US20140346030A1

US20140346030A1 - Methods and apparatus for liquefaction of organic solids

Info

Publication number: US20140346030A1
Application number: US14/119,384
Authority: US
Inventors: Ben Zion Livneh
Original assignee: ECOKAP TECHNOLOGIES LLC
Current assignee: ECOKAP TECHNOLOGIES LLC
Priority date: 2011-05-23
Filing date: 2012-05-22
Publication date: 2014-11-27
Also published as: WO2012162302A1

Abstract

Methods of liquefying solid organic materials, such as coal, biomass and shale are described. Also described are apparatus useful to effect such changes.

Description

This application is a continuation of and claims priority to U.S. Provisional Patent Application No. 61/488,975, filed May 23, 2011, the entire contents of which are incorporated herein by reference.

FIELD OF THE INVENTION

This disclosure relates generally to methods of liquefying organic minerals, such as coal, biomass and shale. This disclosure also relates to apparatus useful to effect such changes.

BACKGROUND OF THE INVENTION

Increasing oil prices and the drive to reduce the U.S.'s energy dependence has led to renewed interest in coal-to-liquid (CTL) technology, for economic, strategic, political and environmental reasons. However, CTL technology has not been well received due to inefficiencies in the process.
This application uses the term “coal” in a conventional sense to mean a combustible black or brownish black sedimentary rock comprising carbon. The term “peat” is used to denote partially carbonized vegetation with high water content. The term “shale” is used to denote a sedimentary rock with a large organic concentration. The term “biomass” is used to denote materials of biological origin. The term “solid organic material” is used to denote carbonaceous materials which are in a solid physical state at ambient temperature and pressure, such as, without limitation, any one or more of the group comprising coal, peat, shale or biomass.
There is a continuing need to develop effective methods for converting coal, and other solid organic materials, into useful liquid or gas products.

