# Patent

## Title
Energy efficient, low emissions shale oil recovery process

## Abstract

A process for the energy efficient, environmentally friendly recovery of liquid and gaseous products from solid or semi-solid hydrocarbon resources, in particular, oil shale or tar sands. The process involves non-oxidative pyrolysis to recover fluid energy values, oxidative combustion to recover energy values as recoverable heat, and environmental sequestration of gases produced.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation from International Application under the PCT designating the United States, Application No. PCT/US08/58112, filed 25 Mar. 2008, published as WO2008118904 on 2 Oct. 2008, which claims priority from United States Provisional Patent Application 60/896,933, filed 25 Mar. 2007. The Application under the PCT is hereby incorporated by reference.


BACKGROUND
Recovery of oil from oil shale involves heating the oil shale rock to sufficient temperature such that kerogen, the organic material contained in oil shale, converts to gases, liquids and residue. The residue, which may be a form of coke, is left deposited on the mineral matter of the oil shale. In the prior art the principal objectives of such processes are to (a) efficiently get the heat into the oil shale rock and (b) separate the desirable products from the spent oil shale.
The process of heating oil shale to conversion temperatures is generally called retorting, a word of European origin that describes a process for distillation or destructive distillation. The retorting process may be conducted in-situ by supplying heat to a bed of ore largely undisturbed. The retorting process may also be conducted by modified in-situ, by first preparing the bed of ore prior to heating. Retorting may also be conducted in surface vessels to which mined ore is introduced.
In the prior art, the methods for recovering oil values have exhibited various problems that adversely affect the efficiency or reliability, which in turn, adversely affect the economics. For example, vertical, solids down-flow, product up-flow processes have proven to be reliable, but yield a relatively low grade of product because the product is required to exit the reactor overhead, forcing the product to remain in the reactor longer than desirable. Vertically-inclined retorts that provide a means for removal of products from the bottom (product down-flow), and counter-currently pump the ore from the bottom by means of a ‘rock pump’ (solids up-flow) have proved to suffer from poor mechanical reliability.
Horizontally-inclined vessels, patterned after rotary kilns, suffer from slow heat transfer and result in much larger vessels than vertically-oriented vessels and are expensive to fabricate. True in-situ methods, while lower in capital costs, are not as controlled and result in uncertainty about legacy environmental issues such as ground water contamination. Modified in-situ methods experience better control than true in-situ, but might result in poorer control than surface processes. Modified in-situ processes are also likely to suffer from lower production efficiency compared to surface processes.
In historic retorting processes the production of CO2 from decomposition of carbonate minerals was not considered an environmental issue. However, it was considered an energy consumption issue in that decarbonation is an endothermic reaction and consumes up to 8% of the energy value available from the ore. Various proposals have been made to limit the amount carbonate decomposition that gives rise to these endothermic reactions, the most common being maintaining a temperature below which decomposition occurs. However, a lower final temperature results in a lower rate of production, and possibly lower product yields.
Tar sands are also processed to recover and convert the organic materials (bitumen) to marketable products. In typical practice tar sands are mined, mixed with water, and the bitumen (tar) is separated from the sand by flotation. In yet other practice pipes are laid, or drill-holes are made into a bed of the resource and steam is injected to raise the temperature of the bed. Viscosity of the bitumen is reduced, which then drains to a second lower pipe where it is withdrawn. While practiced in rich, unconsolidated ores such as those found in Alberta, Canada, not all resources in the United States or Canada are rich or unconsolidated. Some are consolidated, with low permeability and sufficiently lean (lower grade) that only small amounts of bitumen are recovered by water extraction or will drain in a steam stimulation process. In principal, tar sands can also be retorted.
Thus, there remains a need for a process that is efficient, reliable, environmentally friendly and cost-effective for both oil shale and tar sand resources.
SUMMARY
Both the environmental problems with CO2 production and the associated energy losses are solved by means of a three cycle system that is energy self-sufficient and thermodynamically efficient. The cycles are comprised of non-oxidative pyrolysis (NOP), oxidative combustion (OC), and environmental sequestration (ES).
