the role of the primary energy supplier and is largely decomposed pyrolytically into hydrogen (H2) and a compound similar to graphite at temperatures above 1000° C. in the method according to the present invention. The hydrogen is thus withdrawn from the hydrocarbon chain of the mineral oil in the running reactions. The hydrogen may be diverted into pipeline systems of the natural gas industry or stored in hydrogen tanks, for example.
In a second exemplary embodiment, the present invention is applied in connection with a pyrolysis method of Pyromex AG, Switzerland. The present invention may also be used as a supplement or alternative to the oxyfuel method. Thus, for example, using the present invention, heat may be obtained by an energy cascade according to the following approach. In an alteration of the oxyfuel method, additional heat is generated with the addition of Aluminum, preferably liquid Aluminum, and with combustion of oil sand (instead of oil or coal) with oxygen (O2) and, if needed, also nitrogen (N2) (Wacker accident). If the nitrogen coupling to silicon compounds is needed, the pure nitrogen atmosphere is preferably achieved from ambient air by combustion of the oxygen component of the air with propane gas (known from propane nitration).
According to the present invention, Aluminum (Al) may be used. It is currently only possible to obtain Aluminum cost-effectively from bauxite. Bauxite contains approximately 60% Aluminum oxide (Al2O3), approximately 30% iron oxide (Fe2O3), silicon oxide (SiO2), and water. This means the bauxite is typically always contaminated with the iron oxide (Fe2O3) and the silicon oxide (SiO2).
Al2O3 cannot be chemically reduced because of its extremely high lattice energy. However, it is possible to produce Aluminum industrially by fused-salt electrolysis (cryolite-alumina method) of Aluminum oxide Al2O3. The Al2O3 is obtained by the Bayer method, for example. In the cryolite-alumina method, the Aluminum oxide is melted with cryolite (salt: Na3[AlF6]) and electrolyzed. In order not to have to work at the high melting temperatures of Aluminum oxide of 2000° C., the Aluminum oxide is dissolved in a melt of cryolite. Therefore, the operating temperature in the method is only from 940 to 980° C.
In fused-salt electrolysis, liquid Aluminum arises at the cathode and oxygen arises at the anode. Carbon blocks (graphite) are used as anodes. These anodes burn off due to the resulting oxygen and must be continuously renewed.
It is seen as a significant disadvantage of the cryolite-alumina method that it is very energy consuming because of the high binding energy of the Aluminum. The formation and emission of fluorine, which sometimes occurs, is problematic for the environment.
In the method according to the present invention, bauxite may be added to the method to achieve cooling of the process. The excess thermal energy in the system may be handled by the bauxite. This is performed analogously to the method in which scrap iron is supplied to an iron melt in a blast furnace for cooling when the iron melt becomes too hot.
Cryolite may be used as an aid if the method threatens to go out of control (see Wacker accident), in order to thus reduce the temperature in the system in the meaning of emergency cooling.
Like silicon carbide, silicon nitride is a wear resistant material which can be or is used in highly stressed parts in mechanical engineering, turbine construction, chemical apparatus, and engine construction.
Further details on the chemical proceedings and energy processes described may be inferred from the following pages
Quartz sand may be reacted with liquid Aluminum exothermically to form silicon and Aluminum oxide according to the Hollemann-Wiberg textbook:
3SiO2+4 Al (l)→3Si+2 Al2O3 ΔH=−618.8 kJ/Mol (exothermic)
Silicon combusts with nitrogen to form silicon nitride at 1350° C. The reaction is again exothermic
Silicon reacts slightly exothermically with carbon to form silicon carbide.
Si+C→SiC ΔH=−65.3 kJ/Mol (exothermic)
In addition, silicon carbide may be obtained endothermically directly from sand and carbon at approximately 2000° C.:
In order to reclaim Aluminum from the byproduct bauxite or Aluminum oxide Al2O3, liquid Al2O3 (melting point 2045° C.) is electrolyzed without adding cryolite to form Aluminum and oxygen. The reaction is strongly endothermic and is used for cooling the exothermic reactions.
