Abstract:
The crude oil reserves have a calculable time limit. Before, for example, the automobile industry, aviation, the weapons industry, and space travel change their combustion engines over to silanes, which are known to combust with the air nitrogen in a hot chamber and provide atomic hydrogen, a possibility must be found to reduce the high oil prices. The very large reserves of oilbearing sands and jails provide the requirement for this purpose. The hydrocarbons of the minerals are decomposed into hydrogen and hydrocarbon residues to provide primary energy.

Description:
CROSS-REFERENCES TO RELATED APPLICATIONS 
       [0001]    This application claims the priority of the application DE 10 2006 021 960.0 having the title “Ölhaltige Sande und Schiefer und ihre Gemische als Ausgangssubstanzen zur Darstellung von kristallinem Silizium und Wasserstoffgas sowie zur Herstellung von Siliziumnitrid, Siliziumcarbid und Silanen,” which was filed on 10 May 2006; and 
         [0002]    This application further claims the priority of the application EP 06 022 578.6 having the title “Ölhaltige Sande und Schiefer und ihre Gemische als Ausgangssubstanzen zum Binden oder Zerlegen von Kohlenstoffdioxid und Nox, sowie zur Darstellung von kristallinem Silizium und Wasserstoffgas sowie zur Herstellung von Siliziunmitrid, Siliziumcarbid und Silanen”, which was filed on 29 Oct. 2006. Both applications are incorporated herein by reference in their entirety for all purposes. 
       BACKGROUND OF THE INVENTION 
       [0003]    Oil-bearing sands and shales and their mixtures as starting substances for binding or decomposing carbon dioxide and NOx, and for preparing crystalline silicon and hydrogen gas, and for producing silicon nitride, silicon carbide, and silanes 
       BRIEF SUMMARY OF THE INVENTION 
       [0004]    Carbon dioxide is a chemical compound comprising carbon and oxygen. Carbon dioxide is a colorless and odorless gas. At low concentration, it is a natural component of air and arises in living organisms during cell respiration, but also during the combustion of carbonaceous substances with sufficient oxygen. Since the beginning of industrialization, the CO 2  component in the atmosphere has significantly increased. The main reasons for this are the CO 2  emissions caused by humans—known as anthropogenic emissions. 
         [0005]    The carbon dioxide in the atmosphere absorbs a part of the thermal radiation. This property makes carbon dioxide into a greenhouse gas and is one of the causes of the greenhouse effect. 
         [0006]    In addition to this climate-relevant aspect, however, CO 2  also has a negative influence on health. If CO 2  is provided in a concentration in the blood of humans which lies above the physiological concentration (in the meaning of natural), it may result in reduction or even cancellation of the reflex respiratory impulse, for example. However, CO 2  may also result in headaches and dizziness, and at higher concentrations even in accelerated heart rate, elevated blood pressure, difficulty breathing, and loss of consciousness. 
         [0007]    In addition, CO 2  changes the chronological biology of the plant world, which no longer runs synchronously. The stability of the food chain is thus endangered. 
         [0008]    For these and also other reasons, research and development is currently being performed in greatly varying directions to find a way of reducing the anthropogenic CO 2  emissions. There is a great need for CO 2  reduction in particular in connection with energy production, which is frequently performed by the combustion of fossil energy carriers, such as coal or gas, but also in other combustion processes, for example, during garbage combustion. Hundreds of millions of tons of CO 2  are released into the atmosphere every year by such processes. 
         [0009]    The fuels required for producing heat generate CO 2 , as explained at the beginning. Up to this point, no one has arrived at the idea of using the sand provided in oil-bearing sands (SiO 2 ), oil-bearing shale (SiO 2 +[CO 3 ] 2 ), in bauxite, or tar-bearing sands or shales, and other mixtures to reduce the CO 2  discharge and, in addition, obtain new raw materials from the products of such a novel method. 
         [0010]    Instead of using naturally occurring mixtures of sand and oil in this novel method, industrial or natural waste containing hydrocarbons, possibly after admixing with sand, may also be used. 