BRIEF SUMMARY OF THE INVENTION

Embodiments of the present invention feature methods and apparatus for forming liquid or gas hydrocarbons from solid organic materials such as coal, peat, shale, and biomass. As used herein, the term “non-solid” refers to the physical state of being a liquid or gas at or about standard ambient temperatures and pressures. The term “hydrocarbon” is used in the normal chemical sense of a composition having at least one carbon atom and one hydrogen atom. In one embodiment, the present invention relates to a process for making non-solid hydrocarbons comprising the steps of subjecting a solid organic material and a magnetite-type composition to electromagnetic radiation or similar radiation to form one or more reaction products which include at least one non-solid hydrocarbon composition. In one embodiment, the electromagnetic radiation is microwave radiation typically at frequencies starting at less than 0.9 GHz (L Band) up to 40 GHz (Ka Band). In another embodiment the electromagnetic frequency may be as high as 100 GHz (W Band). In another embodiment, the electromagnetic radiation is radio frequency radiation. The non-solid hydrocarbon compositions formed are suitable for use as a fuel, or a starting material for further reactions and processes typically used by oil refineries producing material for other purposes for which non-solid hydrocarbons are used.
One embodiment of the present invention features a process for making one or more non-solid hydrocarbons. The process comprises the steps of forming a reaction mixture comprising a solid organic material and, in the presence of magnetite-type compositions and electromagnetic radiation, forming reaction and catalysis conditions that cause the reaction mixture to form reaction products comprising one or more non-solid hydrocarbons.
The reaction conditions are selected from one or more of the group consisting of liquefaction conditions and gasification conditions. The reaction mixture further comprises one or more further reactants selected from the group consisting of water and oxygen.
Embodiments of the present process feature reaction conditions comprising gasification conditions and liquefaction conditions. One embodiment features liquefaction conditions comprising Fischer-Tropsch synthetic conditions.
One embodiment features a reaction mixture in the presence of magnetite-type composition subjected to electromagnetic radiation prior to the liquefaction stage. That is, the reaction mixture undergoes a gasification process and enters a liquefaction stage with the presence of the appropriate catalysis agent. Although embodiments of the present invention feature reactants of solid organic matter selected from the group consisting of coal, shale, peat, biomass, and combinations thereof; the reactants can possess non-solid hydrocarbons such as oils, tar, waxes and paraffins in free form or embedded in solids such as clay.
The magnetite-type composition comprises magnetite, that is iron oxide in any variation (such as, without limitation, Fe₃O₄, or FeO.Fe₂O₃) and may further comprise one or more metals such as nickel, cobalt, copper, silver, gallium, indium, manganese, zinc, platinum, palladium, gold, ruthenium, rhodium, iridium, and combinations thereof. The magnetite-type composition is held in an immobilized matrix or can be dispersed in the reaction mixture. Preferably, the magnetite-type composition is recovered and recycled.
Embodiments of the present processes require no solvent to be added as a reactant or to facilitate the reactions.
The electromagnetic radiation may take several forms. One embodiment features microwave radiation. Another embodiment features radio frequency radiation.
A further embodiment of the present invention features an apparatus for making one or more non-solid hydrocarbons. The apparatus has at least one vessel and electromagnetic radiation means. The at least one vessel has at least one opening for receiving reactants and discharging a non-solid hydrocarbon. The reactants comprise solid organic material, water and oxygen. The at least one vessel contains a magnetite-type composition as a mixture with said reactants or as an immobilized matrix. The electromagnetic radiation means is in communication with the at least one vessel for placing electromagnetic radiation into the vessel to create reaction conditions. The reaction conditions cause the reaction mixture to form one or more non-solid hydrocarbons.
The reaction conditions are selected from the group consisting of gasification and liquefaction; for example, without limitation, Fischer-Tropsch (F-T) synthetic conditions.
Embodiment of the present apparatus features a vessel suited for batch or continuous processing. For continuous processes, one embodiment features the at least one vessel having at least one input opening for receiving the solid organic material, water and oxygen and at least one output opening for discharging the at least one non-solid hydrocarbon.
The electromagnetic radiation means may take several forms such as a microwave radiation emitter and/or a radio frequency radiation emitter. The emitter may be inside the vessel or emit through one or more windows into the vessel.
One embodiment of the present apparatus comprises an electromagnetic zone vessel and a reaction vessel. The electromagnetic radiation vessel has at least one opening for receiving reactants comprising solid organic material, water and oxygen, and is further in fluid communication with the reaction vessel. The electromagnetic zone vessel is in communication with said electromagnetic radiation means to receive electromagnetic radiation. The reaction vessel receives the reactants from the electromagnetic zone vessel and completes the reactions to form one or more non-solid hydrocarbons.
In one embodiment, the present invention relates to a process for converting organic matter into liquid or gas synfuels that involves (a) subjecting an organic material and magnetite to electromagnetic radiation; and (b) subjecting the organic material from step (a) to liquefaction conditions.
In one embodiment, the organic matter is coal. In one embodiment, the process involves the addition of oxygen and water. In one embodiment, the process involves a gasification and a liquefaction (e.g., an F-T) step.
In another aspect, the present invention relates to an apparatus useful for the conversion of organic matter to liquid or gas synfuels.
These and other features and advantages will be apparent to those skilled in the art upon viewing the drawings, summarized in the section below, and upon reading the detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an exemplary process flow diagram and apparatus for coal liquefaction wherein the F-T gasifier chamber and electromagnetic radiation cavity are combined.

FIG. 2 shows an exemplary process flow diagram and apparatus for coal liquefaction wherein the feed mixture is preheated in an electromagnetic radiation cavity prior to entering the F-T gasifier chamber.

