Oil shale derived pollutant control materials and methods and apparatuses for producing and utilizing the same

Pollution control substances may be formed from the combustion of oil shale, which may produce a kerogen-based pyrolysis gas and shale sorbent, each of which may be used to reduce, absorb, or adsorb pollutants in pollution producing combustion processes, pyrolysis processes, or other reaction processes. Pyrolysis gases produced during the combustion or gasification of oil shale may also be used as a combustion gas or may be processed or otherwise refined to produce synthetic gases and fuels.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to the production of pollutant sorbents, the reduction of pollutants, and energy providing fuels. Generally, the invention relates to the use of oil shale and oil shale products as sorbents or reductants for reducing pollutants, and, in particular, to the thermal processing of oil shale to produce pollutant absorbing and adsorbing solids and combustible or reducing gases.

2. State of the Art

Coal, oil, natural gas, oil shale, oil sands, and other carbon-containing fuel feedstock materials (for example: forestry industry products, byproducts, and residues; agriculture crops, byproducts, and residues; animal wastes and carcasses; municipal solid waste, sewage sludge solids, construction and demolition debris, waste tires, and other forms of refuse-derived fuel) can be converted from chemical potential energy to heat and gaseous products that can be used to generate electrical power, or to produce higher value chemicals and components.

In the context of this document, the term “thermal conversion” generally implies any gaseous or solid process that liberates or transforms the chemical potential energy into heat, hot gases, combustible gases, combustible liquids, combustible solids such as char, and/or non-combustible solids such as ash or calcined minerals, or any subset of these.

Thermal conversion of such gaseous and solid materials produces various pollutants, such as nitrogen compounds or sulfur compounds, which are believed to be involved in the formation of smog and acid rain. If the fuel includes mercury, the combustion also produces mercury compounds, which have been identified by the Environmental Protection Agency (“EPA”) as a significant toxic pollutant. Air pollutant control legislation, such as the Clean Air Act (“CAA”), the Clean Air Interstate Regulation (“CAIR”), and the Clean Air Mercury Regulation (“CAMR”), regulate emissions of many of the pollutants released from thermal conversion processes.

The composition of the pollutant species produced by thermal conversion processes is a strong function of the availability of oxygen in the process. Under the reducing conditions of pyrolysis and gasification, sulfur bound in the fuel is typically converted to reduced forms of sulfur, such as hydrogen sulfide, carbonyl sulfide, and carbon disulfide. Nitrogen contained in the fuel is converted to reduced nitrogen compounds, including ammonia, hydrogen cyanide, and molecular nitrogen. Most of the mercury in a fuel is converted to volatile elemental mercury (“Hg°”) and speciated mercury, such as mercury chloride (“HgCl2”). Under reducing conditions, phosphorus (“P”) reacts with metals to form phosphate compounds, and may also be converted to phosphine (“PH3”), phosphonium compounds, and other reduced forms of phosphorus. Chlorine (“Cl”) may react with alkali metals (such as sodium and potassium), alkali-earth metals (such as calcium and magnesium), and other metals (such as mercury, zinc, and iron), but it is also converted to diatomic chlorine gas (“Cl2”) and hydrochloric acid gas (“HCl”). Fluorine, bromine, and iodine behave similar to chlorine.

Under the oxidizing conditions of combustion, sulfur bound in the fuel is converted to gaseous sulfur dioxide or sulfur trioxide. These sulfur compounds quickly equilibrate with moisture (“H2O”) to form sulfuric acid (“H2SO4”). Nitrogen bound in the fuel is converted to nitric oxide and nitrogen dioxide or other oxides of nitrogen. Combustion with air also results in nitrogen oxides as a result of high temperature reactions of atomic oxygen (“O”) and hydroxide radicals with molecular nitrogen. Phosphorus, chlorine, fluorine, bromine, and iodine are readily converted to phosphoric acid (“H3PO4”), hydrochloric acid (“HCl”), and hydrofluoric acid (“HF”), bromous acid (“HBrO”), and iodic acid (“HIO3”), as well as other reactive volatile compounds. These acid gases are corrosive to equipment used in combustion processes, such as in a combustion device or in boiler tubes in a combustor. Therefore, it is desirable to limit the formation of the acid gases or to remove the acid gases close to their point of generation in a combustion device or thermal conversion process.

Various technologies have been developed to decrease emissions from coal-fired powerplants. Limestone has been used as a sorbent for SOxpollutants, as disclosed in U.S. Pat. No. 3,995,006 to Downs et al., U.S. Pat. No. 5,176,088 to Amrhein et al. (“Amrhein”), and U.S. Pat. No. 6,143,263 to Johnson et al. This technology is known as limestone injection multiple burner (“LIMB”) technology or limestone injection dry scrubbing (“LIDS”) technology. The limestone is injected into a region of a furnace having a temperature of 2,000° F. to 2,400° F.

Limestone (mainly CaCO3) and dolomite (“CaCO3—MgCO3”) and their derivatives have also been shown to react with H2S. Either uncalcined limestone or dolomite, half-calcined dolomite, fully calcined limestone or dolomite, lime, or hydrated lime (“CaOH”) will react to form calcium sulfide (“CaS”) or magnesium sulfide (“MgS”).

Organic and amine reducing agents, such as ammonia or urea, are used to selectively reduce NOxpollutants, as disclosed in U.S. Pat. No. 3,900,554 to Lyon. This technique is known as selective noncatalytic reduction (“SNCR”). The reducing agent is injected into a furnace at a temperature from about 975 K to about 1375 K so that a noncatalytic reaction selectively reduces the NOxto molecular nitrogen (“N2”). The ammonia is injected into a region of the furnace having a temperature of 1,600° F. to 2,000° F.

The LIMB and SCNR technologies have been combined to simultaneously remove the NOxpollutants and the SOxpollutants. The limestone is used to absorb the SOxpollutants while the ammonia is used to reduce the NOxpollutants. However, this combination technology is expensive to implement and adds increased complexity to the process.

NOxreburning has also been used to remove the NOxpollutants, as disclosed in U.S. Pat. No. 5,139,755 to Seeker et al. In NOxreburning, the coal is combusted in two stages. In the first stage, a portion of the coal is combusted with a normal amount of air (about 10% excess), producing the NOxpollutants. In the second stage, the remaining portion of the coal is combusted in a fuel-rich environment. Hydrocarbon radicals formed by combustion of the coal react with the NOxpollutants to form N2. Fuel/air staging has also been used to reduce the NOxpollutants. Fuel and air are alternately injected into a combustor to provide a reducing zone where the nitrogen in the fuel is evolved, which promotes the conversion of the nitrogen to N2. The air is injected at a separate location to combust the fuel volatiles and char particles. By staging or alternating the fuel and the air, the local temperature and the mixture of air and fuel are controlled to suppress the formation of the NOxpollutants. Fuel/air staging attempts to prevent NOxformation while NOxreburning promotes NOxreduction and destruction.

To absorb mercury or mercury-containing pollutants, activated carbon is used as a sorbent, as disclosed in U.S. Pat. No. 5,827,352 to Altman et al., and U.S. Pat. No. 6,712,878 to Chang et al. The activated carbon is present as a fixed or fluidized bed or is injected into the flue gas.

Oil shale is a sedimentary rock that includes an inorganic matrix of carbonate, oxide, and silicate compounds impregnated with a polymeric material called kerogen. Kerogen is an organic substance that is insoluble in petroleum solvents. When heated, the kerogen pyrolyzes to produce gas, oil, bitumen, and an organic residue. Pyrolyzing the kerogen is also known as retorting. Oil shale also includes carbonate minerals, such as calcium carbonate, and other hydrocarbon materials, such as paraffins, cycloparaffins, aliphatic and aromatic olefins, single ring aromatics, aromatic furans, aromatic thiophenes, hydroxyl-aromatics, dihydroxy aromatics, aromatic pyrroles, and aromatic pyridines, and other polynuclear aromatic hydrocarbons. Oil shale is typically co-located with coal and oil and is found in various regions of the western United States, such as in Utah, Colorado, and Wyoming, and in the eastern United States, such as in Virginia and Pennsylvania. Large deposits of oil shale are also found in Canada, Australia, Europe, Russia, China, Venezuela, and Morocco. Given the abundance of oil shale throughout the world, its value would be significant if beneficial uses are identified and employed. Oil shale utilization has not been presently appreciated due to the high cost of recovering the kerogen from the shale.

When oil shale containing considerable amounts of calcium carbonate is heated, the calcium carbonate undergoes calcination, which is an endothermic reaction in which the calcium carbonate (“CaCO3”) is converted to lime (“CaO”). For each kilogram of calcium carbonate that is calcined, as much as 1.4 MJ to 1.6 MJ (or about 600 British Thermal Units (“BTU”) to 700 BTU per pound mass) of the available heat energy is consumed. This loss of energy translates to a process efficiency penalty when limestone or dolomite is used as an injected sorbent. In the case of oil shale, the kerogen can be oxidized to offset the heat sink associated with carbonate calcination.

To extract energy from the oil shale, the oil shale can be heated in a retorting zone of a fluidized bed reactor vessel to a temperature sufficient to release, but not combust, volatile hydrocarbons from the oil shale, as disclosed in U.S. Pat. No. 4,373,454 to Pitrolo et al. The temperature used in the retorting zone provides minimal calcination of the calcium carbonate. The volatile hydrocarbons flow to a combustion zone of the fluidized bed combustor, where the volatile hydrocarbons are combined with excess air and are combusted. Calcination of the calcium carbonate occurs in the combustion zone. During retorting, nitrogen compounds in the oil shale are converted to NOxcompounds and are reduced to nitrogen and water or oxygen by the volatile hydrocarbons.

Oil shale has been used to absorb SO2and HCl in a circulating fluidized bed, as disclosed in “Combustion of Municipal Solid Wastes with Oil Shale in a Circulating Fluidized Bed,” Department of Energy Grant No. DE-FG01-94CE15612, Jun. 6, 1996, Energy-Related Inventions Program Recommendation Number 612, Inventor R. L. Clayson, NIST Evaluator H. Robb, Consultant J. E. Sinor and in “Niche Market Assessment for a Small-Scale Western Oil Shale Project,” J. E. Sinor, Report No. DOE/MC/11076-2759.