2Al2O3(l)→4Al(l)+3O2(g) ΔH=+1676,8 kJ/Mol (endothermic)
Production of the silanes:
Magnesium reacts with silicon to form magnesium silicide:
2 Mg+Si→Mg2Si
Magnesium silicide reacts with hydrochloric acid to form monosilane SiH4 and magnesium chloride:
Mg2Si+4HCl(g)→SiH4+2 MgCl2
This synthetic pathway must actually also function with Aluminum: as a result, Aluminum silicide Al4Si3 arises as an intermediate product.
Higher silanes are possibly only accessible via polymerization of SiCl2 with SiCl4 and by subsequent reaction with LiAlH4, as the preceding work documents.
Producing silicon carbide and silicon nitride from oil sand
The ceramic materials silicon nitride Si3N4 and silicon carbide SiC may be obtained from an oil sand having approximately 30 wt.-percent petroleum via a multistage process. In order to be able to deal with the mixture of greatly varying hydrocarbon compounds known as petroleum, which is very chemically complex, in a stoichiometrically meaningful way, the formula C10H22, which actually stands for decane, is used in place of the petroleum. Sand, a material which is exactly described by the formula SiO2, is in a weight ratio of 70% to 30% with the petroleum contained therein. The oil sand is thus described in a coarse approximation by the formula SiO2+C10H22, SiO2 contributing a molecular weight of 60 g/mole and decane contributing a molecular weight of 142 g/mole. If one takes 100 g oil sand, 70 g SiO2 and 30 g “decane” or petroleum are provided. If the material quantities of SiO2 and “decane” contained therein are worked out, one obtains for SiO2:
n=(70 g)/(60 g/mole)≈1.167 mole SiO2
And for petroleum:
n=(30 g)/(142 g/mole)≈0.211 mole C10H22
If both mole numbers are multiplied by 5, 1 obtains 5.833 mole for SiO2 and 1.056 mole for C10H22, which makes about 6 mole SiO2 for a mole of C10H22. Therefore, the formula 6 SiO2+“1” C10H22 may be used in a good approximation for oil sand.
The preparation of silicon nitride Si3N4 from oil sand is performed as follows: firstly, the oil sand is heated together with dichloromethane CH2Cl2 in an oxygen-free atmosphere to 1000° C. Silicon changes the bonding partner and forms of silicon tetrachloride according to equation (I):
6SiO2+C10H22+12CH2Cl2→6SiCl4+12 CO+10CH4+3H2 (I)
In a second step, the silicon chloride obtained is hydrogenated at room temperature with lithium Aluminum hydride [1], according to equation (II).
SiCl4+LiAlH4→SiH4+LiAlCl4 (II)
Finally, the monosilane SiH4 obtained is combusted in pure nitrogen, equation (III):
3SiH4+4N2→Si3N4+4NH3 (III)
In order to obtain silicon carbide SiC, instead of the high temperature reaction (equation IV), which occurs at 2000° C. and consumes a large amount of energy, a more energetically favorable reaction pathway may also be found.
SiO2+3C→SiC+2CO (IV)
In this case, one again starts from silicon tetrachloride SiCl4, which is obtained from equation (I), and reacts it with graphite or methane:
SiCl4+CH4→SiC+4HCl (V)
or:
SiCl4+2C−>SiC+CCl4 (VI)
If one starts with 1 kg oil sand, 700 g silicon dioxide and 300 g “decane” are contained therein. Converted into the material quantities, n=11.67 mole results for silicon dioxide and n=2.11 mole results for “decane”.
According to equation (I), the following relative molecular weights apply for the compounds:
Since the material quantity for silicon tetrachloride SiCl4 is the same because of the identical stoichiometric factor, a quantity of SiCl4 results from 1 kg oil sand of:
m(SiCl4)=11.67 mole*169.9 g/mole=1.982 kg SiCl4
Because of the double material quantity of CO in relation to SiO2, a mass of CO results as follows:
m(CO)=2*11.67 mole*28 g/mole=653 g CO
Because of the tenfold material quantity of CH4 in relation to “decane”, a mass of CH4 results as follows:
m(CO)=10*2.11 mole*16 g/mole=338 g CH4
Because of the halved material quantity of H2 in relation to SiO2, a mass of H2 results as follows:
m(CO)=½*11.67 mole*2 g/mole=11.67 g H2
Furthermore, since all stoichiometric factors are equal to one in equation (II):
Since, in equation (III) the initial material quantity of silicon dioxide of 11.67 mole is still present, and the material quantity of Si3N4 is a third that of SiH4, in this case:
The material quantity of N2 is 4/3 that of SiH4: a mass of nitrogen may thus be calculated of:
m(N2)= 4/3*11.67 mole*28 g/mole=435.5 g N2
Converted to volume, these 435.5 g N2 correspond, at a molar volume of 22.41, to: V=348.41 N2.