DETAILED DESCRIPTION

The present inventor has discovered an efficient single step process which incorporates electromagnetic radiation (EMR) energy for converting solid organic minerals, such as coal and biomass, into liquid or gas products. The single step EMR process offers a cleaner, more attractive and cost effective approach to producing synthetic fuels. The processes described herein are also referred to as “F-T Gasification Processes.”
Thus, in one aspect, the present invention relates to an improved process for the conversion of organic matter, such as coal, biomass, or other organic solids to liquid or gas products. Coal liquefaction has its roots in Germany in the early 1900s. U.S. Pat. No. 1,746,464, issued to Franz Fischer and Hans Tropsch in 1930, describes a process for converting carbon monoxide and hydrogen to hydrocarbons in the presence of a catalyst. This process subsequently became known as the F-T Process. According to the '464 patent, temperature plays a decisive role in the reaction products. For example, at high temperatures (such as 430° C.) only methane is produced, while at lower temperatures (such as 300° C.) the reaction products include methane (˜10%), but are predominantly paraffin hydrocarbons (˜90%) with more than one carbon atom.
An alternative route for converting syngas to liquid fuels via the synthesis of methanol was developed in the 1970s by Mobil Oil. See, e.g., U.S. Pat. No. 4,035,281. However, the F-T Process remains the preferred route for converting coal to liquid, producing more suitable products for automotive and avionic fuels.
Generally, solid fossil fuel such as coal can be oxidized (burnt) in two main methods: combustion and gasification. The products of these processes are very different. For example, the complete combustion of coal produces carbon dioxide, water, nitrogen dioxide and sulfur dioxide. Gasification of coal produces carbon monoxide, hydrogen, nitrogen and hydrogen sulfide. The products obtained from combustion of coal have little or no commercial value, and in recent years have attracted a negative value: the production of green-house gas (GHG) carbon dioxide became a liability in terms of environmental considerations and public image. By contrast, the products obtained from gasification of coal have significant commercial value as a substitute to natural gas for heat or to generate electricity by driving gas turbines (such as in the integrated gasification combined cycle process [IGCC] where the coal is gasified to drive a gas turbine, and the heat produced is used to generate steam to drive a steam turbine). Through other processes, gasified coal can be converted to liquid fuels, which substantially increase the economic value of the coal.
Traditionally, synthetic fuels (synfuel) production incorporates two separate steps: (1) gasification and (2) liquefaction through either the F-T Process or the Mobil methanol synthesis.

Coal Gasification

Coal gasification involves the breakdown of the coal structure in an oxygen deficient environment in the presence of water (steam). The chemical reactions that occur in coal gasification are summarized in the table below.


No.	Reaction	Description	ΔH (kJ/mol)

1	C + O₂→ CO₂	Oxidation	−394.5
2	C + ½ O₂→ CO	Oxidation	−111.0
3	C + CO₂→ 2 CO	Reduction	+172.5
4	C + H₂O → CO + H₂	Reduction	+135.6
5	CO + ½ O₂→ CO₂	Oxidation	−280.0

The desired chemical products of gasification, which can be further converted to liquid fuels by the F-T Process, are carbon monoxide, which is produced in reactions 2, 3 and 4, and hydrogen, which is produced in reaction 4. The sum of these reactions is endothermic, thus, heat is required in order to maintain the process. The necessary heat is typically produced by the full combustion of coal reaction 1 and the partial combustion of coal reaction 2, which are exothermic. However, the production of carbon dioxide is not desirable, as it reduces the carbon efficiency of the process, and reduces the heat value of the synthetic gas product. Coal will spontaneously convert to the desired products only under conditions of high temperature and pressure, which must be maintained inside the gasification reactor.
Syngas has a very different composition to natural gas, and has a significantly lower heat value. For example, according to Babcock and Wilcox, syngas contains 14.0% hydrogen, 27.0% carbon monoxide, 4.5% carbon dioxide, 0.6% oxygen, 3.0% methane and 50.9% nitrogen and has a higher heating value (HHV) of 163 BTU/scf. Natural gas, on the other hand, contains 90.0% methane, 5.0% nitrogen and 5.0% ethane and has a HHV of 1,002 BTU/scf. Due to the lack of hydrogen and carbon monoxide, the gas-to-liquid (GTL) F-T synthesis for natural gas requires an initial gas reforming stage, where the methane gas is converted to carbon monoxide and hydrogen.
Typical coal gasifiers suffer from inherent physical problems. For example, the continuous feed of coal solids and continuous removal of ash solids in a system that produces gas are physically difficult to perform. The internal process conditions inside the gasifier are too complex to use in a batch type process, as the buildup of these conditions is energy intensive and requires long process time to achieve.
Two alternative solutions have been proposed to resolve the physical difficulties of gasifiers: (1) coal is fed into the gasifier in a dry form through a complex chambers configuration, and (2) coal is fed as coal-water slurry. However, each of the proposed solutions still suffers from disadvantages. For example, dry coal feed limits the particle size of the coal inlet to particles bigger than 0.5″-1.0″, which eliminates a large portion of the mined coal. Small particles must then go to waste or be used for other applications, such as power generation, if possible. On the other hand, the oxygen required by slurry-feed gasifiers is higher than that of dry-feed gasifiers. In any case, gasification is a complex unit operation, both dirty and difficult to operate.

Gas Liquefaction

The chemical reactions that occur in the syngas liquefaction process via the F-T synthesis are summarized in the table below.