         [0011]    Using natural asphalt (also referred to as mineral pitch) instead of the oil component is also conceivable. A mixture made of asphalt with pure sand or with construction rubble which contains a sand component is especially preferable. 
         [0012]    However, water glass, a mixture of sand with acid or base, may also be used, the water glass being admixed with mineral oils in order to provide the hydrocarbon component necessary for the present invention (microemulsion method). 
         [0013]    The reserves of oil-bearing sands (SiO 2 ) and shales (SiO 2 +[CO 3 ] 2 ) are known to exceed the world oil reserves multiple times over. The technical methods applied for separating oil and minerals are currently ineffective and too costly. Natural asphalt occurs at multiple locations of the earth, but is currently mined at commercial scale primarily in Trinidad. 
         [0014]    Sand occurs in greater or lesser concentrations everywhere on the surface of the earth. A majority of the sand occurring comprises quartz (silicon dioxide; SiO 2 ). 
         [0015]    The object of the present invention is to provide such possible raw materials and describe their technical production. The chemical findings used in the method are characterized in that the hydrocarbons present in the sand and shales and other mixtures participate in a reaction, and also the SiO 2  is chemically changed by the reaction. 
         [0016]    1) Aluminum oxide (Al 2 O 3 ) and silicon (Si) may be produced from the oil-bearing sands or the other cited mixtures by combustion together with liquid Aluminum or hot Aluminum dust. Strongly simplified, the following reaction occurs: 
         [0000]      SiO 2 +Al→Si+Al 2 O 3    
         [0017]    2) The mineral oil of the sands is pyrolyzed at high temperatures to form “illuminating gas”. This gas mixture is largely free of CO and CO 2 , if a slight hydrogen excess is used during the combustion of the Aluminum, for example. The gas mixture thus predominantly comprises hydrogen, which originates from the carbon chains of the mineral oils. The carbon itself precipitates at suitable operating temperature as a residue similar to graphite and may be used as an anode, for example. 
         [0018]    3) The heat released at the furnace in the thermal reaction of the main process may drive the turbine of a generator as strongly compressed water steam, for example. 
         [0019]    4) The most important ceramics used in technology—silicon nitride (Si 3 N 4 : having a hardness similar to diamond) and silicon carbide (SiC: having its noteworthy thermal conductivity)—may be obtained in the same reaction start by other reaction conditions, as explained in numbers 5 through 7. 
         [0020]    5) If needed, the crystalline silicon (e.g., as a powder at suitable temperature) may be reacted after ignition directly with pure (cold) nitrogen (e.g., nitrogen from the ambient air) to form silicon nitride, because the reaction is strongly exothermic. (Si 3 N 4  is a solid noble gas [Plichta].) The heat thus arising may be used as described in number 3. One may for instance use a method for obtaining nitrogen which is known from making stainless steel using propane gas (propane nitration). 
         [0021]    6) The carbonaceous residue resulting in number 2 may also be reacted exothermically with the crystalline silicon obtained to form silicon carbide. 
         [0022]    7) The available crystalline silicon has surfactant properties and may be treated catalytically (e.g., using magnesium and/or Aluminum as a catalyst) with hydrogen, monosilane resulting. This monosilane may be removed from the reaction chamber and subjected once again at another location to a catalytic pressure reaction. According to the equation 
         [0000]      Si+SiH 4 →(Using catalysts such as Pt, etc.)→Si(SiH 44 )+SiH n (SiH 4 ) m +Si n H m    
         [0023]    long-chain silanes may be prepared, which may be used in the technology of fuel cells, in engines based on ceramic, and also in scram jet drives. 
         [0024]    This is also suitable for the combustion of nitrogen with silanes. 
         [0025]    Further details and advantages of the present invention are described in the following on the basis of exemplary embodiments. 
     