The material quantity of NH3 is also 4/3 that of SiH4:
m(NH3)= 4/3*11.67 mole*17 g/mole=264.4 g NH3
Converted to volume, these 435.5 g NH3 again correspond, at a molar volume of 22.41, to: V=348.41 NH3.
Finally, the initial material quantity of 11.67 mole again applies for silicon tetrachloride for equation (V):
Converted to volume, these 186.7 g CH4 correspond, at a molar volume of 22.4 1, to: V=261.3 1 CH4.
m(HCl)=4*11.67 mole*36.5 g/mole=1.703 kg HCl
When calculated in the scale of tons, the units g may be replaced by kg, kg by tons t, and liters by m3, without anything changing in the numeric values.
The data for calculating the reaction enthalpy or heat tonality ΔH and the Gibbs free enthalpy ΔG originate from the standard work by Landolt and Börnstein [2]. Hess's law applies for calculating ΔH from the standard formation enthalpy Δh° of the individual compounds:
ΔH=ΣniΔh°i (products)−ΣmiΔh°i(educts)
ni, mi representing the relevant stoichiometric factors.
Entirely analogously, to calculate the entropy change ΔS and the heat capacity change ΔCp:
ΔS=ΣniΔS°i(products)−ΣmiΔS°i(educts)
ΔCp=ΣniΔCpi(products)−ΣmiΔCpi(educts)
S°i representing the standard entropy at room temperature (T=298 K) of the compound i.
If the enthalpy change is not sought at the standard temperature T of 298 Kelvin, but rather at another temperature, Kirchhoff's law applies under the aspect of the isobaric condition:
ΔCp representing the molar change of the heat capacity at constant pressure. If the entropy change is not sought at the standard temperature T of 298 Kelvin, but rather at another temperature, Kirchhoff's law applies analogously under the aspect of the isobaric condition:
The free Gibbs enthalpy G indicates in what regard a reaction runs spontaneously or non-spontaneously. The free enthalpy change ΔG is calculated by the formula:
ΔG=ΔH−T*ΔS
If a value for ΔG<0 results, a spontaneous, i.e., exergonic reaction exists.
If a value for ΔG>0 results, a nonspontaneous, i.e., endothermic reaction exists.
The following thermodynamic variables apply for equation (I):
6SiO2+C10H22+12CH2Cl2−>6SiCl4+12CO+10CH4+3H2 (I)
ΔH=6*(−577.4)+12*(−110.5)+10*(−74.85)−6*(−859.3)−(−249.7)−12*(−117.1) kJ/mol,
ΔH=+1271.8 kJ/mol
The following value is obtained for ΔS:
ΔS=6*331.4+12*197.4+10*186.19+3*130.6−6*42.09−540.5−12*270.2 J/mol Kelvin
ΔS=+2575.46 J/mol Kelvin
The entropy is increased, thus equation (I), at least favored by the driving force of entropy, will probably react toward the product side. In order to definitively answer this question, the free enthalpy change ΔG must still be calculated, the following formula being used
ΔG=ΔH−T*ΔS
The standardized 298 Kelvin is used for the temperature T. Therefore, ΔG=+1271.8 kJ/mole−298 K*2575.46 J/mole K=+504.31 kJ/mole. At room temperature, the free enthalpy change ΔG is positive, which indicates that the reaction (I) runs endergonically or non-spontaneously at this temperature. The driving force of the entropy is thus insufficient in the final analysis to displace the reaction toward the product side, since the endothermic contribution of the heat tonality counteracts it too strongly.
But what effect does a temperature increase have on ΔH, ΔS, and ΔG? For this purpose, ΔH (T=1300 K) and ΔS (T=1300 k) are calculated via the change of the heat capacity ΔCp in isobaric conditions.