No.	Reaction	Description	Δ H [kJ/mol]

1	CO + 2H₂→ —CH₂ + H₂O	Paraffin/olefin	−165.0
		formation
2	CO + H₂O → CO2 + H₂		−41.2
3	2 CO + H₂→ —CH₂— + CO₂		−206.0
4	CO + H₂O → CO₂+ H₂	Waster-gas	−36.9
		shift
5	CO2 + 3 H₂→ —CH₂— + 2 H₂O		−125.2
6	CO + 3 H₂→ CH₄+ H₂O	Methane	−206.0
		formation

There are three main issues involved with syngas liquefaction: (1) it is a highly exothermic set of reactions, (2) it consumes carbon monoxide and hydrogen, which constitute about 40% of the syngas to produce liquid fuels, and (3) it could serve as a carbon dioxide sink under the appropriate conditions. Coal liquefaction is a consumer of carbon dioxide, except for reaction 3 where it is produced. The formation of methane gas (reaction 6) is undesirable, and needs to be reformed back to free hydrogen and carbon monoxide through methane reforming reactions.
Control of the hydrogen to carbon ratio (H:C) of the feed gas for the F-T Process is important. This is typically achieved via methane gas reforming processes, which can occur in two different ways: (a) carbon monoxide methane reforming (2CH₄+O₂+CO₂→3H₂+3CO+H₂O) or (b) water methane reforming (4CH₄+O₂+2H₂O→10H₂+4CO).
The coal liquefaction process involves the shifting of the H:C ratio of the fuel from less than 1 to about 2. This is done by adding hydrogen to the hydrogen deficient organic structure of the coal. The process requires the breakdown of the coal matrix to shift the H:C ratio by adding hydrogen to the new coal structure, and the removal of non-organic material from the new product.
To achieve the necessary H:C shift, CTL fuel can be achieved in two different ways: (1) direct CTL and (2) indirect CTL. Historically, direct coal liquefaction was believed to be the most thermally efficient amongst other CTL processes. The prevailing direct CTL process is one in which coal is first dissolved in a solvent at a temperature of 750° F. and very high pressure of 275 bar, then the solution is hydrocracked with hydrogen and a catalyst. This process is said to have 60-70% thermal efficiency. The products of this approach to direct CTL are, however, of a poor quality and cannot be used for transportation of fuels without intensive upgrading processes.
In one embodiment, the present invention relates to a process for converting organic matter to liquid or gas synfuels that includes subjecting an organic material and magnetite to EMR.
In one embodiment, the present invention relates to a process for converting organic matter into liquid or gas synfuels that involves (a) subjecting an organic material and magnetite to EMR; and (b) subjecting the organic material from step (a) to liquefaction conditions.
In one embodiment, the process involves a combination of a gasification process and a liquefaction process (e.g., F-T Process).

The Organic Material

In certain embodiments, the organic material is any organic material that contains sufficient organic matter that can be liquefied. In one embodiment, the organic material is any organic material that contains sufficient organic matter that can be liquefied economically.
Suitable examples of organic material, include, but are not limited to, biomass, shale, natural and refined oil products, coal, and any combination thereof. In one embodiment, the organic material is coal. In one embodiment, the organic material is shale. In one embodiment, the organic material is oil. In one embodiment, the organic material is biomass.

The EMR Energy

In the processes described herein, energy is provided to initiate the gasification process by applying EMR to a mixture of materials including coal and magnetite. In addition, EMR energy facilitates and expedites the chemical reactions inside the reaction chamber.
The fundamentals of EMR heating are very different to those of thermal heating. The energy absorbed per unit time and per unit volume by the payload (e.g., the magnetite-coal mixture), which contributes to microwave heating, depends on the internal characteristics of the payload under given conditions.
If the power and frequency of the EMR energy is constant, the magnetite-coal heating rate depends on its internal properties (such as, without limitation, the amount of material, the coal to magnetite ratio, the particle size and shape, the internal voltage stress of the mixture in volts per meter, and the dielectric constant), all of which determine the ability of the material to absorb EMR energy and convert it to heat. Increasing the EMR power, for example, may not increase the heat rate of the magnetite-coal mixture payload beyond its capacity to absorb the energy based on the mentioned parameters. However, changing the EMR frequency may change the heat rate.
One important advantage that EMR energy has over thermal sources of energy is that the intensity of the radiation is easily controlled, with a very quick response time. This affords the processes described herein an operating dimension that is not currently available in standard CTL processes. For example, the energy input can be dynamically changed to meet with the chemistry needs of the process.
In one embodiment, the EMR energy may be varied by changing the intensity of the electrical and magnetic fields inside the F-T gasifier. In one embodiment, the EMR energy may be varied by changing the duration of the radiation, for example, by pulsating the EMR.
In one embodiment, the EMR energy is applied to the payload continuously. In another embodiment, the EMR energy is applied to the payload in pulses, in which, in additional embodiments, the on-period and the off-period can be independently varied.
In one embodiment, the source of EMR energy is electricity. In one embodiment, the electricity is generated from fossil fuels. In another embodiment, the electricity is generated from renewable sources, such as, for example, wind, solar and bio-fuels, thereby allowing further reductions in green-house gas emissions for the processes described herein.
The EMR energy can have any frequency in the range allocated for industrial applications by the Federal Communications Commission (FCC), or other process-relevant appropriate frequencies, in a closed and leak-free chamber. Suitable frequencies include, but are not limited to, the range of about 300 MHz to about 300 GHz. For example, suitable frequencies for use in the processes described herein, as authorized in various countries, are listed in the table below.