Many of the pulverized coal combustors in operation do not meet the new standards promulgated by the United States Environmental Protection Agency under CAIR and CAMR. Upwards of about 75 percent of all currently existing pulverized coal combustors may have to be phased out or retrofit to satisfy the new pollutant standards.

BRIEF SUMMARY OF THE INVENTION

The present invention relates to a method of decreasing pollutants produced in a pyrolysis, combustion, gasification, stream reforming, retorting, calcination, metal refining, ore smelting, cement production, or any other thermal conversion process, which processes are collectively referred to herein as a “thermal conversion” processes. The term “thermal conversion” encompasses equivalent derivate nouns, adjectives, and verb conjugations of this term, such as “combusting” or “combusted,” “gasifying” or “gasified,” “reforming” or “reformed,” “retorting” or “retorted,” “calcining” or “calcined” and “pyrolyzing” or “pyrolyzed.” The method comprises thermally converting coal or any other carbon-containing fuel in a thermal conversion chamber to produce at least one pollutant selected from the group consisting of a nitrogen-containing pollutant, sulfuric acid, sulfur trioxide, carbonyl sulfide, carbon disulfide, chlorine, hydroiodic acid, iodic acid iodine, hydrofluoric acid, fluorine, hydrobromic acid, bromous acid, bromine, phosphoric acid, phosphorous pentaoxide, phosphine, phosphonium compounds, elemental mercury, and mercuric chloride.

According to some embodiments, oil shale particles are introduced into the thermal conversion chamber and are thermally converted to produce sorbent particulates and a reductant or reactive gas. The shale sorbent particulates and the reductant may generally be produced by thermally converting the oil shale particles at a temperature necessary to pyrolyze, retort, or devolatilize kerogen, for example, at a temperature of greater than or equal to approximately 200° C.

In some embodiments, the oil shale particles may be introduced into a thermal conversion process used to react with any carbonaceous fuel, including oil shale itself. Such processes shall be referred to as “in-situ” oil shale conversion processes.

In other embodiments, the oil shale particles may be introduced into a separate, independent, or auxiliary thermal conversion process used to convert the oil shale particles into shale sorbent particles and reactive gas. These sorbent particles and reactive gases may be routed, conveyed, or transported separately or in combination to a coupled carbon-containing fuel thermal conversion process. Such processes may generally be referred to as “ex-situ” oil shale conversion processes. The shale sorbent particles may act as a pollutant sorbent or as a pollutant reductant.

The oil shale particles may be thermally converted to shale sorbent particles and reducing or reactive gas in a close-coupled reactor using the heat or the hot gases produced by a primary carbonaceous fuel thermal conversion process. Such processes can generally be referred to as a “close-coupled” oil shale conversion processes.

The oil shale particles may be introduced into at least one of a burner or combustion zone, a gasification zone, a superheater zone, a reheat zone, or an economizer zone of any tangentially fired, wall-fired, or cyclonic pulverized-coal combustion chamber. The at least one pollutant is contacted with at least one of the sorbent particulates and the reductant to decrease an amount of the at least one pollutant in the combustion chamber. The reductant may chemically reduce the at least one pollutant, such as by reducing the nitrogen-containing pollutant to molecular nitrogen, water, and carbon dioxide. The sorbent particulates may be used to adsorb or absorb the at least one pollutant, such as adsorbing or absorbing at least one of sulfuric acid, sulfur trioxide, carbonyl sulfide, carbon disulfide, chlorine, hydroiodic acid, iodic acid, iodine, hydrofluoric acid, fluorine, hydrobromic acid, bromous acid, bromine, phosphoric acid, phosphorous pentaoxide, phosphine, phosphonium compounds, elemental mercury, and mercuric chloride.

The present invention also relates to a combustion chamber for producing decreased pollutants in a combustion process. The combustion chamber may also comprise a burner zone that is configured to combust coal and to produce at least one pollutant selected from the group consisting of a nitrogen-containing pollutant, sulfuric acid, sulfur trioxide, carbonyl sulfide, carbon disulfide, chlorine, hydroiodic acid, iodic acid, iodine, hydrofluoric acid, fluorine, hydrobromic acid, bromous acid, bromine, phosphoric acid, phosphorous pentaoxide, phosphine, phosphonium compounds, elemental mercury, and mercuric chloride. The burner zone is also configured to thermally convert oil shale particles to produce sorbent particulates and a reductant, which are contacted with the at least one pollutant. The burner zone may be configured to contact the nitrogen-containing pollutant with the reductant to reduce the nitrogen-containing pollutant to molecular nitrogen, carbon dioxide, and water.

The combustion chamber also comprises at least one of a combustion zone, gasification zone, superheater zone and a reheat zone that are each configured to thermally convert the oil shale particles to produce the sorbent particulates and the reductant. The superheater zone and the reheat zone are also each configured to contact the sorbent particulates and the reductant with the at least one pollutant. The combustion chamber also comprises at least one of an economizer zone, an air preheat zone, and a gas cleaning unit, which are each configured to contact the sorbent particulates and the reductant with the at least one pollutant. Each of the superheater zone, the reheat zone, the economizer zone, the air preheat zone, and the gas cleaning zone is configured to contact at least one of sulfuric acid, sulfur trioxide, carbonyl sulfide, carbon disulfide, chlorine, hydroiodic acid, iodic acid, iodine, hydrofluoric acid, fluorine, hydrobromic acid, bromous acid, bromine, phosphoric acid, phosphorous pentaoxide, phosphine, phosphonium compounds, elemental mercury, and mercuric chloride with the sorbent particulates to adsorb or absorb at least one of these pollutants.

In one embodiment, the combustion chamber is configured as a pulverized coal combustor.

In other embodiments of the invention, oil shale may be introduced into a pryolyzer, a gasifier, a combustion reactor, a retorting reactor, a metal refining process, ore smelting process, cement kiln, or any other thermal converter to liberate kerogen from the oil shale, which produces a kerogen-based pyrolysis gas and shale sorbent particles.

In other embodiments of the invention, oil shale may be introduced into a packed bed that is contacted either directly or indirectly with the hot gases produced by a pryolyzer, a gasifier, a combustor, a retort, or any other thermal converter to liberate kerogen from the oil shale, which produces a kerogen-based pyrolysis gas and shale sorbent particles.

The pyrolysis gas produced according to embodiments of the invention may be used as a reductant gas for reducing pollutants such as nitrogen-containing pollutants in various processes. The pyrolysis gas may also be used as a combustion gas or heating gas which may be fed to a combustion process or to various combustion zones of a combustor. In other embodiments, the pyrolysis gas may be processed, refined, or otherwise altered to produce synthetic gas and fuel products such as syngas and synfuels.

The shale sorbents produced according to embodiments of the invention may be used to reduce pollutants produced in a process such as a coal combustion process, a gasification process, a pyrolysis process, a metal refining or smelting process, a cement production process, or other thermal conversion process where nitrogen-containing pollutants, sulfur-containing pollutants, mercury-containing pollutants, or other pollutants are produced. Introduction of the shale sorbent produced according to embodiments of the invention into a process may result in the contact of the shale sorbent with a pollutant such that the shale sorbent absorbs or adsorbs the pollutant, thereby reducing the amount of pollutants in the process.

According to still other embodiments of the invention, the shale sorbent may be used to form cement clinker or other additives used to enhance cement production.

DETAILED DESCRIPTION OF THE INVENTION

Oil shale has been used to decrease or eliminate one or more pollutants produced during combustion of a primary fuel, such as coal, biomass, municipal solid waste (“MSW”), refuse derived fuel (“RDF”), mixtures thereof, or other fuel feed stocks. For example, U.S. Pat. No. 7,384,615, which is incorporated herein in its entirety by reference, describes processes wherein oil shale may be added to a combustion chamber burning a primary fuel to reduce the amount of pollutants within the combustion chamber and the combustion process. During combustion of a primary fuel, the oil shale may function as a sorbent to decrease an amount of the pollutant(s) released from the combustion chamber. Alternatively, combustion of the oil shale may produce a reductant, which reduces the pollutant(s) to a more benign chemical species, decreasing the amount of the pollutant(s) released. By adjusting or controlling a temperature or the gas composition in the combustion chamber, the pollutant(s) may be adsorbed or absorbed onto the oil shale or may be reduced by the reductant produced by the oil shale. The pollutant(s) may be removed from the combustion chamber by contacting the pollutant with the oil shale for a sufficient amount of time for the oil shale to function as a sorbent or for the reductant to chemically reduce the pollutant(s). The amount of time sufficient to remove the pollutant(s) is referred to herein as a residence time or a contact time. Pollutants that may be decreased or eliminated by the addition of oil shale to a thermal conversion process chamber may include, but are not limited to, nitrogen-containing pollutants, sulfur-containing pollutants, acid gases, and metals. Nitrogen-containing pollutants may include, for example, NO, NO2, N2O, N2O5, or mixtures thereof. Sulfur-containing pollutants may include, for example, SO2, SO3, H2SO4, H2S, COS, CS2, or mixtures thereof. In some instances, SO2may be a major sulfur-containing pollutant and SO3a minor sulfur-containing pollutant produced during combustion of primary fuels that contain sulfur. In other instances, H2S and COS may be major sulfur-containing pollutants produced during pyrolysis, gasification, or thermal conversion of sulfur-containing primary fuels. Acid gases may include, but are not limited to, halide-containing volatile gases, such as HCl, chlorine (“Cl2”), hydroiodic acid (“HI”), iodic acid (HIO3”) iodine (“I2”), hydrofluoric acid (“HF”), fluorine (“F”), hydrobromic (“HBr”), bromous acid (“HBrO”), bromine (“Br”), or mixtures thereof.