An aspect is an OC cycle where metal carbonates (mostly of Ca, Mg, K, and Na) are allowed to decompose (decarbonation), but are restored to their metal carbonate form through recycle of CO2 rich gas (recarbonation). When recycling CO2 to the inlet of the OC cycle, the resulting recarbonation of metal oxides is exothermic, and this exothermic energy is captured by the gases and is used to raise steam. Thus, the process suffers a lower or no net energy penalty from the initial endothermic decarbonation reactions, while at the same time allowing for high temperature combustion which favors faster reaction kinetics and more efficient energy utilization.
Substantially all of the CO2 produced from decarbonation reactions is reacted with the metal oxides to reverse the decarbonation reaction. Further, by passing the combustion gases through alkali metal oxide/carbonate beds in the OC cycle and in an ES cycle, other pollutants are sequestered. A stoichiometric excess of CO2, produced substantially from the combustion of organic carbon, is collected at the outlet of the ES cycle. The result is a clean, industrial grade CO2 suitable for oil field injection, as a displacement gas for coal-bed methane, as a hydroponic gas, as an inerting gas, or any variety of industrial uses of CO2. Industrial grade CO2 that displaces CO2 produced naturally or by recovery from air serves the purpose of reducing, or at least not adding to the CO2 that otherwise would be released. The pure CO2 may also be sequestered in geologic formations.
Another aspect is configuring the NOP cycle such that oil is recovered from the bottom and gas is recovered from the top by using a flow of heated gas. A suitable gas is steam, because steam has a high vapor heat capacity and is readily separated from produced gases. Other gasses are contemplated, but may be less satisfactory, such as, for example, carbon dioxide, nitrogen, or light hydrocarbons of about 5 carbons or less. Oxidizing gasses cause deleterious effects on product yield and quality. Direct heating the bed using hot inert gasses also allows for precise temperature control where adequate retort rates are achieved while avoiding the premature decomposition of carbonates. Conditions are such that liquid products are not vaporized or atomized into a gas stream, but are allowed to drain through the bed where they can be withdrawn from the bottom. Withdrawing a large portion of the product as in a liquid phase provides several yield and product quality benefits over withdrawing most of the product in a gas phase.
Another aspect is to provide an ES cycle by using the spent oil shale bed as an environmental sequestration bed for oxides of N and S. Fully carbonating the ES bed also leaves a relatively pH neutral spent shale for land fill.
Another aspect is producing industrial grade CO2 from the excess CO2 produced. This is, in part, accomplished by producing the carbon dioxide in a separate OC cycle, where carbon dioxide is produced by combustion and metal carbonate decomposition, whereas the hydrocarbon product is produced in the NOP cycle, where product is produced under conditions where a minimum of carbon dioxide is formed. Accordingly, there is no need to separate hydrocarbon product and carbon dioxide from a single outlet steam. This allows for optimization of the hydrocarbon product without materially comprising the ability to produce a purified, industrial quality carbon dioxide product. In addition, the separate NOP and OC cycles allow for optimum removal of residual hydrocarbons from the bed without compromising the product through excess combustion of product and excess introduction of carbon dioxide into the product stream.
A purified carbon dioxide product is also largely achieved by use of the optional ES cycle, which is used to sequester undesired contaminants from the final carbon dioxide stream.
Another aspect is controlling the system for essentially energy self-sufficient operation. Once the process is started there are no external demands for power or fuel (If liquid fuels are needed additional systems can be provided, for example, an on site upgrader, and fuel preparation facility produces the needed fuels from the liquid product).
Among the advantages of the present process is its energy efficiency. Virtually all of the original energy values in the oil shale are converted to either products or heat energy. The products are high quality and the heat energy (high temperature) is high quality. Thus, utilization of the produced values is economically and thermodynamically enhanced, and losses are reduced to a minimum. Much of the original energy value of the hydrocarbonaceous materials of the ore is recovered as fluid products during the NOP cycle. Remaining energy values in the residual materials are recovered during the OC cycle where these materials are oxidized, producing a high-temperature effluent gas from which heat is recovered by steam production, or the like. Energy consumed by decarbonation of metal carbonates to metal oxides in the OC cycle is recovered by recycling carbon dioxide back into the bed under conditions to convert the metal oxides back to metal carbonates, producing heat that is passed into the effluent gas.



BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a flow sheet of illustrated an ore treating process.
FIG. 2 is in five parts, FIGS. 2A to 2E. When 2B, 2C, 2D, and 2E are arranged as in 2A, they show a mass balance diagram illustrating an exemplary embodiment.
FIGS. 3A, 3B, and 3C are schematics illustrating an exemplary bed of ore treated by an exemplary process.



