NZ628900B2 - Heavy fossil hydrocarbon conversion and upgrading using radio-frequency or microwave energy - Google Patents

Abstract

Disclosed is a method for the conversion of heavy fossil hydrocarbons (HFH) to a variety of value-added chemicals and/or fuels using microwave (MW) and/or radio-frequency (RF) energy comprising: flowing a continuous feed comprising HFH and a process gas through a reaction zone having a pressure greater than 0.9 atm; contacting the HFH and a HFH-to-liquids catalyst in at least the reaction zone; concentrating MW or RF energy in the reaction zone using a microwave or RF energy source; and generating dielectric discharges within the reaction zone; wherein the HFH and the catalyst have a residence time in the reaction zone of less than 30 seconds. ter than 0.9 atm; contacting the HFH and a HFH-to-liquids catalyst in at least the reaction zone; concentrating MW or RF energy in the reaction zone using a microwave or RF energy source; and generating dielectric discharges within the reaction zone; wherein the HFH and the catalyst have a residence time in the reaction zone of less than 30 seconds.

Description

Heavy Fossil Hydrocarbon Conversion and ing Using Radio-Frequency or Microwave Energy Priority This invention claims priority to U.S. Patent No. 13/401,216, filed February 21, 2012, entitled Heavy Fossil Hydrocarbon Conversion and Upgrading Using Radio- Frequency or Microwave Energy.

Statement Regarding Federally Sponsored Research or Development This invention was made with Government support under ARPA Order No.

Z075/00, Program Code 9620 issued by DARPA/CMO under Contract HR00110088.

The U.S. Government has n rights in this invention.

Background Traditional liquefaction methods for coal, and other heavy fossil hydrocarbons (HFH), can be divided into two general categories. The first is ct liquefaction, where the coal is first gasified to synthesis gas that is then used for al and fuel production.

The second method is direct liquefaction, where the coal chemicals and fuels are either extracted/refined from the coal or the coal undergoes a series ofthermochemical reactions.

Most of these traditional methods of coal liquefaction have significant energy requirements and nmental impact. Conventional techniques for direct coal liquefaction will generally result in lower COz emissions compared to indirect techniques, but will typically require vely higher atures and higher pressure hydrogen to obtain significant product yield and quality. Operation at high temperature and high pressure results in high energy requirements, water consumption, and l costs. Therefore, alternative methods 195246NZ AMENDED SPEC SEPT2016000.DOCX for conversion ofHFH to value-added als and fuels are required to reduce the capital costs, the operating costs, and the nmental impact ofHFH liquefaction and in order to make facilities such as coal-to-liquids (CTL) plants le.

Summary This document describes a system that utilizes ave (MW) and/or radio- frequency (RF) energies to convert HFH to a variety of value-added chemicals and/or fuels.

For example, direct generation of acetylene, olefms, naphtha, naphthalenes, benzene, toluene, xylene (BTX), polyaromatics, paraffins, and fuel precursors from flash conversion of coal in inert atmospheres has been observed. on of hydrogen and/or methane can further increase direct fuel production and hydrogenation ofHFH-derived liquids even when operating at atmospheric pressure and at modest temperatures. Variations ofreactants, process parameters, and reactor design, within the scope of the present ion, can significantly influence the ve distribution ofchemicals and fuels generated as the product.

One embodiment is a system for the continuous flash conversion ofHFH using microwave and/or radio-frequency energy. The system comprises a source emitting microwave or RF energy that is concentrated in and/or through a reaction zone having a pressure greater than 0.9 atm, a continuous feed sing HFH and a process gas flowing through the reaction zone, a HFH-to-liquids ) catalyst contacting the HFH in at least the reaction zone, and dielectric discharges within the reaction zone. Contact n the HFH and the catalyst can include physical contact between separate les (or the liquid) entrained in the gas, particles comprising a mix of the HFH and catalyst in close proximity 195246NZ AMENDED SPEC SEPT2016000.DOCX within the process gas, and/or HFH with catalytically active species directly impregnated on the HFH particles and/or within the pores of the HFH. For example, the catalyst or catalyst precursors, which can include various metal/metal oxide salts, organometallic species, or etal/metal oxide particles, can be impregnated in the HFH using aqueous or c solvents. The HFH and the catalyst have a residence time in the reaction zone of less than 5 minutes. Preferably, the residence time is less than 30 seconds when this system is operated, and can be approximately tens ofmicroseconds. In some instances, a plasma can form in or near the reaction zone.