ΔCp=6*90.58+12*29.15+10*35.79+3*20.83−6*44.43−243.1−12*51.1 J/mole Kelvin,
ΔCp=+214.79 J/mole Kelvin
ΔH(T=1300 K)=ΔH(T=298 K)+ΔCp(1300 K−298 K)=+1271.8 kJ/mole+214.79
J/mole*K*1002 Kelvin=+1487 kJ/mole, the reaction remains endothermic.
ΔS(T=1300 K)=ΔS(T=298 K)+ΔCp*ln (1300 K/298 K)=+2575.46 J/mole K+214.79
J/mole*K*ln(4.3624)=+2891.85 J/mole*K
ΔG(1300 K)=ΔH(1300 K)−T*ΔS (1300 K)=+1487 kJ/mole−1300 K*2891.85 J/mole*K
ΔG(1300 K)=−2272.41 kJ/mole, the reaction suddenly becomes exergonic at 1300 K.
The reaction may thus occur at 1300 Kelvin.
The following thermodynamic variables apply for equation (II):
SiCl4+LiAlH4−>SiH4+LiAlCl4
ΔH=(−61.0)+(−1114.15)−(−577.4)−(−100.8)kJ/mole=−496.95 kJ/mole
Equation (II) is thus an exothermic reaction, since ΔH<0.
For ΔS, the value of the entropy change may not be ascertained, since the entropy specified for LiAlH4 was not found [2]. In contrast, this reaction is described in Lehrbuch der Anorganischen Chemie [Textbook of Inorganic Chemistry] by Hollemann-Wiberg [1] as running spontaneously or exergonically at room temperature, which indicates that it must be the case that ΔG<0.
The following thermodynamic variables apply for equation (III):
3SiH4+4N2−>Si3N4+4NH3 (III)
ΔH=(−750.0)+4*(−46.19)−3*(−61.0)−0 kJ/mole=−751.76 kJ/mole
Equation (III) is thus an exothermic reaction, since ΔH<0.
The following value is obtained for ΔS:
ΔS=95.4+4*192.5−3*204.5−4*191.5 kJ/mole Kelvin
ΔS=−514.1 J/mole Kelvin, i.e., the reaction results in an entropy reduction.
With ΔG=ΔH−T*ΔS, the amount ΔG=−496.95 kJ/mole −298 K*(−514.1) J/mole K=−598.56 kJ/mole
Therefore, at room temperature, the free enthalpy ΔG is negative, which indicates that the reaction (III) runs exergonically, i.e., completely spontaneously, without external compulsions at this temperature. Nonetheless, an ignition temperature of approximately 900 K must be selected in order to set the reaction going merely because of the activation energy required for breaking the N2 molecule. The reaction subsequently sustains itself on its own.
The following thermodynamic variables apply for equation (V):
SiCl4+CH4−>SiC+4HCl (V)
ΔH=(−111.7)+4*(−92.31)−(−577.4)−(−74.85) kJ/mole=+171.31 kJ/mole
Equation (V) is thus a reaction which runs endothermically at room temperature, since ΔH>0.
The following value is obtained for ΔS:
ΔS=16.46+4*186.9−331.4−186.19 kJ/mole,
ΔS=+246.47 J/mole Kelvin, i.e., an entropy increase occurs!
With ΔG=ΔH−T*ΔS, the amount ΔG=+171.31 kJ/mole−298 K*246.47 J/mole K=+97.86 kJ/mole.
The reaction is thus both endothermic (ΔH>0) and also endergonic (ΔG>0) at room temperature. It may therefore not occur at room temperature.
ΔCp=26.65+4*29.12−90.58−35.79 J/mole Kelvin=+16.76 J/mole Kelvin
ΔH(T=1300 K)=ΔH(T=298 K)+ΔCp(1300 K−298 K)=+171.31 kJ/mole+16.76
J/mole*K*1002 Kelvin=+188.1 kJ/mole, the reaction remains endothermic.
ΔS(T=1300 K)=ΔS(T=298 K)+ΔCp*ln(1300 K/298 K)=+246.47 J/mole K+16.76
J/mole*K*ln(4.3624)=+271.16 J/mole*K
ΔG(1300 K)=ΔH(1300 K)−T*ΔS(1300 K)=+188.1 kJ/mole−1300 K*271.76 J/mole*K
ΔG(1300 K)=−164.4 kJ/mole, the reaction suddenly becomes slightly exergonic at 1300 K.