Acid gases may also include phosphate-containing gases, such as phosphoric acid (“H3PO4”), phosphorus pentaoxide (“P2O5”), phosphine (“PH3”), any phosphonium compounds, or mixtures thereof. Metal pollutants may include one or more elemental metals or one or more metal compounds including, but not limited to, elemental mercury (“Hgo”), mercuric chloride (“HgCl2”), mercury adsorbed on particulate matter, lead (“Pb”) or compounds thereof, arsenic (“As”) or compounds thereof, chromium (“Cr”) or compounds thereof, or mixtures thereof. The oil shale may be used to remove a single pollutant or multiple pollutants from the combustion chamber. In one embodiment, the oil shale is used to remove nitrogen-containing pollutants, H2SO4, SO3, SO2, H2S, COS, CS2, elemental mercury, and mercuric chloride from the combustion chamber.

Pollution control processes used with combustion chambers have included processes where oil shale is fed directly to a combustion chamber and, more particularly, directly to a burner portion of a combustion chamber. In such processes, when the oil shale is heated in the combustion chamber, shale minerals, char particles, and kerogen are produced, as shown in Reaction 1:
oil shale+heat→shale minerals+char particles+kerogen+hydrocarbon derivatives  (1).

A temperature of greater than or equal to approximately 200° C. may be used to pyrolyze or retort the oil shale. As the oil shale is heated, the heat may cause the kerogen to depolymerize and devolatilize while the shale minerals may be calcined. The extent of depolymerization, devolatilization, pyrolysis, and char formation of the oil shale may vary depending on particle heat up rates, particle temperature, surrounding gas temperature, surrounding gas temperature, and an amount of time that the oil shale is heated. When the kerogen is devolatilized or released from the oil shale, a porous matrix of oxides, carbonates, or silicates may remain including, but not limited to, oxides, carbonates, or silicates of calcium (“Ca”), magnesium (“Mg”), sodium (“Na”), potassium (“K”), iron (“Fe”), or zinc (“Zn”). These oxides, carbonates, and silicates are collectively referred to herein as the shale minerals. For the sake of example only, the shale minerals may include, but are not limited to, calcium oxide, magnesium oxide, iron oxide, calcium carbonate, or mixtures thereof. The char particles or particles of residual carbon may also remain after the kerogen is devolatilized from the oil shale. The shale minerals and char particles are collectively referred to herein as sorbent particulates or shale sorbent particles. The sorbent particulates are porous particles that have an increased surface area. As such, the sorbent particulates have an increased adsorption or absorption capability relative to that of the oil shale and may be used to adsorb or absorb mercury and other pollutants, as explained in detail below. Since the sorbent particulates are porous, the pollutants may readily diffuse into the sorbent particulates and react with the oxides, carbonates, and silicates therein.

When oil shale is introduced into a thermal conversion chamber, kerogen in the oil shale is released. The kerogen released from the oil shale may provide a source of the reductant used to reduce the nitrogen-containing pollutants in the thermal conversion chamber. As shown in Reaction 2, the kerogen may be exposed to additional heat to crack or scission the kerogen, forming light and heavy hydrocarbons:
kerogen+heat+radicals→heavy and light hydrocarbons (CxHy)+CO+H2+CO2(2),
where x and y depend on the carbon and hydrogen ratio in the kerogen and temporal conditions. For instance, x may range from 1 to 7 for a light hydrocarbon, from approximately 8 to 13 for an intermediate hydrocarbon, or from approximately 14 to 42 for a heavy hydrocarbon. In correlation, y may range from 1 to 90 and is typically equal to nominally two times “x” for a given hydrocarbon. A temperature of greater than or equal to approximately 350° C. may be used to crack and scission the polymeric kerogen. The heavy hydrocarbons are thus progressively converted to lighter hydrocarbons. The presence of steam helps crack and reform the heavy hydrocarbons. The heavy and light hydrocarbons may be used to reduce the nitrogen-containing pollutants to N2, carbon dioxide (“CO2”), and water (“H2O”) by heating the heavy and light hydrocarbons to a temperature of greater than or equal to approximately 400° C. according to the chemistries shown in Reactions 3 and 4:
CxHy+(2x+y/2)NO→(x+y/4)N2+xCO2+y/2H2O  (3),
CxHy+(x+y/4)NO2→(x/2+y/8)N2+xCO2+xCO2+y/2H2O  (4),
where x is typically 1 or 2 and y is typically 1, 2, 3, or 4. Generally, Reactions 3 and 4 show the reduction of oxidized compounds of nitrogen to a reduced nitrogen compound, such as N2. Oil shale char will also reduce nitrogen-containing pollutants to N2, CO2, and H2O by heterogeneous reactions according or similar to the chemistries shown in Reactions 5 and 6:
Char+(2+x)NO→½(2+x)N2+yCO2+zH2O  (5),
Char+(2+x)NO2→½(2+x)N2+yCO2+zH2O  (6),
where x, y, and z are dependent on the carbon to hydrogen ratio in the char.

The shale minerals or char particles resulting from the combustion of the oil shale may also have an affinity for chemical bonding with mercury or mercury compounds (adsorption) and for physical bonding with mercury or mercury compounds (absorption). Therefore, the shale minerals or char particles produced by the pyrolysis of the oil shale (see Reaction 1) may adsorb or absorb mercury or mercuric chloride according to the chemistries shown in Reactions 7, 8, 9, and 10:
char particles+Hgo→char particles−Hgo(7),
char particles+HgCl2→char particles−HgCl2(8),
shale minerals+Hgo→M-Hgo(9),
shale minerals+HgCl2→M-HgCl2(10),
where M is a metal or metal compound present in the oil shale that has affinity for mercury or mercuric chloride. M may include, but is not limited to, any one of Fe, Zn, lead (“Pb”), silver (“Ag”), aluminum (“Al”), cadmium (“Cd”), chromium (“Cr”), nickel (“Ni”), titanium (“Ti”), selenium (“Se”), arsenic (“As”), or sulfur (“S”), including sulfur that has been captured by the particle. When the shale minerals or char particles come into contact with these pollutants for a sufficient residence time, the sorbent particulates may capture the elemental mercury or mercuric chloride. The adsorption or absorption of the elemental mercury or mercuric chloride by the shale minerals or char particles may also depend on a temperature at which the shale minerals or char particles contact the elemental mercury or mercuric chloride. The temperature may be maintained so that is it favorable for chemical or physical adsorption, so as not to dissociate; for example, at a temperature of less than or equal to approximately 200° C. in some embodiments. This temperature may be achieved in a number of locations in the combustion chamber, such as in a process duct, in a particle cake collected by a gas cleaning unit, such as a baghouse or electrostatic precipitator (“ESP”), or in a packed-bed/gas reactor.

Other volatile and semi-volatile metals that may be removed by the shale sorbent char and inorganic ash produced by the thermal conversion process, include lead, arsenic, beryllium, and other metals liberated from the carbon-containing fuel materials by the thermal conversion process.

Carbonate or oxide compounds produced by the combustion of the oil shale may also be used to remove sulfur-containing pollutants, such as H2SO4, SO3, SO2, H2S, COS, CS2, or mixtures thereof, according to the chemistries shown in Reactions 11-19:
Mx−(CO3)y+heat→Mx−OyyCO2(11),
CaCO3+SO2+½O2→CaSO4+CO2(12),
CaCO3+SO3→CaSO4+CO2(13),
CaCO3+H2SO4→CaSO4+CO2+H2O  (14),
CaCO3+H2S→CaS+H2O+CO2(15),
CaO+SO2+½CaSO4(16),
CaO+SO3→CaSO4(17),
CaO+H2SO4→CaSO4+H2O  (18),
CaO+H2S→CaS+H2O  (19),
where M is a metal, such as Ca, Mg, Na, K, Fe, or Zn, and where x and y vary depending on the metal carbonates present in the oil shale. For instance, x may be 1 or 2 and y may be 1, 2, or 3. While the reactions shown above are between SO2, SO3, H2SO4, or H2S and calcium carbonate or calcium oxide, similar reactions may occur between SO2, SO3, or H2S and carbonates or oxides of Mg, Na, K, Fe, or Zn.

When COS, CS2, or a combination of COS and CS2are present in the gas produced by a thermal conversion process such as a pyrolysis process or a gasifier, COS and CS2may be shifted to H2S using a shift reactor according to the Reactions 20 and 21:
COS+H2O→H2S+CO2(20),
CS2+2H2O→2H2S+CO2(21),
which may be followed by Reactions 15 and 19.

The shift reactions illustrated by Reactions 20 and 21 may be promoted by Ca, Mg, Na, K, Cu, Fe, Al, and other elements or mineral compounds contained in the oil shale or oil shale sorbents.

The shale minerals, such as the carbonate compounds, may be calcined by heating the oil shale to a temperature greater than or equal to approximately 450° C. The adsorption of the sulfur-containing pollutant may occur in a location of the combustion chamber where the temperature is relatively hot. The temperature may be sufficiently high to achieve favorable reaction of the sulfur-containing pollutant with the alkali compounds, alkaline-earth compounds, or other metal oxides present in the oil shale to produce sulfate or sulfide compounds. However, the temperature may be less than the dissociation temperatures of the compounds. To achieve reaction between the shale minerals and the H2SO4, SO2, SO3, H2S, COS, or CS2, a temperature ranging from greater than or equal to approximately 450° C. to less than approximately 1150° C. may be used.

The shale minerals, such as the carbonate or oxide compounds, may also be used to remove HCl and Cl2according to the example chemistries shown in Reactions 22 and 23:
CaO+2HCl→CaCl2+H2O  (22),
CaO+Cl2→CaCl2+½O2(23).

While the reactions shown above are between calcium oxide and chlorine-containing compounds, similar reactions may occur between HCl or Cl2and Mg, Na, K, Fe, or Zn. Similar reactions may also occur with fluorine, fluorine-containing compounds, iodine, iodine-containing compounds, bromine, bromine-containing compounds, phosphate, and phosphate-containing compounds. The adsorption of fluorine, fluorine-containing compounds, iodine, iodine-containing compounds, bromine, bromine-containing compounds, phosphate, and phosphate-containing compounds may occur in a location of the thermal conversion process chamber where the temperature is relatively hot. The temperature may be sufficiently high to achieve favorable reaction of the fluorine, fluorine-containing compounds, iodine, iodine-containing compounds, bromine, bromine-containing compounds, phosphate, and phosphorus-containing compounds with the alkali compounds, alkaline-earth compounds, or other metal oxides present in the oil shale to produce halogen or phosphorus compounds. However, the temperature may be less than the dissociation temperatures of the compounds. For example, for the reaction of HCl with the shale minerals, the temperature of the reaction may be maintained from greater than or equal to approximately 450° C. to less than approximately 1150° C.