Frequency
(GHz)	Tolerance	Country

0.434	0.2%	Austria, Netherlands, Portugal, Germany,
		Switzerland

0.896	10	MHz	United Kingdom
0.915	13	MHz	North and South America
2.375	50	MHz	Albania, Bulgaria, CIS, Hungary, Romania,
			Czech/Slovak Republics,
2.450	50	MHz	World-wide, except where 2.375 MHz is used

3.390

0.6%

Netherlands

5.800

5

MHz

World-wide

6.780

0.6%

Netherlands

24.150	25	MHz	World-wide
40.680	25	MHz	United Kingdom

In further embodiments, the EMR frequency is any frequency that improves performance of the processes described herein.
In one embodiment, the EMR is microwave radiation. In another embodiment, the EMR is radio frequency radiation.

The Magnetite

In certain embodiments of the processes described herein, the magnetite-type composition, such as magnetite, acts in a dual role. In one embodiment, the magnetite acts as a promoter for the gasification process. In another embodiment, the magnetite acts as a catalyst for the F-T Process. In a further embodiment, the magnetite acts as both a promoter for the gasification process and as a catalyst for F-T synthesis.
Without wishing to be bound by theory, Applicant believes that, unlike other industrial microwave applications where microwave radiation is typically used for dewatering and drying, in the processes described herein, the EMR facilitates a rapid increase in temperature of the coal-magnetite mixture to a level were gasification processes can occur. Applicant also believes that the specific characteristics of magnetite, when subjected to EMR, allows for generation of the energy necessary to gasify the organic matter (e.g., coal).
In one embodiment, the temperature of the magnetite is raised at a rate of over 450° C. (750° F.) per minute under microwave energy. At this rate, a mixture of coal and magnetite can reach the temperature required for gasification in about 2 minutes.
In additional embodiments, the magnetite-type composition includes one or more additional chemical element(s). In further embodiments, the magnetite-type composition may include, for example, nickel, cobalt, copper, silver, gallium, indium, manganese, zinc, platinum, palladium, gold, ruthenium, rhodium, iridium, and combinations thereof. In certain embodiments, the properties of the magnetite-type composition can be tailored by inclusion of additional elements in order to produce the most appropriate catalysis environment for the process. In other embodiments, the properties of the magnetite-type composition can be tailored by inclusion of additional elements in order to improve the overall product blend.
In traditional F-T synthesis, different process temperatures typically yield different products. Since the heat dissipated by the F-T Gasification Processes described herein is a function of the material properties in the chamber, a tighter control over the products mix may be attainable for the processes described herein, which is not the case with traditional F-T synthesis.
In further embodiments, the magnetite is regenerated. In some embodiments, the magnetite is recycled back to the process.
In certain embodiments, the processes described herein do not require addition of a solvent, for example, an organic solvent. In other embodiments, the processes described herein are conducted in the absence of a solvent, such as an organic solvent.
In additional embodiments, the processes described herein do not require the addition of hydrogen. In one embodiment, hydrogen is not added to the reactor during the processes described herein. In another embodiment, hydrogen is added to the reactor during the processes described herein.
Applicant has also developed new apparatus for the direct conversion of organic matter, such as CTL or gas products. The apparatus are compact and efficient chambers.
Therefore, in another aspect, the present invention relates to an apparatus for the direct liquefaction of organic minerals, such as coal.
In one embodiment, the processes described herein are operated in a batch mode. In another embodiment, the processes described herein are performed in a continuous mode.
In one embodiment, the apparatus described herein is designed to be operated in a batch mode. In one embodiment, the apparatus described herein is designed to be operated in a continuous mode.
In one embodiment, the processes described herein are operated in a batch mode utilizing a combined F-T gasifier and microwave reactor. In one embodiment of a batch mode operation, the unheated feed mixture flows into the combined F-T gasifier and EMR reactor and is exposed to EMR inside the F-T gasification chamber.
In one embodiment, the processes described herein are operated in a continuous mode. In one embodiment of a continuous mode operation, the feed mixture is pre-heated in an EMR cavity before reaching the main F-T reaction chamber.
In another embodiment, the processes described herein are operated in a hybrid of batch and continuous modes, where the preheated feed mixture is subjected to EMR inside the F-T gasifier to achieve different process selectivity.
FIG. 1 shows an exemplary process flow diagram and apparatus for coal liquefaction wherein the F-T gasifier chamber and EMR cavity are combined.