The reaction may thus occur at 1300 Kelvin.
The following thermodynamic variables apply for equation (VI):
SiCl4+2C−>SiC+CCl4 (VI)
ΔH=(−111.7)+(−106.7)−(−577.4)−0 kJ/mole=+359.0 kJ/mole
Equation (VI) is thus a reaction which runs endothermically at room temperature, since ΔH>0.
The following value is obtained for ΔS:
ΔS=16.46+309.7−331.4−2*5.74 kJ/mole Kelvin
ΔS=−16.72 J/mole Kelvin, i.e., a slight entropy reduction occurs.
The reaction is thus both endothermic (ΔH>0) and also endergonic (ΔG>0) at room temperature. It may therefore not occur at room temperature. What about at a temperature of 1300 Kelvin?
The following value is obtained for ΔCp:
ΔCp=26.65+83.4−90.58−2*8.53 J/mole Kelvin=+2.41 J/mole Kelvin
ΔH(T=1300 K)=ΔH(T=298 K)+ΔCp(1300 K−298 K)=+359.0 kJ/mole+2.41
J/mole*K*1002 Kelvin=+361.4 kJ/mole, the reaction remains endothermic.
ΔS(T=1300 K)=ΔS(T=298 K)+ΔCp*ln(1300 K/298 K)=−16.72 J/mole K+2.41
J/mole*K*ln(4.3624)=−13.17 J/mole*K
ΔG(1300 K)=ΔH(1300 K)−T*ΔS(1300 K)=+361.4 kJ/mole−1300 K*(−13.17 J/mole*K)
ΔG(1300 K)=+378.5 kJ/mole, the reaction remains endergonic, unchanged even at 1300 K.
This last reaction demonstratively illustrates that not every equilibrium may be shifted to the other side with a temperature increase, sometimes everything remains as it was and the suggested reaction pathway must be discarded. This is the case for this reaction, in any case.
The synthetic pathway described under Chapter 2 may be performed using the suggested reaction equations if the appropriate thermodynamic favorable temperatures are maintained, reaction (VI) representing the exception, because it may not occur at any of the calculated temperatures. Therefore, a clear synthetic pathway for preparing silicon nitride Si3N4 and silicon carbide SiC has been shown, which will be described once again supplemented with the required operating temperatures. Firstly, the oil sand is heated together with dichloromethane CH2Cl2 in an oxygen-free atmosphere to 1300 Kelvin (1000° C.). Silicon changes the binding partner and forms silicon tetrachloride according to equation (I):
In a second step, the silicon chloride obtained is hydrogenated at room temperature with lithium Aluminum hydride (Hollemann, A. F. et al., Lehrbuch der Anorganischen Chemie [Textbook of Inorganic Chemistry], 91st-100th Edition, Walter de Gruyter-Verlag, Berlin, N.Y., pp. 743, 749 et seq. (1985)), according to equation (II).
Finally, the monosilane SiH4 obtained is combusted in pure nitrogen, equation (III), the ignition temperature having to be approximately 600 K above room temperature because of the activation energy required for breaking the nitrogen molecule:
In order to obtain silicon carbide SiC, one starts again from silicon tetrachloride SiCl4, which is obtained from equation (I), and reacts it with methane at 1300 K:
Instead of the monosilane obtained in equation (I), according to (Hollemann, A. F. et al., Lehrbuch der Anorganischen Chemie [Textbook of Inorganic Chemistry], 91st-100th Edition, Walter de Gruyter-Verlag, Berlin, N.Y., pp. 743, 749 et seq. (1985)), higher silyl chlorides may also be obtained via polymerization reactions of SiCl2 and higher silanes may also be obtained by the following hydrogenation with LiAlH4, as the following reaction equations indicate:
Higher silanes (from Si7H16) provide the advantage that they are no longer self-igniting and maybe combusted in a much more controlled way than SiH4. Accordingly, combustion with pure nitrogen is also preferred if higher silanes reach this reaction.
Number | Date | Country | Kind |
---|---|---|---|
DE102006021960.0 | May 2006 | DE | national |
EP06022578.6 | Oct 2006 | EP | regional |