     DETAILED DESCRIPTION OF THE INVENTION 
       [0026]    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 CO 2  discharge arising therein while obtaining energy. 
         [0027]    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 CO 2  is consumed and/or bound in significant quantities. 
         [0028]    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. CO 2  is blown into this chamber. In the first exemplary embodiment, this CO 2  may be the CO 2  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 H 2 O at over 407° C. may be supplied to the method. 
         [0029]    Furthermore, nitrogen is to be blown in at another point in the method, or the combustion chamber, respectively. 
         [0030]    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: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0031]    This means that the quartz component present in the sand or shale is converted into crystalline silicon. 
         [0032]    The mineral oil of the sand used assumes the role of the primary energy supplier and is largely decomposed pyrolytically into hydrogen (H 2 ) 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. 
         [0033]    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 (O 2 ) and, if needed, also nitrogen (N 2 ) (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). 
         [0034]    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 (Al 2 O 3 ), approximately 30% iron oxide (Fe 2 O 3 ), silicon oxide (SiO 2 ), and water. This means the bauxite is typically always contaminated with the iron oxide (Fe 2 O 3 ) and the silicon oxide (SiO 2 ). 
         [0035]    Al 2 O 3  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 Al 2 O 3 . The Al 2 O 3  is obtained by the Bayer method, for example. In the cryolite-alumina method, the Aluminum oxide is melted with cryolite (salt: Na 3 [AlF 6 ]) 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. 
         [0036]    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. 
         [0037]    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. 
         [0038]    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. 
         [0039]    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. 
         [0040]    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. 
         [0041]    Further details on the chemical proceedings and energy processes described may be inferred from the following pages 
         [0042]    Quartz sand may be reacted with liquid Aluminum exothermically to form silicon and Aluminum oxide according to the Hollemann-Wiberg textbook: 
         [0000]      3SiO 2 +4 Al (l)→3Si+2 Al 2 O 3  ΔH=−618.8 kJ/Mol (exothermic) 
         [0043]    Silicon combusts with nitrogen to form silicon nitride at 1350° C. The reaction is again exothermic 
         [0000]    
       
                 
         
             
             
         
       