In processes such as those described in U.S. Pat. No. 7,384,614, the oil shale used in and fed to combustion chambers may include ore that is obtained from a conventional oil shale mine and pulverized into particles. The oil shale may be obtained from a source, such as mines in Utah, Colorado, or Wyoming that yield approximately 10 gallons of oil per ton of ore to approximately 80 gallons of oil per ton of ore. Other sources of oil shale around the world may also be used, each of which contain varying concentrations of kerogen and other minerals. The oil shale may initially be ground or milled to a desired coarse particle size of less than or equal to approximately 5 cm (approximately 2 inches). The oil shale may be ground using conventional techniques, similar to the crushing and grinding techniques used in coal mining. The oil shale particles may be further pulverized into microsize particles having a particle size ranging from approximately 2 μm to approximately 150 μm, which are introduced into the combustion chamber. The microsize particles may be pulverized, classified, and entrained in an air stream using conventional techniques, similar to the techniques for pulverizing, classifying, and entraining coal in an air stream. As such, existing coal pulverizers, classifiers, and injectors may be used to produce and inject the oil shale particles into the combustion chamber. The oil shale particles may be unreacted, in that the oil shale particles have not been pyrolyzed or devolatilized. However, oil shale retort (devolatilized oil shale particles) may also be used in the combustion chamber.

To decrease the amount of the pollutants produced by combustion of a primary fuel, oil shale particles may be introduced into a combustion chamber, for example, a pulverized coal combustor (“PCC”), a furnace, a boiler, a fluidized bed combustor or gasifier, a circulating bed combustor or gasifier, a staged reactor combustor or gasifier, an entrained-flow combustor or gasifier, an offgas duct, an offgas cleanup transport reactor, a packed-bed combustor or gasifier, a rotary-bed combustor or gasifier, or calcining devices such as a cement kiln. Oil shale particles may also be used in a metallurgical process, such as during the production of iron ore or the smelting or refining of metals. A combustion chamber may be configured to combust coal or other fossil fuels, biomass, MSW, RDF, or other carbon-containing feedstock materials. While some embodiments herein describe using the oil shale particles in a PCC, oil shale particles may be used in other types of thermal conversion chambers as long as the thermal conversion chamber is capable of producing the temperatures at which the reactions with the oil shale particles occur. In addition, while the embodiments herein describe using coal as a primary fuel, other fuels, such as oil, natural gas, oil shale, oil sands, and other carbon-containing fuel feedstock materials (for example: forestry industry products, byproducts, and residues; agriculture crops, byproducts, and residues; animal wastes and carcasses; municipal solid waste, sewage sludge solids, construction and demolition debris, waste tires, and other forms of refuse-derived fuel) may be used.

PCCs are designed to burn coal as a primary fuel and to convert the chemical energy (enthalpy) of the burning coal into heat, which is transferred to steam tubes to produce super-heated, high pressure steam. PCCs typically produce from approximately 50 MWeto approximately 1000 MWeof energy. PCCs typically comprise a long, vertical burner box that is lined with the steam tubes or has pendant arrangements of the steam tubes. PCCs are known in the art and, therefore, are not discussed in further detail herein. A schematic illustration of a PCC100into which oil shale particles120may be introduced is shown inFIG. 1. The PCC100includes a burner zone106, a superheater zone108, a reheat zone110, an economizer zone112, an air preheat zone114, and a gas cleaning unit116. To decrease the pollutants produced by combusting the coal in the PCC100, the temperature in each of these zones may be controlled to achieve the desired reactions between the pollutants and the kerogen and between the pollutants and the sorbent particulates.

Pulverized coal128may be introduced into the burner zone106of the PCC100and combusted with air130. An amount of pulverized coal128added to the PCC100may depend on an efficiency of the PCC100and its desired power output. A feed rate at which the pulverized coal128is introduced into the PCC100may be calculated based on the efficiency of the PCC100and desired power output, as known in the art. The pulverized coal128may be entrained with the air130and injected into the PCC100through multiple burners (not shown), which are also referred to in the art as burner registers or burner boxes. Alternatively, the pulverized coal128may be injected into the burner zone106through primary ports (not shown). The air130may be injected with the pulverized coal128or may be injected through secondary or tertiary ports (not shown). To combust the pulverized coal128, the burner zone106may be maintained at a temperature ranging from approximately 1085° C. to approximately 1625° C. (approximately 2000° F. to approximately 3000° F.). Upon combustion, nitrogen present in the pulverized coal128and the air130may be converted to nitrogen-containing pollutants. Sulfur in the pulverized coal128, such as organically bound sulfur or inorganic or pyrite-phase sulfur, may be released and oxidized or converted to the sulfur-containing pollutants, such as H2SO4, SO2, SO3, H2S, COS, CS2, or mixtures thereof. Chlorine in the pulverized coal128may be converted to HCl, Cl2, or other volatile chlorine compounds. Iodine in the pulverized coal128may be converted to HI, I2, or other volatile iodine compounds while fluorine in the pulverized coal128may be converted to HF, F, or other volatile fluoride compounds. Bromine in the pulverized coal128may be converted to HBr, Br, or other volatile bromide compounds. Phosphorus in the pulverized coal128may be converted to phosphorous-containing compounds. Mercury present in the pulverized coal128may be released as Hgoor HgCl2. Arsenic, lead, beryllium, and other toxic metals may be released as volatile and semi-volatile compounds.

The oil shale particles120may be entrained and injected into the PCC100in at least one of the burner zone106, the superheater zone108, and the reheat zone110, depending on the temperature profile of the PCC100and the properties of the oil shale. For the sake of clarity and simplicity, the oil shale particles120are shown inFIG. 1as being injected into the superheater zone108. The oil shale particles120may be injected into the PCC100through multiple burners (not shown), primary ports (not shown), or secondary or tertiary ports (not shown). The oil shale particles120are not injected into a zone of the PCC100where the oil shale particles120would fuse and slag since this may affect the ability of the oil shale particles120to capture the pollutant in later stages of the gas exit path. A feed rate at which the oil shale particles120are introduced into the PCC100may depend on the efficiency of the sorbent reactions. This feed rate may be determined as known in the art. In one embodiment, the oil shale particles120are injected into an upper region of the burner zone106or a lower region of the superheater zone108. Oil shale retort (devolatilized oil shale particles) may also be injected into the reheat zone110. After being injected into the PCC100, the oil shale particles120may begin to devolatilize and release the kerogen, which reacts with the nitrogen-containing pollutant as described in Reactions 1-4. The temperature in at least one of the burner zone106, the superheater zone108, and the reheat zone110may be maintained so that it is favorable to chemical reduction of the nitrogen-containing pollutants to N2, CO2, and H2O, significantly decreasing the amount of the nitrogen-containing pollutants that exit the PCC100.

The shale minerals produced after the kerogen is released may react with gaseous H2SO4, SO3, SO2, HCl, H2S, COS, CS2, or mixtures thereof as described in Reactions 9-17. Calcium oxide, magnesium oxide, iron oxide, and other metal oxides from the oil shale may react and capture the H2SO4, SO3, SO2, HCl, H2S, COS, CS2, or mixtures thereof when the reaction kinetics and thermodynamics are favorable for the formation of CaSO4or CaS. Generally, favorable reactions may occur at a temperature ranging from approximately 450° C. to approximately 1125° C. Temperatures within this range may occur in at least one of the superheater zone108, the reheat zone110, and the economizer zone112. Therefore, the capture of the HCl, H2SO4, SO3, SO2, H2S, COS, CS2, or mixtures thereof may occur as the oil shale particles120pass out of the superheater zone108and into the reheat zone110and the economizer zone112. The capture of the HCl, H2SO4, SO3, SO2, H2S, COS, CS2, or mixtures thereof may also continue into a lower portion of the air preheat zone114. A residence time or contact time between the shale minerals and the pollutants may be greater than or equal to approximately 5 seconds to capture these pollutants.

Mercury or mercuric chloride may react with the shale minerals or char particles by two mechanisms: physical absorption or chemical adsorption. As the shale minerals or char particles pass into portions of the PCC100having cooler temperatures, mercury or mercuric chloride may be adsorbed or absorbed, as described in Reactions 5-8. For instance, mercury or mercuric chloride may be adsorbed or absorbed by the sorbent particulates in the air preheat zone114or the gas cleaning unit116. These reactions may occur when the temperature drops below approximately 200° C. (approximately 392° F.). Since temperatures within this range may occur in the air preheat zone114or the gas cleaning unit116, these portions of the PCC100may be the most effective in removing mercury or mercuric chloride. To effectively capture these pollutants, the contact time between the sorbent particulates and the mercury or mercuric chloride may be greater than approximately 30 seconds. Such long contact times may be achieved in the gas cleaning unit116.

The hot gases and entrained flyash particles produced by combusting the pulverized coal128may exit the burner zone106and pass into the superheater zone108, where the hot gases contact the steam tubes140. The steam tubes140extract heat from the hot gases and increase the steam temperature. In the superheater zone108, the temperature of the hot gases ranges from approximately 975° C. to approximately 1320° C. (from approximately 1800° F. to approximately 2400° F.). The hot gases and entrained flyash particles may pass into the reheat zone110, which is a transition zone between the superheater zone108and the economizer zone112. Steam tubes140may also be present in the reheat zone110. The temperature in the reheat zone110may vary from approximately 650° C. to approximately 980° C. (from approximately 1200° F. to approximately 1800° F.). The hot gases may be cooled in the economizer zone112by additional steam tubes140. The temperature of the hot gases in the economizer zone112may range from approximately 535° C. to approximately 650° C. (from approximately 1000° F. to approximately 1200° F.).