a) The Combined F-T Gasifier Process Modules

As shown in FIG. 1:
(A) The F-T Gasifier is a chamber in which the gasification and liquefaction processes occur. This module operates at high temperature and pressure, to sustain the necessary process conditions for the gasification and liquefaction processes to occur.
(B) The Cavity is a section of the F-T Gasifier chamber in which EMR energy is transformed to heat the magnetite and elevate the internal temperature to the level required for the gasification and liquefaction processes to occur.
(C) The Solids Separator/Regenerator is a system that separates the solid effluent streams, for example, the coal ash, from the magnetite. In one embodiment, the separation is performed by a magnetic separator. This module is also designed to regenerate and clean the magnetite effluent from sulfur, hydrocarbons and other contaminants, for recycling.

b) The Combined F-T Gasifier Process Streams

As shown in FIG. 1:
(1) represents a coal-magnetite mixture. In one embodiment, the particle size of the mixture is greater than about 210 microns. In another embodiment, the particle size of the mixture is about 50 microns. In further embodiments, the ratio of coal to magnetite (C:M) in the mixture is between about 10% and about 90%, for example, between about 30% and about 70%.
(2) represents an oxygen inlet. In one embodiment, the oxygen feed is adjusted to control an oxygen lean atmosphere to produce carbon monoxide, and reduce the production of carbon dioxide to a minimum.
(3) represents a steam inlet. In one embodiment, steam acts as the main source of hydrogen in the process. In one embodiment, the steam feed is controlled to adjust the H:C ratio of the reactant.
(4) represents a carbon dioxide injection inlet. In one embodiment, injection of carbon dioxide maintains a fluidized bed of the coal mixture. In another embodiment, the carbon dioxide acts as another source of carbon for the process.
(5) represents an EMR energy input. In one embodiment, the EMR energy is created by a standard industrial microwave generator. In another embodiment, the EMR energy is created by radio frequency.
(6) represents an input for cooling water to the jacket of the gasifier. In certain embodiments, cooling water is added to the jacket of the gasifier to maintain a temperature inside the chamber suitable for the processes described herein.
(7) represents a steam outlet from the cooling water jacket. The exothermic reactions which occur inside the reaction chamber will produce high temperature that will convert the cooling water in the jacket to steam. In certain embodiments, the steam is used to (1) control the gasifier/cavity temperature, and (2) to generate electricity to feed the microwave generator.
(8) represents an outlet, whereby synfuel and syngas products are removed for oil and chemical workup to refine the products of the process to a desired marketable product range.
(9) represents a solid waste outlet. In certain embodiments, solid waste produced in the process includes combustion ash and magnetite.
(10) represents ash for disposal. Coal ash may be directed to disposal facilities.
(11) represents a magnetite outlet stream. In certain embodiments, magnetite is regenerated to remove residual hydrocarbons and recycled back to the process feed.
FIG. 2 shows an exemplary process flow diagram and apparatus for coal liquefaction wherein the feed mixture is preheated in an EMR cavity prior to entering the F-T gasifier chamber.