     
         [0044]    Silicon reacts slightly exothermically with carbon to form silicon carbide. 
         [0000]      Si+C→SiC ΔH=−65.3 kJ/Mol (exothermic) 
         [0045]    In addition, silicon carbide may be obtained endothermically directly from sand and carbon at approximately 2000° C.: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0046]    In order to reclaim Aluminum from the byproduct bauxite or Aluminum oxide Al 2 O 3 , liquid Al 2 O 3  (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. 
         [0000]      2Al 2 O 3 (l)→4Al(l)+3O 2 (g) ΔH=+1676,8 kJ/Mol (endothermic) 
         [0000]    Production of the silanes: 
         [0047]    Magnesium reacts with silicon to form magnesium silicide: 
         [0000]      2 Mg+Si→Mg 2 Si 
         [0048]    Magnesium silicide reacts with hydrochloric acid to form monosilane SiH 4  and magnesium chloride: 
         [0000]      Mg 2 Si+4HCl(g)→SiH 4 +2 MgCl 2    
         [0049]    This synthetic pathway must actually also function with Aluminum: as a result, Aluminum silicide Al 4 Si 3  arises as an intermediate product. 
         [0050]    Higher silanes are possibly only accessible via polymerization of SiCl 2  with SiCl 4  and by subsequent reaction with LiAlH 4 , as the preceding work documents. 
         [0051]    Producing silicon carbide and silicon nitride from oil sand 
       1. INTRODUCTION AND “FORMULA” FOR OIL SAND 
       [0052]    The ceramic materials silicon nitride Si 3 N 4  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 C 10 H 22 , which actually stands for decane, is used in place of the petroleum. Sand, a material which is exactly described by the formula SiO 2 , 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 SiO 2 +C 10 H 22 , SiO 2  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 SiO 2  and 30 g “decane” or petroleum are provided. If the material quantities of SiO 2  and “decane” contained therein are worked out, one obtains for SiO 2 : 
         [0000]        n =(70 g)/(60 g/mole)≈1.167 mole SiO 2    
         [0053]    And for petroleum: 
         [0000]        n =(30 g)/(142 g/mole)≈0.211 mole C 10 H 22    
         [0054]    If both mole numbers are multiplied by 5, 1 obtains 5.833 mole for SiO 2  and 1.056 mole for C 10 H 22 , which makes about 6 mole SiO 2  for a mole of C 10 H 22 . Therefore, the formula 6 SiO 2 +“1” C 10 H 22  may be used in a good approximation for oil sand. 
       2. SYNTHETIC PATHWAY 
       [0055]    The preparation of silicon nitride Si 3 N 4  from oil sand is performed as follows: firstly, the oil sand is heated together with dichloromethane CH 2 Cl 2  in an oxygen-free atmosphere to 1000° C. Silicon changes the bonding partner and forms of silicon tetrachloride according to equation (I): 
         [0000]      6SiO 2 +C 10 H 22 +12CH 2 Cl 2 →6SiCl 4 +12 CO+10CH 4 +3H 2   (I) 
         [0056]    In a second step, the silicon chloride obtained is hydrogenated at room temperature with lithium Aluminum hydride [1], according to equation (II). 
         [0000]      SiCl 4 +LiAlH 4 →SiH 4 +LiAlCl 4   (II) 
         [0057]    Finally, the monosilane SiH 4  obtained is combusted in pure nitrogen, equation (III): 
         [0000]      3SiH 4 +4N 2 →Si 3 N 4 +4NH 3   (III) 
         [0058]    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. 
         [0000]      SiO 2 +3C→SiC+2CO  (IV) 
         [0059]    In this case, one again starts from silicon tetrachloride SiCl 4 , which is obtained from equation (I), and reacts it with graphite or methane: 
         [0000]      SiCl 4 +CH 4 →SiC+4HCl  (V) 
         [0000]    or: 
         [0000]      SiCl 4 +2C−&gt;SiC+CCl 4   (VI) 
       3. STOICHIOMETRIC CALCULATIONS 
       [0060]    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”. 
         [0061]    According to equation (I), the following relative molecular weights apply for the compounds: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0062]    Since the material quantity for silicon tetrachloride SiCl 4  is the same because of the identical stoichiometric factor, a quantity of SiCl 4  results from 1 kg oil sand of: 
         [0000]        m (SiCl 4 )=11.67 mole*169.9 g/mole=1.982 kg SiCl 4    
         [0063]    Because of the double material quantity of CO in relation to SiO 2 , a mass of CO results as follows: 
         [0000]        m (CO)=2*11.67 mole*28 g/mole=653 g CO 
         [0064]    Because of the tenfold material quantity of CH 4  in relation to “decane”, a mass of CH 4  results as follows: 
         [0000]        m (CO)=10*2.11 mole*16 g/mole=338 g CH 4    
         [0065]    Because of the halved material quantity of H 2  in relation to SiO 2 , a mass of H 2  results as follows: 
         [0000]        m (CO)=½*11.67 mole*2 g/mole=11.67 g H 2    
         [0066]    Furthermore, since all stoichiometric factors are equal to one in equation (II): 
         [0000]    
       
                 
         
             
             
         
       