DETAILED DESCRIPTION
Referring to FIG. 1, a hydrocarbonaceous containing rubblized ore is treated successively in three cycles, a non-oxidative pyrolysis (NOP) cycle, an oxidative combustion (OC) cycle, and an environmental sequestration (ES) cycle.
Reference is now made to FIG. 2, which is a mass balance chart exemplifying a process. In a reactor space an NOP cycle is conducted with a fixed or moving bed of oil shale. The bed is heated by direct contact with steam, introduced through suitable injectors, such as for example, slotted pipes, nozzles, grates or other convenient means. Steam is introduced until the bed is heated to temperatures high enough to achieve substantial conversion of kerogen to oil and gas with minimal decomposition of carbonate minerals found in the oil shale, e.g. at a maximum temperature greater than about 700 degrees F., for example, between about 700 and 1000 degrees F. The bed is so configured as to allow produced liquids to drain to the bottom of the bed by gravity, where they are withdrawn through a suitable outlet. Gases are withdrawn from the upper portion of the bed by gas lines, or any convenient means.
The reactor space conditions are then changed for an OC cycle. In the OC cycle an oxidizing gas, such as air, oxygen-enriched air, or oxygen, is introduced to the bed through the same or different injectors used for the introduction of steam. Residual hydrocarbonaceous material left on the mineral surface from the kerogen conversion is combusted to generate heat and which during the process of combustion forms CO2, H2O, oxides of sulfur and nitrogen, as well as small amounts of other constituents. During the OC cycle high temperatures are desired in order to accelerate the oxidation reaction rate and provide for efficient heat utilization. In the high temperature combustion zone, metal carbonates, principally alkali metal carbonates, are allowed to decompose to CO2 and their corresponding metal oxides. The hot gas so produced during combustion, consisting predominantly of CO2 and H2O, if oxygen is used and N2, CO2 and H2O if air is used, as well as lesser amounts of oxides of nitrogen and sulfur, is withdrawn from the reactor through gas withdrawal lines. Heat is recovered from the hot OC combustion gas to produce steam using steam generators of any suitable construction. The steam can then be cycled for use in the NOP cycle. Excess steam may be used to produce power, by, for example, steam turbines, or can be used directly where shaft power is required to power the process, such as compression of air in the air separation process, blowing of the oxidizing gas, or flue gas to the ES cycle or for driving electrical generators. The electricity is also used on-site to power the process; and excess electricity is sold to the electric grid.
During the OC cycle CO2 is produced both from the combustion of the residual organic matter and the decomposition of carbonates. After recovery of heat from the OC gas a portion of the cool CO2-laden gas is recirculated along with the air or oxygen to the bottom of the OC bed, where it cools the lower bed and restores the alkali metal oxides to their carbonate form. Oxides of nitrogen and sulfur contained in the stream are deposited on the combusted shale where they react to form alkali metal salts. Oxides of N and S, being more acidic than oxides of C or H, will preferentially displace carbonates or hydrates on the combusted shale. Excess CO2 not required for conversion of alkali metal oxides to carbonates absorbs heat from the upper bed and along with newly formed combustion gases and is directed to the steam generators as the combustion gas stream. The flow rate of the CO2-laden gas recycled into the OC cycle can be selected to adjust the temperature of the exit gases to a desired temperature or to adjust the rate of heat generation to coincide with the desired rate of steam production for the retorting in the NOP cycle and electric power generation.
As the OC cycle progresses, starting at the bottom of the bed a zone becomes cooled and metal oxides are there converted to carbonates from the cooled carbon dioxide in the gas recycle. As this cooled recarbonation zone progresses up through the bed, the hot combustion zone where residues are oxidized and metal oxides formed travels up and above the cooler zone. When the combustion zone reaches the top, or when the OC cycle has consumed essentially all of the available fuel (residue material) in the bed the reactor zone is switched to an ES cycle. At the same time, a reactor bed operating under a NOP cycle is switched to OC cycle, and a freshly prepared bed is started on the NOP cycle, thus making a semi-continuous process from a series of batch processes.
Accumulations of CO2-laden gas (that also contains oxides of nitrogen and sulfur) greater than that necessary for the OC and NOP cycle are sent to a third, ES cycle, which follows the OC cycle. In the ES cycle, the CO2-laden gas is injected into the bed through the piping or inlet system previously installed. Additional cleaning of the CO2 occurs and essentially all of the remaining oxides of nitrogen and sulfur are sequestered. The cleaned CO2 gas is withdrawn by suitable means as product. If oxygen is utilized as the oxidizing gas in the OC cycle, relatively pure CO2 is produced for sale or use. If air is used, a clean, enriched stream of CO2 in N2 is produced which is suitable for recovery of CO2 by conventional gas separation technologies. Whether to separate the N2 from CO2 at the tail end of the process or to separate the N2 from O2 at the beginning of the process is a matter of economic optimization. In either case highly concentrated CO2 can be produced for industrial use.
Reference is now again made to FIG. 2, which is a mass-balance diagram. This diagram is based upon preliminary modeling and can be understood with reference to the above discussion. In Table I is a listing describing the stream names. The NOP cycle is shown by the box on the right, with heated steam stream S2, which has been heated by combustion vapors S29 from the OC cycle (shown as the middle box). Some of the exhaust vapors S28 are used to generate steam for plant power requirements. Cooled exhaust vapors S19 from the OC cycle are dewatered to S31 and split into two streams, one a recycle to the OC reactor S32, and the other, the excess CO2 stream S14 is directed to the ES cycle (box on the left). Obviously, control of heat duties is conducted to make operational use of heat available.