The gases that exit the economizer zone112are referred to in the art as flue gas. At this point, the flue gas may include air, combustion products, water vapor, carbon dioxide, mercury, and particulate matter. The flue gas may be substantially free of the nitrogen-containing pollutants, the sulfur-containing pollutants, and HCl because these pollutants are removed in the burner zone106, the superheater zone108, or the reheat zone110. The flue gas may be further cooled by gas-to-gas heat exchangers (not shown) in the air preheat zone114to preheat the incoming combustion air. The temperature of the flue gas in the air preheat zone114may range from approximately 120° C. to approximately 230° C. (from approximately 250° F. to approximately 450° F.). Flue gas150may flow into the gas cleaning unit116, such as the baghouse or electrostatic precipitator (ESP), to remove the particulate matter, such as the flyash152. The flyash152may be collected on a filter in the gas cleaning unit116.

Since introducing the oil shale particles120into the PCC100utilizes many existing coal handling and processing technologies, this method of decreasing levels of pollutants in the flue gas150may be readily implemented in existing PCCs because it does not require the installation of new equipment. The use of the oil shale particles120may also be incorporated into future PCC designs without significant costs.

As described above, the oil shale particles120may be used to decrease the amount of a single type of pollutant, such as a nitrogen-containing pollutant, H2SO4, SO3, SO2, H2S, COS, CS2, mercury, or mercury chloride, in the flue gas150. The oil shale particles120may also be used to decrease the amount of different types of pollutants in the flue gas150. Therefore, the oil shale particles120may provide multi-pollutant control. In addition, since pyrolization of the oil shale particles120produces porous sorbent particulates, higher pollutant loadings may be achieved. As such, lower injection rates of the oil shale particles120may be used, which decreases the amount of solid material for disposal. While the oil shale particles120effectively decrease the pollutant levels in the flue gas150, the oil shale particles120may also be used in combination with other technologies to further decrease the amounts of the pollutants, such as the LIMB, LIDS, SNCR, and NOxreburning technologies.

In addition to removing the pollutants, the oil shale particles120may add enthalpy (i.e., heating value) since the oil shale particles120are combusted along with the primary fuel. The char particles and the heavy and light hydrocarbons, which are produced during the combustion of the oil shale, may be fully or partially combusted to provide additional heat, as shown by Reactions 24-31:
CxHy+(x+y/4)O2→xCO2+y/2H2O  (24),
CO+½O2→CO2(25),
CxHy+x/2O2→xCO+y/2H2(26),
CxHy+xH2O→xCO+(x+y/2)H2(27),
Char carbon+O2→CO2(28),
Char carbon+½O2→CO  (29),
Char carbon+CO2→2CO  (30),
Char carbon+H2O→CO+H2(31).

While not all of Reactions 24-31 are exothermic, the reactions either produce heat or produce reactive gases that may be used to produce heat. The oil shale may provide a net positive heat of combustion that ranges from approximately 4.7 MJ/kg (or approximately 2,000 BTU/lb) to approximately 9.3 MJ/kg (or approximately 4,000 BTU/lb). The energy provided by the combustion of the oil shale may offset the heat lost due to the pollutant sorption reactions.

The unreacted heavy and light hydrocarbons may be completely reacted in the superheater zone108or the reheat zone110with excess oxygen or air (not shown) that is introduced. In addition, supplementary oxygen (not shown) may be added to the superheater zone108or the reheat zone110as needed to combust the heavy and light hydrocarbons. Most combustion chambers are equipped with soot blowing air injectors or air lances, which may be used to adjust the oxygen concentration to achieve complete combustion of the heavy and light hydrocarbons.

Using the oil shale particles120in the combustion process may also improve the disposal of flyash produced during the combustion of the primary fuel. The combustion of the oil shale may also produce flyash152and slag154(coal and oil shale byproduct mineral matter). The oil shale particles120may be used to make the flyash152or the slag154suitable for disposal in a landfill. During combustion, the oil shale particles120are calcined and converted to a pozzolanic material that includes oxide compounds. The pozzolanic material may encapsulate and immobilize the metals, slag154, and flyash152produced during the combustion. The flyash152may also be used as a road bed material or a construction material.

Not only may oil shale be used as an agent to reduce pollution in a combustion process, metal pyrolysis process, calcination process, or other processes, devolatilized oil shale may also be used as a pollutant control material. Kerogen in oil shale may be reacted and devolatilized in an ex-situ thermal conversion process to produce shale minerals and char particles and a combustible kerogen-based fuel. The shale minerals and char particles may be fed to a separate, coupled thermal conversion process, such as, but not limited to, a combustion process, a cement kiln, or ore smelting or metals refining processes, to absorb or adsorb pollutants in much the same way that the shale minerals produced by the addition of oil shale to a combustion process absorb and adsorb pollutants. In addition, the kerogen-based fuel may also be fed to the process to act as a reduction agent to remove pollutants. Alternatively, the kerogen-based fuel may be used as a heating fuel or may be processed into useful fuel products.

Embodiments of the invention involve the devolatilization of kerogen from oil shale to produce a shale sorbent and a kerogen-based fuel. The devolatilization of kerogen from oil shale may be controlled such that desired characteristics of shale sorbent and kerogen released from the oil shale may be produced.

According to certain embodiments of the invention, the gasification, pyrolysis, devolatilization, or retorting of oil shale may be performed to produce a solid ash, or shale sorbent, having pollutant sorbent qualities. Oil shale may be introduced to a gasification process to controllably release kerogen from the oil shale. The controlled release of kerogen from the oil shale may result in the formation of a solid ash having pollutant control characteristics. For instance, the shale sorbent may act as a sorbent for pollutants or as a reductant for pollutants.

For example, oil shale may be introduced to a gasification process where the oil shale undergoes gasification to release kerogen from the oil shale. The gasification may be controlled to release large amounts of kerogen stored in the oil shale. Devolatilized oil shale exits the gasification process as a shale sorbent. The shale sorbent may be ground or otherwise processed to produce a shale sorbent having the desired size for use with processing operations to adsorb or absorb pollutants or to otherwise be used as a pollution sorbent. In some embodiments, the shale sorbent may be fed to a process to control pollutants in the process or contacted with process products to reduce pollutants therein.

According to other embodiments of the invention, the gasification of oil shale may be controlled to produce solid particles of pollutant sorbent, wherein the particles include fixed carbon which may assist in the absorption or adsorption of pollutants. The gasification of the oil shale may be controlled to ensure that portions of the oil shale are charred to produce a shale sorbent having an amount of carbon contained within or on the shale sorbent particles. The charred shale sorbent may be collected and used as a pollutant control sorbent.

According to still other embodiments of the invention, the gasification of oil shale may produce a reducing gas that may be used for pollutant control. For example, a gas that may be used in the reduction of NOxemissions may be produced according to embodiments of the invention. The devolatilization of kerogen from oil shale introduced to a gasification process to produce a reducing gas may include control and optimization of the devolatilization process to produce a gas having high quantities of reduced forms of carbon, such as CH4, C2H4, C2H6, C3H8, and low quantities of heavy hydrocarbons. The reducing gas may be fed directly to a process or process product streams where it may be used as a reducing gas or it may be stored according to conventional methods and used with other processes.

In other embodiments of the invention, a hydrocarbon gas may be produced by the gasification of oil shale. The devolatilization of kerogen from oil shale may be controlled to produce hydrocarbon gases. The devolatilization conditions may be controlled such that particular amounts of desired hydrocarbons are produced from the gasification process. In this manner, hydrocarbon gases may be formed that can be separated and marketed as synthetic natural gases or that can be altered to produce synthetic gases and gas products. Hydrocarbon gas streams may also be produced which may be cooled, condensed, and then distilled, cracked, or hydrogenated to produce higher value synthetic petroleum crude products.

FIG. 2illustrates a simplified material flow diagram of a pyrolysis or gasifier system that may be used to carry out embodiments of the invention. As illustrated inFIG. 2, ground oil shale210may be introduced into a gasifier200with steam212and one or more oxidizer gases214. The gasification of the oil shale210introduced into the gasifier200may cause the devolatilization of kerogen from the oil shale210, which may result in the production of a pyrolysis gas220and a shale sorbent230. The pyrolysis gas220may be removed from the gasifier200and stored, burned, utilized, or otherwise processed as desired. Similarly, the shale sorbent230may be used as a pollution sorbent according to embodiments of the invention or may be used with other processes.

The gasifier200represented by the block diagram illustrated inFIG. 2may include any type of gasifier200or thermal conversion unit capable of devolatilizing the kerogen from oil shale and capable of calcining the shale to produce a shale sorbent. For example, conventional fixed-bed gasifiers, fluid-bed gasifiers, or entrained-flow gasifiers may be used with embodiments of the invention. Other conventional gasifiers or rotary-driven pyrolysis operations may also be used with embodiments of the invention.

According to those embodiments of the invention where the oil shale210is being devolatilized of kerogen to produce a shale sorbent230to capture pollutants from other processes, a fixed-bed or bubbling fluidized-bed gasifier may be used to gasify the oil shale210. The use of such a gasifier200may even be preferred if the oil shale210particles being devolatilized of kerogen include crushed, coarse oil shale210particles with sizes, for example, between about 0.5 mm to 10 mm in diameter. The use of a fixed-bed or bubbling fluidized-bed gasifier may help to produce high quality shale sorbent230wherein most of the kerogen contained in the oil shale210is removed from the oil shale210within the gasifier200. The shale sorbent230produced in such a manner may have a high “loss on ignition” value. Other types of gasifiers may also be used to produce such shale sorbents230.

In those embodiments of the invention where the oil shale210includes a finely ground oil shale210, such as oil shale having particle sizes between about 0.001 mm to about 0.01 mm diameter, an entrained gasifier may be used as gasifier200to devolatilize kerogen from the oil shale210. For example, oil shale210particles having a diameter of between about 0.001 mm and about 0.01 mm may be introduced into an entrained gasifier200to devolatilize kerogen therefrom. The pyrolysis gases220produced from the devolatilization process may be burned within the gasifier200to aid in the devolatilization process.