     
         [0067]    Since, in equation (III) the initial material quantity of silicon dioxide of 11.67 mole is still present, and the material quantity of Si3N 4  is a third that of SiH 4 , in this case: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0068]    The material quantity of N 2  is 4/3 that of SiH 4 : a mass of nitrogen may thus be calculated of: 
         [0000]        m (N 2 )= 4/3*11.67 mole*28 g/mole=435.5 g N 2    
         [0069]    Converted to volume, these 435.5 g N 2  correspond, at a molar volume of 22.41, to: V=348.41 N 2 . 
         [0070]    The material quantity of NH 3  is also 4/3 that of SiH 4 : 
         [0000]        m (NH 3 )= 4/3*11.67 mole*17 g/mole=264.4 g NH 3    
         [0071]    Converted to volume, these 435.5 g NH 3  again correspond, at a molar volume of 22.41, to: V=348.41 NH 3 . 
         [0072]    Finally, the initial material quantity of 11.67 mole again applies for silicon tetrachloride for equation (V): 
         [0000]    
       
                 
         
             
             
         
       
     
         [0073]    Converted to volume, these 186.7 g CH 4  correspond, at a molar volume of 22.4 1, to: V=261.3 1 CH 4 . 
         [0000]        m (HCl)=4*11.67 mole*36.5 g/mole=1.703 kg HCl 
         [0074]    When calculated in the scale of tons, the units g may be replaced by kg, kg by tons t, and liters by m 3 , without anything changing in the numeric values. 
       4. THERMODYNAMIC CALCULATIONS 
       [0075]    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&#39;s law applies for calculating ΔH from the standard formation enthalpy Δh° of the individual compounds: 
         [0000]      Δ H=Σn   i   Δh°i  (products)−Σ m   i   Δh°i (educts) 
         [0000]    n i , mi representing the relevant stoichiometric factors. 
       If a value for ΔH&lt;0 results, it is an exothermic reaction. 
     If a value for ΔH&gt;0 results, it is an endothermic reaction. 
       [0076]    Entirely analogously, to calculate the entropy change ΔS and the heat capacity change ΔC p : 
         [0000]      Δ S=Σn   i   ΔS°i (products)−Σ m   i   ΔS°i (educts) 
         [0000]      Δ C   p   =Σn   i   ΔC   pi (products)−Σ m   i   ΔC   pi (educts) 
         [0077]    S° i  representing the standard entropy at room temperature (T=298 K) of the compound i. 
       If a value of ΔS&lt;0 results, there is an entropy reduction. 
     If a value of ΔS&gt;0 results, there is an entropy increase. 
       [0078]    If the enthalpy change is not sought at the standard temperature T of 298 Kelvin, but rather at another temperature, Kirchhoff&#39;s law applies under the aspect of the isobaric condition: 
         [0000]    
       
         
           
             
               Δ 
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         [0079]    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&#39;s law applies analogously under the aspect of the isobaric condition: 
         [0000]    
       
         
           
             
               Δ 
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         [0080]    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: 
         [0000]      Δ G=ΔH−T*ΔS    
         [0081]    If a value for ΔG&lt;0 results, a spontaneous, i.e., exergonic reaction exists. 
         [0082]    If a value for ΔG&gt;0 results, a nonspontaneous, i.e., endothermic reaction exists. 
         [0083]    The following thermodynamic variables apply for equation (I): 
         [0000]      6SiO 2 +C 10 H 22 +12CH 2 Cl 2 −&gt;6SiCl 4 +12CO+10CH 4 +3H 2   (I) 
         [0000]    
       
         
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 SiO 2   
                 C 10 H 22 (g) 
                 CH 2 C 12 (g) 
                 SiCl 4 (g) 
                 CO(g) 
                 CH 4 (g) 
                 H 2 (g) 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 Δh° 
                 −859.3 
                 −249.7(g) 
                 −117.1 
                 −577.4 
                 −110.5 
                 −74.85 
                 0 
               
               
                 kJ/mol 
               
               
                 S° J/mol 
                 42.09 
                 540.05(g) 
                 270.2 
                  331.4(g) 
                 197.4 
                 186.19 
                 130.6 
               
               
                 Kelvin 
               
               
                 C p  J/mol 
                 44.43 
                  243.1(g) 
                 51.1 
                  90.58(g) 
                 29.15 
                 35.79 
                 28.83 
               