TABLE I





Stream Names
















S1
Oil shale feed, or initial charge


S2
Hot steam or other inert gas


S3
liquid products and water


S4
vapor products and steam


S4a
condensed vapor products and water


S5
primary oil products


S6
retort water for recycle


S7
non-condensable hydrocarbon gases


S8
condensed light overhead product and water


S9
condensed light hydrocarbon product


S10
condensed water for recycle


S11
makeup water (could derive from S27a)


S12
condensed water from combustion gas


S13
secondary oil products


S14
excess combustion gas for ES cycle


S15
oxidizing gas for OC cycle


S16
vapors from OC cycle


S17
oxidizing gas for afterburner on OC cycle


S18
hot combustion gas


S19
combined cooled and condensed combustion gas


S20
combined water to steam generator


S21
pure CO2 or pure CO2 + N2 (may contain filterable particulates)


S22
intermittent recycle for process control purposes


S23
CO2 product


S24
combined oil products (optional)


S25
solids at completion of NOP cycle


S26
solids at completion of OC cycle


S27
cooling water


S27a
warm cooling water


S28
hot combustion gas split for steam turbine exchanger


S28a
cool combustion gas from turbine steam exchanger


S29
hot combustion gas split for retort steam exchanger


S29a
cool combustion gas from retort steam exchanger


S30
solids at completion of ES cycle


S31
dewatered combustion gasses


S32
combustion gas recycled to OC cycle









In another example based upon preliminary modeling, a 50,000 bbl/day plant charging 25 gpt oil shale results in the following overall mass balance (assume 85% efficiency on Fischer assay, but recover the remaining 15% as combustion heat, before losses). This balance assumes all CO2 produced from carbonate decomposition is sequestered on the spent shale. This is a model of a modified in-situ process where there is lower energy lost to the environment. While it is not possible to run any system with absolutely no energy loss due to edge effects, (e.g., piping, loses to surrounding), an in-situ process would be expected to show lower energy loss than a surface process, which may show slightly greater energy loss. The mass and energy balances are shown in TABLE II







TABLE II







Mass balance









In




Organic matter in =
14,979


Oxygen consumed =
12,100



27,079
ton/day


Out


Noncondensible gases =
1,486


Naphtha =
3,775


Mid distillate shale oil =
4,134


Heavy shale oil =
1,396


CO2 (98% indust. grd) =
13,064


Water (to tailings) =
2,854


NO2 (sequestered) =
291


SO3 (sequestered) =
79



27,079
ton/day







Energy balance (no energy imported)









In




Energy available in oil shale =
5.61 × 1011
Btu/day


Out


Energy in oil and gas products =
4.04 × 1011
Btu/day


Electric energy produced =
11,000
MW-hr/day (537 MW




plant)