The choice of gasifiers200for use with embodiments of the invention may also depend upon the pyrolysis gases220desired from the process. For example, when the pyrolysis gases220are to be burned or otherwise used as reducing gases to reduce the presence of NOxpollutants or other pollutants in other gas streams, the gasifier200or other thermal conversion process may be selected to optimize the production of reduced forms of carbon, such as CH4and C2H4.

The production of heavy hydrocarbons in a pyrolysis gas may not be desired; therefore, a gasifier200or other thermal conversion process may be selected to limit the production of such heavy hydrocarbons. For instance, the presence of heavy hydrocarbons in a feed stream from a gasifier200to a secondary process may cause unwanted condensation of the feed stream. In some embodiments, the pyrolysis gas220exiting the gasifier200or other thermal conversion process may be routed to a tar cracker (not shown) or a gas reformer (not shown) to further break down or otherwise remove the heavy hydrocarbons from the pyrolysis gas220. Conventional processes may be used to alter or change the heavy hydrocarbons in a pyrolysis gas220stream before the pyrolysis gas220stream is routed to another process.

In other embodiments of the invention, the production of reduced forms of hydrocarbons in the pyrolysis gas220may not be desirable. For example, in syngas and synfuel production processes, the amount of hydrocarbons in the pyrolysis gas220is preferably minimized. Instead, the production of carbon monoxide (“CO”) and hydrogen (“H2”) is preferably maximized. Therefore, a gasifier200or other thermal conversion process may be selected to maximize the production of carbon monoxide and hydrogen during the pyrolysis of the oil shale210in the gasifier200. In some embodiments, the gasifier200may even be selected or operated to produce an optimized ratio of carbon monoxide and hydrogen for Fischer-Tropsch synthetic fuel production processes.

The introduction of oil shale210, steam212, and oxidizer gas214to a gasifier200as illustrated inFIG. 2may result in a number of different reactions within the gasifier200or other thermal conversion process. For example, when oil shale210is heated in the gasifier200or other thermal conversion process, shale minerals, char particles, and kerogen are produced. The shale minerals and char particles make up the shale sorbent230. The production of the shale minerals, char particles, and kerogen is similar to the reaction that occurs when oil shale210is introduced directly into a combustion chamber or other thermal conversion process, such as a combustion chamber of a pulverized coal boiler. The formation of the shale sorbent230and kerogen may be represented by Reaction 32:
oil shale+heat→shale sorbent+kerogen  (32).
A temperature of greater than or equal to approximately 200° C. may be used to pyrolyze the oil shale210in a gasifier200or other thermal conversion process. As the oil shale210is heated, the heat may cause the kerogen to depolymerize and devolatilize while the shale minerals may be calcined. The extent of depolymerization, devolatilization, pyrolysis, and char formation of the oil shale210may vary depending on particle heat up rates, particle temperature, surrounding gas temperature, and the amount of time that the oil shale210is heated in the gasifier200or other thermal conversion process. When the kerogen is devolatilized or released from the oil shale210, a porous matrix of oxides, carbonates, or silicates may remain including, but not limited to, silicon dioxide (“SiO2”), and oxides, and carbonates of calcium (“Ca”), magnesium (“Mg”), sodium (“Na”), potassium (“K”), iron (“Fe”), or zinc (“Zn”). For the sake of example only, the shale minerals may include, but are not limited to, calcium oxide, magnesium oxide, iron oxide, calcium carbonate, or mixtures thereof. The char particles or particles of residual carbon may also remain after the kerogen is devolatilized from the oil shale210. The shale sorbent230comprises the shale minerals and char particles. The shale sorbent230may include porous particles that have an increased surface area. As such, the shale sorbent230may have an increased adsorption or absorption capability relative to that of the oil shale210and may be used to adsorb or absorb mercury and other pollutants. In addition, the shale sorbents230may be porous, allowing pollutants to diffuse into the shale sorbent230and react with the oxides, carbonates, and silicates therein.

The introduction of steam212into the gasifier200or other thermal conversion process may react with the char particles of the shale sorbent230, forming activated carbon within, or on, the shale sorbent230as represented by Reaction 33:
oil shale+heat→shale minerals+char particles+kerogen+hydrocarbon derivatives  (33).

Kerogen in the oil shale210may be released within the gasifier200. Kerogen released from the oil shale210may provide a source of a reductant used to reduce pollutants in other processes. As shown in Reaction 34, the kerogen may be exposed to additional heat to crack or scission the kerogen, forming light and heavy hydrocarbons:
kerogen+heat+radicals→heavy and light hydrocarbons (CxHy)+CO+H2(34),
where x and y depend on the carbon and hydrogen ratio in the kerogen and temporal conditions. For instance, x may range from 1 to 7 for a light hydrocarbon, from 8 to 12 for an intermediate hydrocarbon, or from 12 to 42 for a heavy hydrocarbon. In correlation, y may range from 1 to 90 and is typically equal to two times x for a given hydrocarbon. A temperature of greater than or equal to approximately 350° C. may be used to crack and scission the polymeric kerogen. The heavy hydrocarbons are thus progressively converted to lighter hydrocarbons. The presence of steam helps crack and reform the heavy hydrocarbons.

Embodiments of the invention may be incorporated with any pollution producing processes to reduce the amount of pollution produced in a process. For example, a gasifier200for converting oil shale210to pyrolysis gases220and shale sorbent230may be incorporated with a pulverized coal boiler, a cement production process, a synfuels or syngas production process, a metallurgy pyrolysis process, a pulverized coal combustor, a furnace, a boiler, fluidized bed combustor or gasifier, a circulating bed combustor or gasifier, a staged reactor combustor or gasifier, an entrained-flow combustor or gasifier, an offgas duct, or an offgas cleanup transport reactor. The embodiments of the invention may be used to produce a shale sorbent230for absorbing or adsorbing pollutants produced in the respective processes or to produce a kerogen-based fuel that may be used with the processes. Embodiments of the invention are not limited to these recited uses and it is understood that a gasifier for producing shale sorbents230, pyrolysis gases220, or pollutant reduction gases may be incorporated with many conventional processes and especially processes which produce pollutants which are desired to be controlled.

The incorporation of a gasifier200or other thermal conversion process according to embodiments of the invention with a pollutant forming process is illustrated inFIG. 3. As illustrated, a gasifier200or other thermal conversion process may be incorporated with a pulverized coal boiler system300. The incorporation of a gasifier200or other thermal conversion process according to embodiments of the invention with a pulverized coal boiler system300may be used to provide shale sorbent230, pyrolysis gas220, or reduction gases to the pulverized coal boiler system300. Although the system illustrated inFIG. 3includes a gasifier200or other thermal conversion process incorporated with a coal boiler system300, it is understood that embodiments of the invention may be incorporated with many different systems where pollutants are generated and where reduction of such pollutants is desired.

As illustrated inFIG. 3, a conventional coal boiler system300may include a burner zone306, a superheater zone308, a reheat zone310, an economizer zone312, an air preheat zone314, and a gas cleaning unit316. Coal328, such as pulverized coal, may be introduced into the burner zone306where it may undergo combustion, forming gases and slag354. Air330may also be introduced into the burner zone306to facilitate the combustion of the coal328in the coal boiler system300. The introduction of air330may include the introduction of combustion air, primary air, and infiltration air as known with a conventional coal boiler system300. Slag354produced in the burner zone306may be removed from the coal boiler system300as conventionally known.

The coal328may be combusted in the burner zone306, which may be maintained at a temperature of about 800° C. to about 1650° C. Reactions within the burner zone306include reactions related to the combustion of coal328, such as Reactions 35 through 44:
C+O2→CO2(35),
2H+½O2→H2O  (36),
N+½O2→NO  (37),
2N→N2(38),
2Cl+H2O→2HCl+½O2(39),
S+O2→SO2(40),
2O→O2(41),
2FeS2+1½O2→Fe2O3+4SO2(42),
HgS→Hgo+SO2(43),
Carbonates→Oxide+CO2(44).
As indicated by the reactions which occur during the combustion of coal328, pollutants such as SO2, NO, and HCl may be produced. Other pollutants may also be formed. The pollutants are undesirable and may be removed by the burning of pyrolysis gases220from a gasifier200or other thermal conversion process according to embodiments of the invention or by the introduction of shale sorbent230into the coal boiler system300.

Gases and particulates formed during the combustion of the coal328exit the burner zone306and enter the superheater zone308. The gases and particulates from the superheater zone308pass into the reheat zone310and then into the economizer zone312before entering the air preheat zone314. Temperatures in each of the zones may be controlled by the presence of steam tubes340in each of the zones. Flue gases350exiting the air preheat zone314may be fed to a gas cleaning unit316, such as a baghouse or electrostatic precipitator (ESP). Particulate matter, such as flyash352, may be collected from the gas cleaning unit316and the waste gases from the coal boiling system300may be released or fed to other gas cleaning processes.

According to embodiments of the invention, pollutants produced in the burner zone306and throughout the remainder of the coal boiler system300may be reduced by the introduction of shale sorbent230or pyrolysis gases220into the coal boiler system300or into product streams produced by the coal boiler system300. For example, NOxpollutants formed in the burner zone306of the coal boiler system300may be reduced by the simultaneous burning of pyrolysis gases220formed from the gasification of oil shale210in the burner zone306. The pyrolysis gases220from a gasifier200may be fed from the gasifier200to an input in the burner zone306of the coal boiler system300. When fed or otherwise injected into the burner zone306, the pyrolysis gases220may be oxidized by the presence of NOR, thereby reducing the nitrogen-containing pollutants to N2or other nitrogen-containing compounds, carbon dioxide (“CO2”), and water (“H2O”) in accordance with Reactions 3 and 4 previously described.