               
                 Kelvin 
               
               
                   
               
             
          
         
       
     
       The value is calculated as follows for ΔH: 
       [0084]      Δ H= 6*(−577.4)+12*(−110.5)+10*(−74.85)−6*(−859.3)−(−249.7)−12*(−117.1) kJ/mol, 
         [0000]      Δ H=+ 1271.8 kJ/mol 
       Equation (I) is thus a reaction running endothermically at room temperature, since ΔH&gt;0. 
       [0085]    The following value is obtained for ΔS: 
         [0000]      Δ S= 6*331.4+12*197.4+10*186.19+3*130.6−6*42.09−540.5−12*270.2 J/mol Kelvin 
         [0000]      Δ S=+ 2575.46 J/mol Kelvin 
         [0086]    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 
         [0000]      Δ G=ΔH−T*ΔS    
         [0087]    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. 
         [0088]    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. 
         [0000]      Δ C   p =6*90.58+12*29.15+10*35.79+3*20.83−6*44.43−243.1−12*51.1 J/mole Kelvin, 
         [0000]      Δ C   p =+214.79 J/mole Kelvin 
         [0000]      Δ H ( T= 1300 K)=Δ H ( T= 298 K)+Δ C   p (1300 K−298 K)=+1271.8 kJ/mole+214.79 
         [0000]      J/mole*K*1002 Kelvin=+1487 kJ/mole, the reaction remains endothermic. 
         [0000]      Δ S ( T= 1300 K)=Δ S ( T= 298 K)+Δ C   p *ln (1300 K/298 K)=+2575.46 J/mole K+214.79 
         [0000]      J/mole*K* ln (4.3624)=+2891.85 J/mole*K 
         [0000]      Δ G (1300 K)=Δ H (1300 K)− T*ΔS ( 1300 K)=+1487 kJ/mole−1300 K*2891.85 J/mole*K 
         [0000]      Δ G (1300 K)=−2272.41 kJ/mole, the reaction suddenly becomes exergonic at 1300 K. 
         [0089]    The reaction may thus occur at 1300 Kelvin. 
         [0090]    The following thermodynamic variables apply for equation (II): 
         [0000]      SiCl 4 +LiAlH 4 −&gt;SiH 4 +LiAlCl 4   
         [0000]    
       
         
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 SiCl 4   
                 LiAlH 4   
                 SiH 4   
                 LiAlCl 4   
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Δh° 
                 −577.4 
                 −100.8 
                 −61.0 
                 −1114.15 
               
               
                   
                 kJ/mol 
               
               
                   
                 S° J/mol 
                 331.4 (g) 
                 ? 
                 204.5 
                 225.2 
               
               
                   
                 Kelvin 
               
               
                   
                   
               
             
          
         
       
     
         [0000]      Δ H=(− 61.0)+(−1114.15)−(−577.4)−(−100.8)kJ/mole=−496.95 kJ/mole 
         [0091]    Equation (II) is thus an exothermic reaction, since ΔH&lt;0. 
         [0092]    For ΔS, the value of the entropy change may not be ascertained, since the entropy specified for LiAlH 4  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&lt;0. 
         [0093]    The following thermodynamic variables apply for equation (III): 
         [0000]      3SiH 4 + 4 N2−&gt;Si 3 N 4 +4NH 3   (III) 
         [0000]    
       
         
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 SiH 4   
                 N 2   
                 Si 3 N 4   
                 NH 3   
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Δh° 
                 −61.0 
                 0 
                 −750.0 
                 −46.19 
               
               
                   
                 kJ/mol 
               
               
                   
                 S° J/mol 
                 204.5 (g) 
                 191.5 
                 95.4 
                 192.5 
               
               
                   
                 Kelvin 
               
               
                   
                   
               
             
          
         
       