Heat lost to surroundings =
4.7 × 1010
Btu/day








Estimated First Law efficiency =
(56.1-4.7)/56.1 = 92%









In the practice of the process in which fixed beds are utilized, it can be operated with three reactors that will operate simultaneously. In the figure, a first, second and third reactors are provided. In the first reactor at this point in operation, an NOP cycle is in progress, which receives steam produced from the heat, energy generated for the second OC reactor. In the third reactor an ES cycle is in progress and finishes the cleanup of the produced CO2 gases. The cycles continue until all of combustible, residual material in the OC cycle in the second reactor has been combusted, at which time the second reactor changes from an OC cycle to an ES cycle. The NOP cycle in the first reactor is changed to an OC cycle. A new NOP cycle is brought on-line. In practice of a fixed bed configuration, four units can make a convenient full cycle, with one unit being discharged and recharged, and, freshly prepared in anticipation of its next use, during the time the other three are on their respective cycles.
In an optional operation of multiple reactors, the temperature and heat flows are controlled in such a fashion as to facilitate steady-state operation and to complete NOP cycles simultaneously with the completion of OC cycles. Upon completion of the NOP and OC cycles, the cycle in the respective reactors is switched and NOP and OC cycles initiated in different reactors. For example, previous NOP reactor becomes the next OC reactor. The previous OC reactor becomes the next ES reactor. The previous ES reactor may be taken off-line or used as an additional ES reactor for further sequestration of NOx and SOx produced in miscellaneous flue-gases throughout the process.
The fixed bed may be configured in surface vessels situated side by side and operated in a swing configuration, or three modified in-situ cells. The modified in-situ cells may be constructed by the staged blasting technique of Geokinetics, the partial mining and rubblization concept forwarded by Occidental oil shale, or an engineered cell, for example, engineered cells similar to Red Leaf capsule technology.
In principle, the process could be applied to reactor units engineered for true in-situ, especially if some form of gaseous or liquid communications is provided. Such communications could be provided through vertical or horizontal drill- or boreholes, conduits, hydraulic fracturing, or other convenient means. Variations may include an initial short-term combustion cycle to open up the fractures that would facilitate larger, successive steam flows. Upon completion of the NOP cycle the permeability of the bed is greatly enhanced, allowing for an efficient combustion cycle and efficient sequestration in the ES cycle.
In a modified in-situ system an inclined, engineered, permeable bed of oil-bearing ore is constructed and the permeable bed may be encapsulated between impervious layers. The engineered impervious layers may be omitted if geophysical and hydrological conditions allow. A bed under NOP cycle conditions is heated by introducing steam through a first porous pipe, situated in the lower portion of the bed. A second porous pipe, situated in the upper portion of the bed accepts vapors produced in the process. As many porous pipes as are needed for effective recovery may be laid in the bed. Heating of the bed continues until a desired temperature is reached and a desired reaction is complete.
Vapors, which may consist of condensable hydrocarbons, non-condensable gases, and water vapor, are cooled; non-condensable gases are collected for sale, further processing, or used on-site. Condensed liquids are sent to a separator where light hydrocarbons are decanted in an overflow, and water is withdrawn from the underflow for recycle to the steam generator. Liquids, consisting of both an oil and aqueous phase, produced within the bed drain to a sump at the lower end of the bed where they are pumped to the surface for separation into their respective phases. The oil phase is sold or further processed.
When the bed is switch to OC cycle conditions, the oxidation (combustion) reaction is initiated in the vicinity of the first porous pipe and air or oxygen is injected at a controlled rate. The air or oxygen is diluted with an amount of CO2 for purposes of (a) controlling combustion temperature, (b) converting alkali metal oxides to their respective carbonates, and (c) controlling heat recovery from the hot, combusted shale. The oxygen inflow rate is controlled to be sufficient to support combustion, but insufficient to cause premature breakthrough of the oxygen in the exit gas. Hot gases from the combustion flow by pressure differential toward a second porous pipe where they are withdrawn and used to generate steam, preheat water, or other beneficial use of heat. The OC cycle is allowed to continue until all, or a practical amount, of the combustible fuel left from the NOP cycle is consumed. The now relatively cool cell resulting from the now complete OC cycle is switched to serve as the ES cell. Additional liquids that may be produced during the OC cycle are sold, processed separately from liquids produced in the NOP cycle, or combined with liquids produced in the NOP cycle for sale or further processing.
When the bed is operated under ES cycle conditions, cool flue gas (vapor products from the OC cycle or other surface combustion process) is introduced to the first porous pipe. The vapors are allowed to contact the partially cooled bed where the CO2, NOx, SOx, and H2O substantially react with the activated ore where they are sequestered respectively as carbonates, nitrates, sulfates, hydrates, and related compounds.