Additional oxidizing reactions may also occur with the introduction of pyrolysis gas220to the burner zone306. For example, Reactions 45 and 46 may occur within the burner zone306, in addition to the reduction of NOxshown in Reactions 3 and 4:
CxHy+(x+y4)O2→xCO2+y/2 H2O  (45),
CO+½O2→CO2(46),
where x may range from 1 to 7 for a light hydrocarbon, from approximately 8 to 12 for an intermediate hydrocarbon, or from approximately 13 to 42 for a heavy hydrocarbon. In correlation, y may range from 1 to 90 and is typically equal to nominally two times x for a given hydrocarbon. In some instances, the pyrolysis gases220may be introduced into the burner zone306in two or more locations. The introduction of pyrolysis gases220in more than one location may facilitate both the reduction reactions of NOxpollutants as shown by Reactions 3 and 4 and the oxidation reactions of Reactions 45 and 46. An illustrative example of multiple pyrolysis gas220feed inputs into the burner zone306is represented by the two pyrolysis gas220feed inputs220(a) and220(b) illustrated inFIG. 3. As illustrated, one or more of the pyrolysis gas220feed inputs220(b) may be located on a dividing zone between the burner zone306and the superheater zone308or may be located at the entrance of the superheater zone308from the burner zone306.

Gasses and particulate matter from the burner zone306may pass into the superheater zone308where additional reactions occur. The superheater zone308may be maintained at between about 675° C. and about 1320° C. Steam tubes340may be positioned in the superheater zone308to provide heat as known with conventional coal boiler systems300.

Pollutants in the gases and particulate matter produced in the burner zone306may be at least partially removed by adsorption or absorption of the pollutants by shale sorbent230introduced into the superheater zone308. Shale sorbent230from the gasifier200may be introduced into the superheater zone308in one or more locations. For instance, shale sorbent230from the gasifier200may be introduced into the superheater zone308of the coal boiler system300to absorb and adsorb pollutants transferred from the burner zone306to the superheater zone308. The shale sorbent230may be ground to a desired size and entrained in air such that it may be injected into the coal boiler system300. An example of the introduction of shale sorbent230is illustrated inFIG. 3, where the shale sorbent230from the gasifier200is injected into the superheater zone308at inlet230(a). Although only one shale sorbent230inlet230(a) into the superheater zone308is illustrated, it is understood that one or more inlets may be used and that the positioning of the inlets to feed shale sorbent230into the superheater zone308may be customized to maximize or customize the removal of pollutants from the gases and particulate matter in the superheater zone308.

Pollutants passed from the superheater zone308to the reheat zone310of the coal boiler system300may also be at least partially removed by the introduction of shale sorbent230into the reheat zone310. Shale sorbent230from a gasifier200may be introduced into the reheat zone310through one or more inlets230(b) in much the same manner that it may be introduced into the superheater zone308. Shale sorbent230may also be introduced into the economizer zone312or air preheat zone314to help remove pollutants from the gases and particulates in the coal boiler system300.

Shale sorbent230in the air preheat zone314may help to capture mercury and mercury-based pollutants in particulate matter passed to the air preheat zone314. Shale sorbent230may be introduced into the air preheat zone314from a gasifier200or other source. In addition, shale sorbent230introduced in earlier process steps of the coal boiler system300may be passed into the air preheat zone314where the shale sorbent230may react with mercury-containing pollutants in the particulate matter found therein. The reactions of shale sorbent230with mercury may include reactions such as those shown by Reactions 5 through 8 herein.

In other embodiments of the invention, the shale sorbent230need not be fed to the coal boiler system300directly from the gasifier200or other thermal conversion process. Instead, shale sorbent230produced in a gasifier200or other thermal conversion process according to embodiments of the invention may be stored for later use and the stored shale sorbent230may be introduced to the coal boiler system300at a desired time and in a desired manner. For example, stored shale sorbent230from a storage facility may be introduced into one or more shale sorbent230inlets230(a) in a superheater zone308of a coal boiler system300and into one or more shale sorbent230inlets230(b) in a reheat zone310of a coal boiler system300.

The introduction of shale sorbent230into a coal boiler system300may reduce pollutants present in the products of the coal boiler system300, such as particulate matter and gases. The shale sorbent230may adsorb or absorb some of the pollutants and may react with others. For example, shale sorbent230comprising calcium and magnesium may decrease pollutants according to Reactions 47 and 48:
Ca/MgO+SO2+½O2→Ca/Mg-Sulfates  (47),
Ca/MgO+2HCl→Ca/MgCl2+H2O  (48).

The shale sorbent230may be introduced into a coal boiler system300by entraining the shale sorbent230with air and injecting the shale sorbent230into the coal boiler system300in an air stream. The size of the shale sorbent230used may be dependent upon the desired reactions and the pollutant control desired for the type of coal328being combusted in the coal boiler system300. For example, in many coal boiler systems300, the shale sorbent230introduced into the coal boiler system300may have a diameter of about 0.002 mm to about 0.015 mm. Shale sorbent230having a desired size may be produced in the gasifier200or other thermal conversion process by introducing oil shale210having sizes which result in the production of the desired shale sorbent230sizes into the gasifier200or other thermal conversion process. In other embodiments, the shale sorbent230produced by the gasifier200or other thermal conversion process may be ground to a desired size prior to introduction of the shale sorbent230into the coal boiler system300. For example, as illustrated inFIG. 3, a grinder/classifier290may be incorporated with embodiments of the invention to grind the shale sorbent230produced by the gasifier200into desired particle sizes. Entrainment air291may also be introduced to the grinder/classifier290to entrain the shale sorbent230for delivery to the coal boiler system300. In other embodiments of the invention, pyrolysis gases220may be used to help fire the burners in the burner zone306or may be burned to heat water and form steam that is fed to the steam tubes340. For example, some or all of the pyrolysis gases220produced by the gasifier200or other thermal conversion process during the gasification of oil shale210may be fed directly to the coal boiler system300as a source of fuel for burners or for steam generation processes. The pyrolysis gases220from the gasifier200or other thermal conversion process may also be treated or otherwise processed to produce a desired fuel composition in the pyrolysis gases220before such gases are used as fuel for the coal boiler system300.

According to still other embodiments of the invention, shale sorbent230and pyrolysis gases220from a gasifier200or other thermal conversion process may be introduced into a cement kiln or other calcining process to help control pollutants formed in cement kilns and cement production processes. For example, many cement kiln processes do not meet the new pollution control requirements being promulgated by the Environmental Protection Agency. Incorporation of embodiments of the invention within such cement kiln processes may effectively retrofit the cement kiln processes such that the pyrolysis gases220and shale sorbent230may be used to reduce pollutants from the cement kiln processes.

A gasifier200or other thermal conversion process incorporated with a cement kiln400according to particular embodiments of the invention is illustrated inFIG. 4. The cement kiln400may include any type of conventional cement kiln or kiln designed for producing cement or cement clinker. As illustrated inFIG. 4, the cement kiln400may include a dehydration zone410, a calcination zone420, and a clinkering zone430. Clay402for producing cement clinker may be introduced into the dehydration zone410at a solids input404according to conventional methods. Moisture in the clay402is removed from the clay402in the dehydration zone410of the cement kiln400. The temperature in the dehydration zone410may be controlled to achieve a desired amount of dehydration based upon the moisture content of the clay402being fed to the cement kiln400. For instance, the temperature in the dehydration zone410may be set at between about 400° C. to about 500° C.

Dehydrated clay402is transported from the dehydration zone410into the calcination zone420where the temperature may also be controlled. The temperature in the calcination zone420may be between, for example, about 500° C. and about 1250° C. The clay402is calcined in the calcination zone420according to conventional calcination techniques.

Calcined clay402may advance into the clinkering zone430where the final heating of the calcined clay402forms clinker450that may be used with cement. The temperature in the clinkering zone430may be controlled between about 1250° C. to about 1550° C. The clinker450may exit the cement kiln400and may be used according to conventional processes.

Heat may be provided to the cement kiln400according to conventional processes, such as by use of gas/oil burners440located in or around the clinkering zone430of the cement kiln400. The combustion of gas or oil in the gas/oil burners440may be controlled such that the desired temperatures are achieved in the clinkering zone430, the calcination zone420, and the dehydration zone410.

Effluent gases460generated in the cement kiln400may exit the cement kiln400and be fed to a process for cleaning the effluent gases460of pollutants before being released into the environment or biosphere. For example, as illustrated inFIG. 4, the effluent gases460may exit the cement kiln400and be fed to a reactor470capable of scrubbing the effluent gases460or otherwise reducing the amount of pollutants, if any, in the effluent gases.

According to embodiments of the invention, pyrolysis gases220from the gasifier200or other thermal conversion process may be burned in the gas/oil burners440to provide heat to the cement kiln400. As illustrated inFIG. 4, a portion of the pyrolysis gases220from the gasifier200or other thermal conversion process may be fed to the gas/oil burners440. The gasifier200or other thermal conversion process may be operated such that pyrolysis gases220produced within the gasifier200or other thermal conversion process may be easily burned in the gas/oil burners440of the cement kiln400. In this manner, additional sources of heating gas for the gas/oil burners440may be provided by the pyrolysis or gasification of oil shale210in a gasifier200or other thermal conversion process according to embodiments of the invention.

In other particular embodiments of the invention, at least a portion of the pyrolysis gas220produced by the gasifier200or other thermal conversion process may be fed to one or more zones of the cement kiln400to help reduce pollutants in the various zones of the cement kiln400. Introduction of the pyrolysis gases220into the various zones of the cement kiln400may oxidize the pyrolysis gases220and reduce pollutants contained in the gases and solids within the cement kiln400. For instance, pyrolysis gases220introduced into various zones of the cement kiln400may be oxidized in the presence of NOxin the cement kiln400, thereby reducing the nitrogen-containing pollutants to N2or other nitrogen-containing compounds, carbon dioxide (“CO2”), and water (“H2O”) in accordance with Reactions 3 and 4 previously described. Additional oxidization reactions, such as those of Reactions 45 and 46, may also occur as a result of the introduction of pyrolysis gas220or pyrolysis gas220products into the various zones of a cement kiln400. Such reactions may be used to reduce the amount of pollutants in the cement kiln400.