Another embodiment includes a method for continuous flash conversion ofHFH.

The method comprises the steps of flowing a continuous feed sing HFH and a process gas through a reaction zone. The pressure in the reaction zone is greater than 0.9 atm. The HFH and an HFHTL catalyst are contacted in at least the reaction zone. The method further comprises concentrating microwave or RF energy in the reaction zone and generating dielectric discharges within the on zone. The HFH and the catalyst have a residence time in the reaction zone of less than 30 seconds.

In the method the process gas ses a hydrogen-containing gas.

In the method the catalyst comprises iron.

In the method the st comprises char.

In the method the catalyst comprises a promoter of dielectric discharge.

In the method the HFH and the catalyst are d.

In the method the process generating a plasma in or near the reaction zone.

In the method the pressure in the reaction zone is up to 7 atm.

In the method the nce time is greater than or equal to 5 milliseconds. 195246NZ AMENDED SPEC SEPT2016000.DOCX Said concentrating comprises emitting microwave or RF energy from a source into the reaction zone in a direction parallel to the continuous feed through the reaction zone.

A system for continuous flash conversion of heavy fossil hydrocarbons (HFH) comprising: a reaction zone having a pressure greater than 0.9 atm; a source emitting microwave or RF energy concentrated in the reaction zone; a source of a uous feed comprising HFH and a process gas, the continuous feed passing through the reaction zone; a HFH-to-liquids st contacting the HFH in at least the reaction zone; dielectric discharges within the reaction zone; wherein, the HFH and the catalyst have a residence time in the reaction zone of less than 30 seconds.

As used herein, continuous refers to systems and methods in which reactants are continuously fed through the reaction zone and continuously emerge as products and/or waste in a flowing stream.

Examples of suitable process gases include, but are not limited to, nitrogen, carbon dioxide, methane, natural gas, recycle gas, carbon monoxide, argon, , water vapor, , and combinations thereof. Preferably, the process gas comprises a hydrogen- ning gas. As used , pyrolysis refers to the chemical decomposition of HFH material without the ipation of Os. In instances where the process gas includes water vapor and/or Oz, some combustion may occur. However, the ratio of 0 to C less than one and pyrolysis is still the predominant reaction, and the process may be herein broadly 195246NZ AMENDED SPHC SEPT2016000.DOCX referred to as "pyrolysis" or "conversion." Generally, the HFH concentration in the total process gas should be sufficient for reactor operation while the gas feed can be as low as possible to ensure steady operation. In a particular embodiment, the HFH concentration in the total gas flow is greater than or equal to 0.1 wt% and less than 100 wt%. When the process gas comprises hydrogen-containing reactive gases, the concentration is preferably greater than 3 grams ofHFH per gram of reactive gas. In some embodiments, the concentration may be greater than 6 grams ofHFH per gram of reactive gas.

The reaction zone can exist within a reactor having a variety of configurations including, but not limited to, a fluidized bed reactor, an entrained flow reactor, a free fall reactor, or a moving bed reactor. The re in the reaction zone is, preferably, less than 7 atmospheres. The residence time ofreactants in the on zone is, preferably, greater than or equal to 5 milliseconds and under 30 s. The source can be arranged to emit microwave or RF energy at any angle from parallel to perpendicular to the flow direction in the on zone. The microwave or RF energy is emitted in a parallel direction to the continuous feed h the reaction zone. Furthermore, the energy can pass through the reactor walls defining, in part, the reaction zone. Alternatively, the energy can be d directly from or into the reaction zone by proper placement of the , or by proper placement of an antenna or waveguide at or within the reaction zone. on directly into the reaction zone improves ency and eliminates the need to transmit through reactor walls, and one or more sources configured to pass a HFH-to-liquids catalyst and a continuous feed comprising HFH and a process gas to the reaction zone.