In ordinary practice it is contemplated that there be at least three modified in-situ beds, and the cycles are performed in semicontinuous, sequential fashion. That is, a first bed having advanced to the ES stage would receive cooled flue gas whose heat has been recovered for beneficial use that was, produced in a second OC bed, which in turn, had previously completed the NOP cycle in a third bed. While the process is operating a new NOP cycle is being prepared in anticipation of a changeover of cycles. Thus, the process achieves a near steady state by marching the sequence of cycles through beds constructed in the resource zone. If the resource geometry allows, multiple simultaneous sequences are operated, staged in such a fashion as to produce steady product flow and make efficient use of labor and equipment.
In another aspect, a moving bed system is provided where the three cycles may be performed in three surface vessels. One vessel serves as a continuous NOP reactor, the second as a continuous OC reactor and the third as a continuous ES reactor. Prepared ore is charged to the top of the NOP vessel. Steamed or heated ore is removed from the bottom of the NOP vessel and charged to the top of the OC vessel. Hydrocarbon-free, reduced-temperature solids are removed from the bottom of the OC vessel and charged to the top of the ES vessel. Finishing of CO2 purification and cooling occurs in the ES vessel. Cool, environmentally benign solids are discharged from the bottom of the ES vessel and sent back to the mine area for storage and land reclamation.
In an aspect of the semicontinuous, sequential operation of several beds of ore, once an operation with three cycles (NOP, OC, and ES) is in operation a new bed is prepared for a new NOP-cycle. The new NOP cycle bed can be initially preheated to make use of low grade heat as available. This new bed is brought into the operation once the initial NOP bed is completely reacted, at which time the initial NOP bed is switched to an OC cycle and the previous OC cycle is switched to an ES cycle. In instances where the optional ES cycle is not used, the sequence is similar, but without the ES cycle. If surface-engineered reactors are used, the prior ES zone is then converted to the next NOP zone and thus, the process cycles more or less continuously. If the zones are subsurface (in-situ or modified in-situ) there is no need to complete the initial ES cycle before a new NOP cycle is initiated. In principle there could be at any given time several NOP cycles in various stages of heatup, several OC cycles in various stages of oxidation and several stages of ES cycles in various stages of cooldown and sequestration.
Reference is now made to FIGS. 3A, 3B, and 3C, which are schematics that illustrate an exemplary bed of ore as it is treated by an exemplary process. In FIG. 3A is a rubblized bed of ore 101 containing hydrocarbonaceous materials. In the NOP cycle, a heated gas is introduced through line 103, which heats the ore producing a fluid product, the liquid portion being withdrawn through line 105 and the vapor portion being withdrawn through line 107.
Referring now to FIG. 3B, in the OC cycle, heated oxygen containing gas is introduced through line 203, to create a combustion zone 221 in the bed 201. The heating and the combustion/oxidation of remaining hydrocarbons in the bed creates temperatures in the combustion zone where a portion of carbonates in the ore decompose to oxides, forming carbon dioxide gas. The gaseous combustion products and carbon dioxide are withdrawn as an effluent gas stream through line 207. After heat is recovered from stream 207 through suitable means 213, the effluent gas stream is split to form an ES steam 209, and recycle stream 211. The cooled recycle stream is introduced into the bed below the combustion zone and creates a recarbonation zone 223 in the bed. The carbonation zone occurs where the combustion zone has already depleted the ore of hydrocarbons and formed metal oxides, and is at temperature conditions lower than in the combustion zone due to introduction of the cooled recycle stream. Under these conditions carbon dioxide in the recycle stream combines with metal oxides that were formed when the combustion zone passed up through the same region ore. The combustion zone with the recarbonation zone behind it passes up through the reactor until the combustion zone reaches to the top and the combustion and decomposition reactions cease. Whatever the kinetics or equilibrium thermodynamics of the recarbonation of various alkali oxides, there is a temperature zone in the cooler recarbonation process which is favorable to the recarbonation reaction, which is also enhanced by an excess of CO2 in the recycle gas.
Referring to FIG. 3C, an ES stream, which may originate from another bed of ore being treated, such as 209 in FIG. 3B, is introduced into the recarbonated ore bed 301 through line 303 and as gas from the ES stream passes up through the bed metal oxides in the bed sequester nitrogen and sulfur oxides in the gas. A cleaned gas stream is withdrawn through line 315. Piping and conduits can optionally be used for dual purposes. For example, lines 107 and 207 may be the same or different conduits, and likewise for lines 103, 203, and 303.
While this invention has been described with reference to certain specific embodiments and examples, it will be recognized by those skilled in the art that many variations are possible without departing from the scope and spirit of this invention, and that the invention, as described by the claims, is intended to cover all changes and modifications of the invention which do not depart from the spirit of the invention.