According to still other embodiments of the invention, pyrolysis gases220may be fed to a cement kiln400from a storage facility or other delivery process. For example, pyrolysis gases220produced by a gasifier200or other thermal conversion process according to embodiments of the invention may be stored by conventional methods before being used with a cement kiln400as gas or fuel feed to a gas/oil burner440or as a pollutant control gas in the various zones of the cement kiln400. Pyrolysis gases220from a gasifier200or other thermal conversion process according to embodiments of the invention may also undergo further processing before being fed to a cement kiln400according to embodiments of the invention. For instance, the pyrolysis gases220may be processed to form syngas or synfuels that may be used as a fuel for the gas/oil burners440of a cement kiln400.

The burning of pyrolysis gas220in a cement kiln400may also reduce the burning of waste tires in a cement kiln400, which is conventionally done to increase the heat within a cement kiln400and to reduce NOxpollutants. The heat that may be provided by pyrolysis gas220may replace the heat generated by the burning of waste tires while still reducing NOxpollutants. In addition, the removal of the burning of waste tires in the cement kiln400may reduce the amounts of sulfur-containing pollutants and mercury-containing pollutants in the cement kiln400, which are produced by the burning of waste tires.

In other particular embodiments of the invention, pollutants formed or released in a cement kiln400may be reduced by the introduction of shale sorbent230into the cement kiln400. Shale sorbent230may be introduced into a cement kiln400with the introduction of clay402or at other locations in the cement kiln400. As illustrated inFIG. 4, shale sorbent230from a gasifier200or other thermal conversion process may be combined with clay402and introduced in the cement kiln400or introduced with the clay402into the cement kiln400. Prior to introduction of the shale sorbent230into the cement kiln400, the shale sorbent230may be ground or otherwise processed to achieve a desired size for the shale sorbent230entering the cement kiln400. Shale sorbent230introduced into a cement kiln400may act as a reducing agent for NOxpollutants found in the cement kiln400and particularly in the upper end of the cement kiln400around the dehydration zone410and calcination zone420.

According to other embodiments, the shale sorbent230introduced into a cement kiln400clinkering process may entrain pollutants produced in the process. For example, mercury-containing pollutants formed during the clinkering process may be adsorbed or absorbed by the shale sorbent230added to the clinkering process. Mercury or mercuric chloride formed in the cement kiln400and entrained in the cement retort being formed into cement clinker450may come into contact with shale sorbent230added to the clinkering process. Contact between the shale sorbent230and the mercury-containing compounds may result in the capture of the mercury in the shale sorbent230in a manner similar to Reactions 7-10. In those instances where mercury or mercuric chloride pollutant removal are desired, the shale sorbent230may be formed in a gasifier200or other thermal conversion process such that the amount of char or activated carbon in the shale sorbent230is maximized for the reduction or capture of mercury-containing compounds.

The introduction of shale sorbent230into a cement kiln400during a clinkering process may also reduce the amount of other pollutants found in the cement retort or cement clinker450of the cement kiln400according to embodiments of the invention. The shale sorbents230produced by a gasifier200may be tailored such that the amount of char or activated carbon in the shale sorbents230is at a desired level for the particular clinkering process to which the shale sorbent230is being added. In addition, the size of the shale sorbent230particles added to a cement kiln400may be tailored to the desired reactions in the cement kiln400. For example, shale sorbent230from a gasifier200or other thermal conversion process or from a storage facility may be ground or otherwise processed to produce shale sorbent230having a desired particle size for a particular clinkering process.

The introduction of shale sorbent230into the cement kiln400may also provide an additional source of material for forming cement clinker450. The use of oil shale as a cement clinker450production component has been conventionally used. As with the clinkering of oil shale, the clinkering of shale sorbent230may provide a cement clinker450that is desirable. The size of the shale sorbent230used to produce cement clinker450may be controlled, such as by feeding the shale sorbent230formed in gasifier200to a grinder/classifier290prior to introduction of the shale sorbent230into a cement kiln400, as illustrated inFIG. 4.

In still other particular embodiments of the invention, the shale sorbent230produced in a gasifier200or other thermal conversion process may be used to scrub or otherwise remove pollutants from effluent gases460from a cement kiln400. For example, as illustrated inFIG. 4, shale sorbent230produced by gasifier200or other thermal conversion process may be fed to a reactor470where effluent gases460from a cement kiln400may be cleaned of pollutants. The reactor470may include a fixed or transport reactor sorbent bed wherein shale sorbent230is used to remove pollutants such as mercury-containing pollutants, sulfur-containing pollutants, nitrogen-containing pollutants, and hydrochloric acid.

As illustrated inFIG. 4, effluent gases460from a cement kiln400may be fed to the reactor470along with shale sorbent230from a gasifier200or other thermal conversion process or other source. Pollutants in the effluent gases460may react with the shale sorbent230according to Reactions described herein. For example, sulfur-containing pollutants may react with the shale sorbent230in accordance with Reactions 9-15; mercury-containing pollutants may react with the shale sorbent230in accordance with Reactions 7-10; and hydrochloric acid (“HCl”) may react with shale sorbent230in accordance with Reactions 22-23.

Spent shale sorbent230which may have absorbed or adsorbed its limits of pollutants maybe removed232,465from the reactor470and stored or otherwise disposed of according to conventional methods.

Although embodiments of the invention have been described with respect to the use of a shale sorbent230and pyrolysis gas220from a gasifier200or other thermal conversion process as illustrated inFIG. 4, it is also understood that the shale sorbent230or pyrolysis gas220used with the cement kiln400may be obtained from other sources. For example, pyrolysis gas220from a gasifier200or other thermal conversion process may be stored or otherwise processed offsite and delivered to a cement kiln400such as by pipeline or tanker truck. Similarly, shale sorbent230produced by a gasifier200or other thermal conversion process may be stored and later transported to a cement kiln400for use with a clinkering process or as a pollutant control for scrubbing effluent gases460.

Shale sorbent230added to a cement kiln400may also contribute energy to produce heat (or enthalpy) to the cement kiln400system. For example, the addition of shale sorbent230to a cement kiln400may contribute some enthalpy to the cement kiln400in a manner similar to the addition of oil shale to increase enthalpy of a system in accordance with Reactions 24-31.

According to still other embodiments of the invention, the shale sorbent230and pyrolysis gas220products of a gasifier200or other thermal conversion process may be used in the production of synthesis gas, or syngas, and synthesis fuels, or synfuels. As illustrated inFIG. 5, a gasifier200or other thermal conversion process according to embodiments of the invention may be combined with a syngas or synfuels production process500.

In a syngas production process, a feedstock560such as coal, municipal waste, waste tires, biomass, or other synthesis gas feedstock, may be fed to a syngas gasifier550where the feedstock560is burned to form carbon monoxide (“CO”) and hydrogen (“H2”), or a syngas565. The carbon monoxide and hydrogen may then be used in a syngas or synfuels production process. Steam512and oxidizer air514may be fed to the syngas gasifier550to promote the combustion of the feedstock560in the syngas gasifier550. Waste products568from the syngas gasifier550may include pollutants such as mercury-containing pollutants and other metal pollutants.

According to particular embodiments of the invention, the pyrolysis gases220from the gasifier200or other thermal conversion process may be combined with the syngas565in a reactor570, such as a fixed- or fluidized-bed reactor. The combination of the pyrolysis gases220with the syngas565may form a product gas572which may be used in the further processing of syngas and synfuels. For example, the product gas572may include components such as carbon monoxide, carbon dioxide, hydrogen, light hydrocarbons, and heavy hydrocarbons. The product gas572may be processed according to conventional methods to form syngas and synfuels.

Shale sorbent230from the gasifier200or other thermal conversion process may also be fed to the reactor570. The shale sorbent230in the reactor570may be used to absorb or adsorb pollutants from the pyrolysis gas220and syngas565which is combined in the reactor570.

Shale sorbent230from the gasifier200or other thermal conversion process may also be fed to a transport reactor580, such as a fixed- or fluidized-bed reactor. Waste products568from the syngas gasifier550may also be fed to the transport reactor580. The combination of the waste products568with the shale sorbent230in the transport reactor580may allow the shale sorbent230to absorb or adsorb pollutants from the waste products568. For example, the shale sorbent230fed to the transport reactor580may adsorb or absorb pollutants such as sulfur-containing pollutants, halide compounds, mercury-containing pollutants, or other pollutants from the waste products568. The spent shale sorbent231may be reclaimed for construction material or may be discarded in landfills according to conventional processes. In some instances, the pozzolanic nature of the spent shale231will help immobilize the pollutants and contaminants absorbed or adsorbed by the shale sorbent230when stored in a landfill.

Although the transport reactor580illustrated inFIG. 5is a single reactor, a series of transport reactors may be used. In some instances, the temperatures of a series of transport reactors may be controlled such that different pollutants are adsorbed or absorbed by the shale sorbent230fed to each of the transport reactors.

According to still other embodiments of the invention, shale sorbent230and pyrolysis gases220from a gasifier200or other thermal conversion process may be used in metallurgical processes. For example, in a metallurgical process such as an ore smelting or refining process, large amounts of energy are used to provide heat to the process. The process also creates pollutants which must be captured or otherwise reduced from the waste products before being disposed. The combination of a gasifier200or other thermal conversion process according to embodiments of the invention with a metallurgical process may provide a heating gas, a pollutant reduction gas, and a sorbent for adsorbing or absorbing pollutants from the waste products produced by the process.

In a metallurgical process, pyrolysis gases220from a gasifier200or other thermal conversion process may be used as heating gases or fuel to help provide the heat that is necessary for the metallurgical process. The pyrolysis gases220may also be burned or subject to oxidation to reduce pollutants such as NOxpollutants in the process. The shale sorbent230created by the gasifier200may be combined with the process or with the waste products from the process to remove pollutants from the waste products. For example, the shale sorbent230may be used to remove sulfur-containing pollutants, mercury-containing pollutants, halide compounds, metal pollutants, or other pollutants from the waste products.

Embodiments of the invention, therefore, may be used or combined with many different processes to provide additional heating gases, pollutant reduction gases, or pollution sorbents for the processes. Although embodiments of the invention have been described with respect to particular processes, it is understood that the embodiments of the invention, and the pyrolysis gases220and shale sorbents230of the invention, may be combined with other processes, and particularly other processes where additional heating supplies are desired or where additional pollutant control mechanisms are desired.