     
         [0000]      Δ H=(− 750.0)+4*(−46.19)−3*(−61.0)−0 kJ/mole=−751.76 kJ/mole 
         [0094]    Equation (III) is thus an exothermic reaction, since ΔH&lt;0. 
         [0095]    The following value is obtained for ΔS: 
         [0000]      Δ S= 95.4+4*192.5−3*204.5−4*191.5 kJ/mole Kelvin 
         [0000]      Δ S=− 514.1 J/mole Kelvin, i.e., the reaction results in an entropy reduction. 
         [0096]    With ΔG=ΔH−T*ΔS, the amount ΔG=−496.95 kJ/mole −298 K*(−514.1) J/mole K=−598.56 kJ/mole 
         [0097]    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 N 2  molecule. The reaction subsequently sustains itself on its own. 
         [0098]    The following thermodynamic variables apply for equation (V): 
         [0000]      SiCl 4 +CH 4 −&gt;SiC+4HCl  (V) 
         [0000]    
       
         
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 SiCl 4   
                 CH4 
                 SiC 
                 HCl 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Δh° 
                 −577.4 
                 −74.85 
                 −111.7 
                 −92.31 
               
               
                   
                 kJ/mol 
               
               
                   
                 S° J/mol 
                 331.4 
                 186.19 
                 16.46 
                 186.9 
               
               
                   
                 Kelvin 
                 (g) 
               
               
                   
                 Cp J/mol 
                 90.58 
                 35.79 
                 26.65 
                 29.12 
               
               
                   
                 Kelvin 
                 (g) 
               
               
                   
                   
               
             
          
         
       
     
         [0000]      Δ H=(− 111.7)+4*(−92.31)−(−577.4)−(−74.85) kJ/mole=+171.31 kJ/mole 
         [0099]    Equation (V) is thus a reaction which runs endothermically at room temperature, since ΔH&gt;0. 
         [0100]    The following value is obtained for ΔS: 
         [0000]      Δ S= 16.46+4*186.9−331.4−186.19 kJ/mole, 
         [0000]      Δ S=+ 246.47 J/mole Kelvin, i.e., an entropy increase occurs! 
         [0101]    With ΔG=ΔH−T*ΔS, the amount ΔG=+171.31 kJ/mole−298 K*246.47 J/mole K=+97.86 kJ/mole. 
         [0102]    The reaction is thus both endothermic (ΔH&gt;0) and also endergonic (ΔG&gt;0) at room temperature. It may therefore not occur at room temperature. 
         [0000]      Δ C   p =26.65+4*29.12−90.58−35.79 J/mole Kelvin=+16.76 J/mole Kelvin 
         [0000]      Δ H ( T= 1300 K)=Δ H ( T= 298 K)+Δ C   p (1300 K−298 K)=+171.31 kJ/mole+16.76 
         [0000]      J/mole*K*1002 Kelvin=+188.1 kJ/mole, the reaction remains endothermic. 
         [0000]      Δ S ( T= 1300 K)=Δ S ( T= 298 K)+Δ C   p   *ln (1300 K/298 K)=+246.47 J/mole K+16.76 
         [0000]      J/mole*K* ln (4.3624)=+271.16 J/mole*K 
         [0000]      Δ G (1300 K)=Δ H (1300 K)− T*ΔS (1300 K)=+188.1 kJ/mole−1300 K*271.76 J/mole*K 
         [0000]      Δ G (1300 K)=−164.4 kJ/mole, the reaction suddenly becomes slightly exergonic at 1300 K. 
         [0103]    The reaction may thus occur at 1300 Kelvin. 
         [0104]    The following thermodynamic variables apply for equation (VI): 
         [0000]      SiCl 4 +2C−&gt;SiC+CCl 4   (VI) 
         [0000]    
       
         
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 SiCl 4   
                 C 
                 SiC 
                 CCl 4   
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Δh° kJ/mol 
                 −577.4 
                 0 
                 −111.7 
                 106.7 (g) 
               
               
                   