(a) The Preheated F-T Gasifier Process Modules

As shown in FIG. 2:
(A) The EMR zone is a chamber in which the mixture of organic material (e.g., coal), magnetite and other components are heated. In one embodiment, the heating is provided by the absorption of EMR by the magnetite.
(B) The F-T Gasifier is a chamber in which the gasification and F-T synthesis processes occur. This section may also include EMR to improve selectivity.
(C) The Solids Separator/Regenerator is a system that separates the solid effluent streams, for example, the coal ash, from the magnetite. In one embodiment, the separation is performed by a magnetic separator. This module is also designed to regenerate and clean the magnetite effluent from sulfur, hydrocarbons and other contaminants, for recycling.

(b) The Preheated F-T Gasifier Process Streams

As shown in FIG. 2:
(1) represents a coal-magnetite mixture. In one embodiment, the particle size of the mixture is greater than about 210 microns. In another embodiment, the particle size of the mixture is about 50 microns. In further embodiments, the C:M ratio in the mixture is between about 10% and about 90%, for example, between about 30% and about 70%.
(2) represents an oxygen inlet. In one embodiment, the oxygen feed is adjusted to control an oxygen lean atmosphere to produce carbon monoxide, and reduce the production of carbon dioxide to a minimum.
(3) represents a steam inlet. In one embodiment, steam acts as the main source of hydrogen in the process. In one embodiment, the steam feed is controlled to adjust the H:C ratio of the reactant
(4) represents a carbon dioxide injection inlet. In one embodiment, injection of carbon dioxide maintains a fluidized bed of the coal mixture. In another embodiment, the carbon dioxide acts as another source of carbon for the process.
(5) represents an EMR energy input. In one embodiment, the EMR energy is created by a standard industrial microwave generator. In another embodiment, the EMR energy is created by radio frequency.
(6) represents an input for cooling water to the jacket of the gasifier. In certain embodiments, cooling water is added to the jacket of the gasifier to maintain a temperature inside the chamber suitable for the processes described herein.
(7) represents a steam outlet from the cooling water jacket. The exothermic reactions which occur inside the reaction chamber will produce high temperature that will convert the cooling water in the jacket to steam. In certain embodiments, the steam is used to (1) control the gasifier/cavity temperature, and (2) to generate electricity to feed the microwave generator.
(8) represents an outlet, whereby synfuel and syngas products are removed for oil and chemical workup to refine the products of the process to a desired marketable product range.
(9) represents a solid waste outlet. In certain embodiments, solid waste produced in the process includes combustion ash and magnetite.
(10) represents ash for disposal. Coal ash may be directed to disposal facilities.
(11) represents a magnetite outlet stream. In certain embodiments, magnetite is regenerated to remove residual hydrocarbons and recycled back to the process feed.
Additional advantages of any of the processes and/or apparatus described herein include:
1) A very rapid temperature increase to a level of over 1,000° C. (1,800° F.) is attainable, which will start the chemical processes. This will accelerate the CTL process to a high degree, and will facilitate the utilization of simple batch reactors to overcome the complexities of reactor design.
2) The presence of magnetite as an initiator for the gasification processes and its potential use as a catalyst for the F-T synthesis in the same process chamber will facilitate the direct CTL process.
3) Gasification processes are to a large extent endothermic, i.e., they require a constant addition of energy to maintain the process. The F-T Process is highly exothermic, i.e., produces heat in the process. The combination of these processes in one chamber will utilize F-T synthesis heat to fuel the gasification processes.
4) Gasification and the gas loop are the most expensive steps in the CTL process, followed by the cost of the F-T synthesis. Converging the gasification and F-T Process steps into a single step will significantly reduce the capital costs involved in the process and simplify its operation.
5) GHG emissions associated with the separate gasification and liquefaction processes can be significantly reduced due to the fact that heat will be produced by EMR and not by burning coal. Further, microwave is the most efficient form of heating energy, thereby allowing for reduction in heating costs involved in the process.
6) In both the gasification and F-T synthesis, carbon dioxide is converted to carbon monoxide and hydrocarbons. The processes and apparatus described herein can therefore be used as a carbon dioxide sink.
7) The processes described herein can utilize small particles of organic material (e.g., coal) as the starting organic mineral. Restrictions on particle size that are present in dry coal processes are thereby removed and waste is eliminated.
8) The processes described herein will not require the use of any solvent, thereby reducing waste and operating costs.
9) The processes described herein will generate the hydrogen required for the liquefaction process, thereby lowering operating costs.
10) The processes described herein can be operated in either a batch mode (not previously available in CTL technology) or in a continuous mode.
The term “about” or “approximately” means within an acceptable error range for the particular value as determined by one of ordinary skill in the art, which will depend in part on how the value is measured or determined, i.e., the limitations of the measurement system. For example, “about” can mean within one or more than one standard deviation, per practice in the art. Alternatively, “about” with respect to the formulations can mean plus or minus a range of up to 20%, preferably up to 10%, or more preferably up to 5%.
The term “coal” as used herein, includes all materials in the class of bituminous coal, sub-bituminous coal, lignite, pit, and the like.
Any range of numbers recited in the specification or paragraphs hereinafter describing or claiming various aspects of the invention, such as that representing a particular set of properties, units of measure, conditions, physical states or percentages, is intended to literally incorporate expressly herein by reference or otherwise, any number falling within such range, including any subset of numbers or ranges subsumed within any range so recited.
The principles, preferred embodiments, and modes of operation of the present invention have been described in the foregoing specification. The invention which is intended to be protected herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be regarded as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art, without departing from the spirit of the invention.
The contents of all patents and publications cited herein are hereby incorporated herein by reference in their entireties, to the extent permitted.