In s embodiments, the catalyst comprises a promoter ofhydrogenation, a promoter of electrical discharge, and/or a promoter of hydrogen formation. The catalyst can 195246NZ AMENDED SPEC SEPT2016000.DOCX also be a dilution material. Examples of catalysts can include, but are not d to materials containing iron, nickel, cobalt, molybdenum, carbon, copper, alumina, silica, oxygen and combinations. Other catalysts may include iron and/or char. In some embodiments, the catalyst and the HFH can be admixed. In some embodiments, concentrations of the catalyst in the process gas can be between 0 wt% and 30 wt% or between 0.5 wt% and 10 wt%.

As used herein, HFH can refer to bitumen, coal of any rank (i.e., bituminous, sub- bihiminous, lignite, etc.), oil sands (i.e., bitumen containing ores), oil shale, eum resids, asphaltenes and pre-asphaltenes, and any other kerogen-containing materials. HFH can also refer to biomass, plastics, municipal waste, , or other carbon-rich materials.

The purpose of the foregoing abstract is to enable the United States Patent and ark Office and the public generally, especially the ists, engineers, and practitioners in the art who are not familiar with patent or legal terms or phraseology, to determine quickly from a y inspection the nature and essence of the technical disclosure of the application. The abstract is r intended to define the invention of the application, which is measured by the claims, nor is it intended to be limiting as to the scope of the invention in any way.

Various advantages and novel es of the present invention are described herein and will become further readily apparent to those skilled in this art from the following detailed description. In the preceding and following ptions, the various embodiments, including the preferred embodiments, have been shown and described. Included herein is a description of the best mode contemplated for ng out the invention. As will be realized, the invention is capable of modification in various respects without departing from 195246NZ AMENDED SPEC SEPT2016000.DOCX the invention. Accordingly, the drawings and ption of the embodiments set forth hereafter are to be regarded as illustrative in nature, and not as ctive.

This document also describes a method for continuous flash conversion of heavy fossil hydrocarbons (HFH), the method comprising: flowing a continuous feed comprising HFH and a process gas through a reaction zone having a pressure greater than 0.9 atm; contacting the HFH and a HFH-to-liquids catalyst in at least the reaction zone; trating microwave or RF energy in the reaction zone using a microwave or RF energy source; and generating dielectric discharges within the reaction zone; wherein the HFH and the st have a residence time in the reaction zone of less than 30 seconds.

Preferably the method of [0014], wherein the process gas ses a hydro gen - containing gas.

Preferably the method of , wherein the catalyst ses iron.

Preferably the method of [0014], wherein the catalyst comprises char.

Preferably the method of , wherein the catalyst comprises a promoter of dielectric discharge.

Preferably the method of [0014], wherein the HFH and the catalyst are admixed.

Preferably the method of [0014], further comprising generating a plasma in or near the reaction zone. 195246NZ AMENDED SPEC SEPT2016000.DOCX Preferably the method of [0014], wherein the pressure in the reaction zone is up to 7 atm.

Preferably the method of [0014], wherein the residence time is greater than or equal to 5 milliseconds.

Preferably the method of [0014], wherein said concentrating comprises ng microwave or RF energy from a source into the reaction zone in a direction parallel to the continuous feed h the reaction zone.

The document further describes a system for continuous flash conversion of heavy fossil hydrocarbons (HFH) comprising: a reaction zone having a pressure greater than 0.9 atm; a source emitting microwave or RF energy concentrated in the reaction zone; a source of a continuous feed comprising HFH and a process gas, the continuous feed passing through the reaction zone; a HFH-to-liquids catalyst contacting the HFH in at least the on zone; dielectric rges within the reaction zone; n, the HFH and the st have a residence time in the reaction zone of less than 30 seconds.