                 S° J/mol 
                 331.4 (g) 
                 5.74 
                 16.46 
                 309.7 (g) 
               
               
                   
                 Kelvin 
               
               
                   
                 Cp J/mol 
                 90.58 (g) 
                 8.53 
                 26.65 
                  83.4 (g) 
               
               
                   
                 Kelvin 
               
               
                   
                   
               
             
          
         
       
     
         [0000]      Δ H=(− 111.7)+(−106.7)−(−577.4)−0 kJ/mole=+359.0 kJ/mole 
         [0105]    Equation (VI) is thus a reaction which runs endothermically at room temperature, since ΔH&gt;0. 
         [0106]    The following value is obtained for ΔS: 
         [0000]      Δ S= 16.46+309.7−331.4−2*5.74 kJ/mole Kelvin 
         [0000]      Δ S=− 16.72 J/mole Kelvin, i.e., a slight entropy reduction occurs. 
       With ΔG=ΔH−T*ΔS, the amount ΔG=+359.0 kJ/mole−298 K*(−16.72) J/mole K=+364.0 kJ/mole. 
       [0107]    The reaction is thus both endothermic (ΔH&gt;0) and also endergonic (ΔG&gt;0) at room temperature. It may therefore not occur at room temperature. What about at a temperature of 1300 Kelvin? 
         [0108]    The following value is obtained for ΔC p : 
         [0000]      Δ C   p =26.65+83.4−90.58−2*8.53 J/mole Kelvin=+2.41 J/mole Kelvin 
         [0000]      Δ H ( T= 1300 K)=Δ H ( T= 298 K)+Δ C   p (1300 K−298 K)=+359.0 kJ/mole+2.41 
         [0000]      J/mole*K*1002 Kelvin=+361.4 kJ/mole, the reaction remains endothermic. 
         [0000]      Δ S ( T= 1300 K)=Δ S ( T= 298 K)+Δ C   p   *ln (1300 K/298 K)=−16.72 J/mole K+2.41 
         [0000]      J/mole*K* ln (4.3624)=−13.17 J/mole*K 
         [0000]      Δ G (1300 K)=Δ H (1300 K)− T*ΔS (1300 K)=+361.4 kJ/mole−1300 K*(−13.17 J/mole*K) 
         [0000]      Δ G (1300 K)=+378.5 kJ/mole, the reaction remains endergonic, unchanged even at 1300 K. 
         [0109]    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. 
       5. SUMMARY 
       [0110]    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 Si 3 N 4  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 CH 2 Cl 2  in an oxygen-free atmosphere to 1300 Kelvin (1000° C.). Silicon changes the binding partner and forms silicon tetrachloride according to equation (I): 
         [0000]    
       
                 
         
             
             
         
       
     
         [0111]    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). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0112]    Finally, the monosilane SiH 4  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: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0113]    In order to obtain silicon carbide SiC, one starts again from silicon tetrachloride SiCl 4 , which is obtained from equation (I), and reacts it with methane at 1300 K: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0114]    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 SiCl 2  and higher silanes may also be obtained by the following hydrogenation with LiAlH 4 , as the following reaction equations indicate: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0115]    Higher silanes (from Si 7 H 16 ) provide the advantage that they are no longer self-igniting and maybe combusted in a much more controlled way than SiH 4 . Accordingly, combustion with pure nitrogen is also preferred if higher silanes reach this reaction. 
       6. BIBLIOGRAPHY 
       [0000]    
       
         [1] 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) 
         [2] Landolt-Börnstein, Zahlenwerte und Funktionen aus der Physik, Chemie, Astronomie, Geophysik und Technik [Numeric Values and Functions from Physics, Chemistry, Astronomy, Geophysics, and Technology], Volume II: Eigenschaften der Materie in ihren Aggregatzustanden [Properties of Materials in their Aggregate States], Part 4: Kalorische Zustandsgrössen [Caloric State Variables], 6th edition, Springer-Verlag.