## Claims

1. A process for recovery of energy values and liquid and gaseous products from ore comprising solid or semi-solid hydrocarbonaceous materials where the energy values of residues are recovered from a mineral portion, and process emissions of carbon dioxide are minimized, said process comprising: providing multiple reaction spaces containing a bed of rubblized ore and treating the ore bed in each reaction space by the following steps:
(a) operating a non-oxidative pyrolysis (NOP) cycle by heating the bed of rubblized ore using heated vapor introduced near the bottom of the reaction space to produce fluid products from the hydrocarbonaceous materials and a bed depleted of hydrocarbonaceous material, withdrawing a vapor portion of the fluid products near the top of the reaction space and withdrawing a liquid portion of the fluid products near the bottom of the reaction space; the heating to obtain temperature conditions sufficient to convert a major portion the hydrocarbonaceous materials to the fluid products for recovery in the liquid portion and the vapor portion, and insufficient for substantial conversion of metal carbonates to metal oxides in the bed;
(b) operating an oxidative combustion (OC) cycle by forming a combustion zone by heating the bed of ore depleted of hydrocarbonaceous-material from (a) and by introducing an oxidizing gas into the bed to provide the combustion zone,

with temperature conditions in the combustion zone sufficient to oxidize residual hydrocarbonaceous material in the bed to form combustion products and at conditions that can decompose at least a portion of metal carbonates in the bed to form carbon dioxide gas and metal oxides, such that the combustion zone travels up through the bed as the oxidizing and decomposition proceeds,
withdrawing the combustion products and carbon dioxide gas from decomposition in an effluent gas stream and recovering at least a portion of the heat from the effluent stream to heat the heated vapor used to heat a bed of rubblized ore in another reaction space operating in a NOP cycle,
forming a recarbonation zone by recycling a recycle portion of the effluent stream from which heat has been recovered as a recycle stream into the bed to form the recarbonation zone such that the bed is cooled to temperature conditions where carbon dioxide in the recycle stream reacts with metal oxides in the bed to form metal carbonates,

the recarbonation zone travelling up through the bed below the combustion zone as the combustion travels up through the bed producing a recarbonated bed of ore.

2. The process of claim 1 wherein at least a portion of the heat recovered from the recycle stream is used to preheat the ore bed in the reaction space before initiation of NOP cycle in (a) directed to provide heating in (a) for a next NOP cycle in another reactor space.

3. The process of claim 1 wherein a portion of the recovered heat in the effluent stream of the OC cycle is used to produce electricity or provide power requirements for the process.

4. The process of claim 1 wherein the rubblized bed in the reaction space is created in-situ by hydraulic fracturing.

5. The process of claim 1 wherein the rubblized bed in the reaction space is created in-situ by explosive fracturing.

6. The process of claim 1 wherein the rubblized bed in the reaction space is created by mining a portion of the bed, introducing porous or slotted pipes in the mined zone, and explosively rubblizing the remaining bed into the mined voids.

7. The process of claim 1 wherein the rubbilized bed in the reaction space is created by mining, ore sizing, and introducing porous or slotted pipes into the reaction space.

8. The process of claim 1 wherein communication between the multiple reaction spaces is provided by horizontal bore holes between the reaction spaces.

9. The process of claim 1 wherein the heated vapor introduced near the bottom of the reaction space comprises substantially any one of or a mixture of steam, carbon dioxide, nitrogen, or light hydrocarbons of about 5 carbons or less.

10. The process of claim 1 wherein the oxidizing gas comprises substantially oxygen and any one of or a mixture of carbon dioxide and nitrogen.

11. The process of claim 10 wherein the oxidizing gas also contains amounts of oxides of nitrogen and sulfur that are less than combined amounts of oxygen, carbon dioxide, and nitrogen contained in the oxidizing gas.

12. The process of claim 1 where simultaneously an NOP cycle is operating in a first reactor space, an OC cycle is operating in a second reactor space, and an untreated ore bed is being prepared in a third reactor space, with at least a portion of the energy from the OC cycle in the second reactors space being used for heating the vapor in the NOP cycle in the first reactor space.

13. The process of claim 12 wherein the NOP cycle in the first reaction space is initiated when the OC in the second reaction space is initiated after termination of a NOP cycle in the second reaction space.

14. A process for recovery of energy values from ore comprising solid or semi-solid hydrocarbonaceous materials, said process comprising:
(a) operating a non-oxidative pyrolysis (NOP) cycle by heating a bed of rubbilized ore in a first reaction space under non-oxidizing conditions, the heating to a temperature sufficient to convert a major portion of the hydrocarbonaceous materials to recoverable fluid products that are removed from the bed;
(b) operating an oxidative combustion (OC) cycle by heating the bed from (a) while introducing an oxidizing gas into the bed to provide a combustion zone with conditions to oxidize residual unconverted hydrocarbonaceous material in the bed and produce heat and an effluent gas that contains combustion gas from oxidation of the hydrocarbonaceous material, where the conditions may produce carbon dioxide produced from decomposition of metal oxides,
(c) recovering thermal energy from at least a portion of the effluent gas from the OC cycle in the first reaction space and using at least a portion of the recovered thermal energy to heat a rubbilized bed in an NOP cycle in a second reaction space.