Preferably the system of [0024], wherein the process gas comprises a hydrogen- containing gas.

Preferably the system of [0024], wherein the process gas is selected from a group consisting of nitrogen, carbon e, methane, natural gas, e gas, carbon monoxide, argon, water, oxygen, and combinations thereof. 195246NZ AMENDED SPEC SEPT2016000.DOCX Preferably the system of [0024], wherein the HFH concentration in the process gas is between 0.1 wt% and 100 wt%.

Preferably the system of [0024], wherein the system ses a fluidized bed reactor, an entrained flow reactor, a free fall reactor, or a moving bed reactor.

Preferably the system of [0024], wherein the catalyst comprises iron. ably the system of [0024], n the catalyst comprises char.

Preferably the system of [0024], wherein the catalyst is ed from the group consisting of nickel, cobalt, molybdenum, carbon, copper, alumina, silica, oxygen and combinations thereof.

Preferably the system of [0024], wherein the catalyst comprises a promoter of hydrogenation.

Preferably the system of [0024], wherein the catalyst comprises a promoter of electrical discharge.

Preferably the system of [0024], wherein the catalyst ses a promoter of hydrogen formation.

Preferably the system of [0024], wherein the catalyst is a on material.

Preferably the system of , wherein the catalyst and the HFH are admixed.

Preferably the system of [0024], r comprising a plasma in or near the reaction zone.

Preferably the system of [0024], n the pressure in the reaction zone is up to 7 atmospheres.

Preferably the system of [0024], wherein the residence time is greater than or equal to 5 milliseconds. 195246NZ AMENDED SPEC_SEPT2016000.DOCX Preferably the system of [0024], wherein the catalyst has a concentration between 0.5 and 10 wt% relative to the HFH.

Preferably the system of , further comprising a dilution material and the continuous feed at a concentration between 0 and 30 wt%.

Preferably the system of [0024], wherein the microwave or RF energy is emitted in a el direction to the continuous feed through the reaction zone. ably the system of [0024], wherein the dielectric discharges are generated in the reaction zone when the system is operated.

Description of Drawings Embodiments of the invention are bed below with reference to the following anying drawings.

Fig. 1 is a diagram of a static, semi-batch, system for coal conversion using microwave energy.

Fig. 2 is a chromatogram from gas chromatography-mass spectrometry (GCMS) showing products from two samples (MWPyOl 1 and MWPy012) after microwave conversion.

Fig. 3 is a GCMS chromatogram illustrating the effect of nitrogen and hydrogen sweep gas on the composition of the pentane soluble fraction.

Fig. 4 is a m of a system for continuous flash conversion ofHFH, according to one embodiment of the present ion.

Fig. 5 is a diagram depicting a process of continuous sion ofHFH according to embodiments of the present invention. 195246NZ AMENDED SPEC SEPT2016000.DOCX Detailed Description The following description includes the preferred best mode of one embodiment of the present invention. It will be clear from this description of the invention that the invention is not limited to these illustrated embodiments but that the invention also includes a variety of modifications and embodiments thereto. Therefore the present description should be seen as rative and not limiting. While the invention is susceptible of various modifications and alternative constructions, it should be understood that there is no intention to limit the invention to the specific form disclosed, but, on the contrary, the invention is to cover all modifications, ative uctions, and equivalents falling within the spirit and scope of the invention as defined in the claims.

Flash-heating and/or quenching of products can prevent retrogressive reactions typically associated with conventional HFH conversion, while ively heating only the HFH can reduce process and thermal ciencies. Embodiments of the present invention utilize selective flash-heating of the HFH and/or HFHTL catalyst while g the bulk media at temperatures below pyrolytic conditions, thus effectively quenching the volatilized products or oils by the cooler bulk media. The selective flash heating can be accomplished h dielectric discharges d by uneven charge build up between or within HFH and/or catalyst particles, ucing the HFH and/or catalyst into a plasma, or rapid heating as a result of introducing microwave and/or RF ation.