Claims

What is claimed is:

1. A process for making one or more non-solid hydrocarbons, the process comprising subjecting a reaction mixture comprising a solid organic material in the presence of a magnetite-type composition to electromagnetic radiation to form reaction conditions that cause said reaction mixture to form reaction products comprising one or more non-solid hydrocarbons.

2. The process of claim 1 wherein said reaction conditions are selected from one or more of the group consisting of liquefaction conditions and gasification conditions.

3. The process of claim 1 wherein the reaction mixture further comprises one or more further reactants selected from the group consisting of water and oxygen.

4. The process of claim 1 wherein said reaction conditions comprise gasification conditions and liquefaction conditions.

5. The process of claim 1 wherein the liquefaction conditions comprise Fischer-Tropsch synthetic conditions.

6. The process of claim 1 wherein the reaction mixture comprising of solid organic material in the presence of magnetite is subjected to electromagnetic radiation prior to the liquefaction stage.

7. The process of claim 1 wherein the solid organic matter is selected from the group consisting of coal, shale, peat, biomass, and combinations thereof.

8. The process of claim 1 wherein the magnetite-type composition comprises magnetite.

9. The process of claim 8 wherein said magnetite-type composition further comprises one or more metals selected from the group nickel, cobalt, copper, silver, gallium, indium, manganese, zinc, platinum, palladium, gold, ruthenium, rhodium, iridium, and combinations thereof.

10. The process of claim 1 wherein no solvent is added during the process.

11. The process of claim 1 wherein the electromagnetic radiation is microwave radiation.

12. The process of claim 1 wherein the electromagnetic radiation is radio frequency radiation.

13. The process of claim 1 wherein said magnetite-type composition is dispersed in said reaction mixture.

14. An apparatus for making one or more non-solid hydrocarbons comprising:

a.) at least one vessel having at least one opening for receiving reactants and discharging a non-solid hydrocarbon, said reactants comprising solid organic material, water and oxygen, said at least one vessel containing magnetite-type composition as a mixture with said reactants or as a immobilized matrix;

b.) electromagnetic radiation means in communication with said at least one vessel for placing electromagnetic radiation into said vessel to create reaction conditions to cause said reaction mixture to form one or more non-solid hydrocarbons.

15. The apparatus of claim 14 wherein said reaction conditions are selected from the group consisting of gasification and liquefaction.

16. The apparatus of claim 14 wherein said reaction conditions are Fischer-Tropsch synthetic conditions.

17. The apparatus of claim 14 wherein said vessel has at least one input opening for receiving said solid organic material, water and oxygen and at least one output opening for discharging said at least one non-solid hydrocarbon.

18. The apparatus of claim 14 wherein said electromagnetic radiation means is a microwave radiation emitter.

19. The apparatus of claim 14 wherein said electromagnetic radiation means is a radio frequency radiation emitter.

20. The apparatus of claim 14 wherein said at least one vessel comprises a electromagnetic zone vessel and a reaction vessel, said electromagnetic radiation vessel having said at least one opening for receiving said reactants and further in fluid communication with said reaction vessel, said electromagnetic zone vessel in communication with said electromagnetic radiation means, and said reaction vessel receiving said reactants from said electromagnetic zone vessel and completing said reactions to form one or more non-solid hydrocarbons.