15. The process of claim 14 wherein the rubblized bed in the second reaction space is heated by passing a non-oxidizing gas through the bed, and the non-oxidizing gas is heated by heat recovered in (c) from the OC cycle in the first reaction space.

16. The process of claim 14 additionally comprising;
(d) operating an environmental sequestration (ES) cycle by directing a portion of the effluent gas from which energy has been recovered to near the bottom of a recarbonated bed of ore from a completed OC cycle in a third reaction space at conditions that allow for sequestering of carbon dioxide, sulfur oxides and nitrogen oxides and promote the conversion of metal oxides in the bed to metal carbonates, sulfates and nitrates.

17. A process for recovery of energy values and liquid and gaseous products from ore comprising solid or semi-solid hydrocarbonaceous materials where the energy values of residues are recovered from a mineral portion, and process emissions of carbon dioxide are minimized, said process comprising:
providing multiple reaction spaces containing a bed of rubblized ore and treating the ore bed in each reaction space by the following steps;
(a) operating a non-oxidative pyrolysis (NOP) cycle by heating bed of rubblized ore using heated vapor introduced near the bottom of the reaction space to produce fluid products from the hydrocarbonaceous materials and a bed depleted of hydrocarbonaceous material,

withdrawing a vapor portion of the fluid products near the top of the reaction space and
withdrawing a liquid portion of the fluid products near the bottom of the reaction space;
the heating to obtain temperature conditions sufficient to convert a major portion the hydrocarbonaceous materials to the fluid products for recovery in the liquid portion and the vapor portion, and insufficient for substantial conversion of metal carbonates to metal oxides in the bed;
(b) operating an oxidative combustion (OC) cycle by

forming a combustion zone by heating the bed of ore depleted of hydrocarbonaceous-material from (a) and by introducing an oxidizing gas into the bed to provide the combustion zone,
with temperature conditions in the combustion zone sufficient to oxidize residual unrecovered hydrocarbonaceous material in the bed to form combustion products and at conditions that can decompose at least a portion of metal carbonates in the bed to form carbon dioxide gas and metal oxides, such that the combustion zone travels up through the bed as the oxidizing and decomposition proceeds,
withdrawing the combustion products and carbon dioxide gas from decomposition in an effluent gas stream and recovering at least a portion of the heat from the effluent stream to heat the heated vapor used to heat a bed of rubblized ore in another reaction space operating in a NOP cycle, that is divided into a recycle stream and an exit stream,
forming a recarbonation zone by recycling a recycle portion of the effluent stream from which heat has been recovered as a recycle stream recovering heat from the recycle stream and recycling the recycle stream into the bed to form the recarbonation zone such that the bed is cooled to temperature conditions where carbon dioxide in the recycle stream reacts with metal oxides in the bed to form metal carbonates,

the recarbonation zone travelling up through the bed below the combustion zone as the combustion zone travels up through the bed until the combustion zone passes up through the bed producing a recarbonated portion in the bed of ore,
(c) operating an environmental sequestration (ES) by introducing an exit portion of the effluent stream from which heat has been recovered in (b), which is an ES cycle stream, near the bottom of the recarbonated bed of ore from a completed OC cycle in another reaction space at conditions that allow for sequestering of carbon dioxide, sulfur oxides and nitrogen oxides and promote the conversion of metal oxides in the bed to metal carbonates, sulfates and nitrates.

18. The process of claim 17 where simultaneously an NOP cycle is operating in a first reactor space, an OC cycle is operating in a second reactor space, an ES cycle in a third reactor space, and an untreated ore bed is being prepared in a fourth reactor space, with at least a portion of the energy from the OC cycle being used for heating the vapor in the NOP a portion of the effluent gas in the OC cycle is used as the ES exit stream in the ES cycle.

19. The process of claim 18 wherein the NOP cycle in the first reaction space is initiated when the OC in the second reaction space is initiated after termination of a NOP cycle in the second reaction space and the ES cycle is initiated in the third reactor upon termination of an OC cycle in the third reaction space.