Embodiments described in this document encompass adsorption of radio frequency (RF) or microwave energy at a frequency in which heating of re is not the primary mode of heating or absorption ofRF or microwave energy. Rather, heating and 195246NZ AMENDED SPEC SEPT2016000.DOCX absorption of the RF or microwave energy can be ed through nductor materials, which can include a hybrid HFHTL catalyst impregnated within the HFH or the HFH itself, until dielectric collapse occurs within and/or between the HFH, the catalyst particles, and/or the reactor components (e.g., reactor walls, uide ents, or conductive or semiconductor materials placed within the reactor) due to non-uniform charge build up on the HFH particles, catalysts, and/or reactor components. In some instances, the dielectric collapse can result in plasma discharge. Within each discharge, temperatures within the immediate region of the discharge can approach and even exceed 1500°C, but are typically quenched by the surroundings within microseconds. Regardless of the temperature in and near the discharge, there is minimal change to the bulk temperature in the reactor and/or reaction zone. As a result of the discharge, dramatic cleavage and rearrangement of organic ure can occur at the spark rge source particle and the immediate surroundings (ca. 0.1 cm). Any products and le matter are then released from the HFH into the surrounding media, which remains relatively cool. A plasma created locally in the immediate region of a le or preformed in the reaction zone generates reactive ion species (e.g. H, C, CHx, Ar, 0, or N ions) that can readily interact directly with the HFH, with the released ts and volatile matter, or with other reactive ions that can act as a catalytic initiator for the decomposition, hydrogenation, dehydrogenation, and other reactions that converts the HFH and/or reactive gas into different species.

By avoiding excessive heating of the bulk media, retrogressive and decomposition reactions can be reduced, which can improve liquid yields by me flash" conversion and/or conversion. With RF or microwave induced conversion, l energy (e.g., from a combustion source) is minimized or eliminated and the energy that is required 195246NZ AMENDED SPEC SEPT2016000.DOCX for liquefaction is trated and/or targeted within the reaction zone, instead of across the entire reactor and its contents as with a conventional thermal flash pyrolyzer, which has relatively high thermal inefficiencies.

The following tables and figures demonstrate and describe a variety of aspects and embodiments and were obtained using a high volatile bituminous Pitt #8 coal as a representative HFH. Unless specified otherwise the coal was used as received without drying or demineralization. The size of the coal was reduced to 60 mesh (<0.25 mm). To avoid plugging issues, the particle size range of the coal was narrowed to 100-200 mesh (74-149 micron) for most of the examples described . Proximate and Ultimate analysis of the Pittsburgh seam coal used as a representative HFH is shown in Table 1 and Table 2, tively.

Table 1 Proximate is ofPitt #8 Coal 23) as rec'd dry daf dmmf(Parr) % Moisture 2.00 % Ash 9.25 9.44 % Vol. Matter 38.63 39.42 43.53 42.33 % Fixed Carbon 50.12 51.14 56.47 57.67 2.50% equilibrium moisture Table 2 Ultimate Analysis ofPitt #8 Coal (DECS-23) as rec'd dry daf dmmf(Parr) % Ash 9.25 9.44 (12.32% MM) % Carbon 72.72 74.21 81.95 84.64 % Hydrogen 5.00 5.10 5.63 5.82 % Nitrogen 1.32 1.35 1.49 1.54 % Total Sulfur 3.79 3.87 4.27 % Oxygen (diff.) 5.91 6.03 6.66 8.00 195246NZ AMENDED SPEC SEPT2016000.DOCX Referring first to Fig. 1, the diagram depicts a static coal reactor 102 having a static coal bed, continuous flows from gas sources 101, online gas analysis device 105 such as a gas chromatograph, and one or more product collection vessels 104. The reactor 102 is shown within a microwave oven 103 that is used as a radiation source, although in practice the r may be integral with or connected to other types of microwave or RF energy sources. While embodiments described in this document encompass a uous reactor, the static reactor is used to describe and demonstrate various aspects and principles. The microwave oven 103 was modified by removing the turntable and drilling of 2" holes through the top and bottom of the oven cavity to allow the insertion of a quartz reactor tube through the cavity. To avoid microwave leakage outside the microwave oven two aluminum flanges were bolted to the top and the bottom of the ave oven. Each flange had a 1.05" O.D. tube opening that was 4.8" long. This permitted the safe operation of the microwave oven without electromagnetic field emissions as a result of passing the reactor tube h the oven cavity. The pressure in the reactor was greater than or equal to imately 1 atm. Stable performance was maintained at atmospheric pressure through the maximum operating pressure of the test stand of 35 psig (2.4 atm) or 3.4 atm (absolute pressure). Pressures even beyond this are suitable. 1-2 grams of coal (<60 mesh, as rec'd) were inserted between two quartz wool plugs within a 10.5 mm ID (12.5 mm OD) quartz reactor tube. Three Ni-chrome alloy wires of-40 mm in length were y intertwined together to form a single "rope" m in length, with three "spokes" on the top and bottom of the wire rope. The wire elements were typically inserted into the reactor tube prior to loading of the coal around the wires, and served as a microwave "antenna" to direct the ave energy to the coal bed and to aid 195246NZ AMENDED SPEC SEPT2016000.DOCX in the on ofdielectric discharges throughout the coal bed. The reactor hibe was then placed in a larger 0.75"OD (0.625"ID) quartz outer tube and the top and bottom of the reactor tube were sealed within the larger outer tube with Teflon® s (outside the oven cavity). This enabled rapid reactor ound and more accurate mass balance calculations through weighing and loading of the inner tube.

Gas was introduced at a flow rate of 200 seem (total) through the outer quartz tube using mass flow controllers. The Teflon seals placed around the reactor tube force the gas through the static coal bed. The microwave time for the experiments varied between 30 seconds and 10 minutes. Products were ted in a series of cold traps, the first being chilled to ~0°C and the second trap was chilled with dry-ice and propanol to a temperature of-78°C. The gas was then passed through an online-gas GC and then collected in a gas sample bag for further analysis and quantification of the gas formed/consumed during microwave conversion.

Baseline tetrahydrofuran (THF) extractions of as received Pitt #8 (DECS-23) coal in the batch reactor are shown in Table 3. The THF extractions were performed to assess the amount of extractable product without microwave or thermal ents for direct comparison of the improvement in soluble products with ation of various conversion energies. tions #8 with THF yielded between 13 and 16wt% THF soluble tars, with little to no pentane soluble oil yield. 195246NZ AMENDED SPEC SEPT2016000.DOCX Table 3. Baseline THF Extractable Yields from Pitt #8 (as Pitt#8 2.1499 1.9881 0.2546 0.0228 13% 105% rec')L Pitt#8 2.1958 1.9859 0.2272 0.1139 16% 102% Baseline thermal yields ofPitt#8 coal at 350°C were performed at elevated pressures of inert and hydrogen gases, and the s are presented in Table 4. 350°C was selected as the conversion temperature to determine if any pyrolytic or devolatilization reactions would occur during char-vapor separations within heated cyclones during experimental trials. As shown in Table 4, the effect of a conversion temperature of 350°C had little influence on the net conversion of coal and the THF soluble tar yield was similar to the baseline THF extractable yields from Pitt#8. The effect of gas headspace of either nitrogen or hydrogen also showed little impact.

Table 4. Baseline Thermal Conversion Yields ofPitt#8 Coal sit350°C under 450 psi N;and Pitt#8 350°C,lhr,450psiN2 1.01 0.836 82.77 0.0217 2.15 0.131 | 12.97 98.9% Pitt#8 lhr,450psiH2 1.00 0.818 81.80 0.0298 2.98 0.146 | 14.6 99.4% Initial coal conversion experiments were performed with various coal-to-liquids (CTL) sts within a static coal bed under g nitrogen gas in a quartz tube that is placed h an off-the shelf home microwave oven. With no catalyst, little to no coal conversion was observed at microwave exposure times of 5 minutes, as shown in Table 5.

Doping the coal with 2-10wt% ofCTL catalysts (ferrihydrite and ite) and iron filings 195246NZ_AMENDED SPEC SEPT 20 16000.DOCX (40mesh) also showed little to no effect on coal conversion and bed temperatures never exceeded 200°C. This indicated that poor MW energy transfer to the coal bed and/or the CTL catalysts and metal flakes were ineffective for facilitating MW heating or plasma discharges. Only in the case of ment MWPy009 was any significant conversion of coal observed. This was also the only run in which dielectric discharges were observed, indicating that without the presence ofdielectric discharges or a plasma the coal will not undergo any significant conversion.

Table 5. Product Yields from Initial MW Conversion Experiments MW time Coal Gas Yield Solii Yield Gas + t Yield Run ID: Coal Catalyst (min) Load(g) wt wt% wt wt% wt wt% extraction Pitt none 0 2.15 0 0 1.99 92.5% 0.162 7.5% MWPy007 Pitt none 5 1.5 0 0.0% 1.39 92.7% 0.11 7.3% MWPy008 Pitt 20wt% ings 5 1.2 0 0.0% 1.04 86.7% 0.16 13.3% MWPy009 Pitt SS wire 5 1.5 0.15 10.1% 0.80 53.3% 0.70 46.7% NZ AMENDED SPEC SEPT2016000.DOCX Table 6. An incomplete list of appropriate catalysts with summarizations of the performance and certain characteristics of each st.

Class al (size) Discharge Characteristics Catalytic Potential ntermittent rging with blue plasma- nodest hydrogenation activity (CH4), :e-filings (420 micron) nduced glow, some heating lighestBTX yield lot tested in staticsystem, evaluatingin )ramatic discharging for entire 30 second :e-powder (~100 ) :ontinous system- potential to improve luration, sample fused lischarge w/smaller particles CTL tighest hydrogenolysis and deoxygenatic eCS (nanocatalyst) io response Catalysts ty under hydrogen flow :ood deoxygenation activity, modest e-ferrihydrite (nanocatalyst) Jo response ivdrogenolysis activity lighest oil yield w/methane feed eS-JL(nanocataIyst) lo response 28wt%), t ivity to JP-8 itermediates (2/3-ringaromatics) li0(150-250 micron) lo se iwcatalytic potential igh potential CH4 conversion; but liO-ReducedinH2(150-250 iramatic discharging, highest intensity and squires catalyst pretreatment and licron) n icovery Methane i-90: Promoted NiO/A1203 (150- ommerdal methane reforming catalyst - Conversioi lo response 00 ) )w catalyst potential -90: Promoted NiO/A1203 (<88 ^mmercial methane reforming catalyst - inj o response licron) )w catalyst potential Catalysts otential fris/tu upgrading - no discharge SY(<150 micron) o response rtivity otential/nsitu upgrading-no discharge SY (.854-2 mm) o response :tivity morphous Carbon (<150 micron) o response one morphous Carbon (420-841 e indication of improved discharge ime sparking, plasma formation ucron) /larger coal particles leal diluent material to t caking 50 micron) ramatic discharging, intermediate duration Possible id improve discharges/plasma stability Diluentor Tong-localized discharges, highest heat raphite (fines) idication of desired char properties :luidizatior ineration Materials pha-Alumina(~150 micron) o response me licon carbide (23 micron) o response me liconcarbide (100 micron) o response me licon carbide (ISOmicron) o se ine >-5 Silica (fumed silica) D response 3ne - current di I uent to avoid caking Table 6 contains a y of the performance and characteristics of a variety of catalysts, including those that exhibit dielectric discharge, hydrogen formation, and/or dilution characteristics. As described elsewhere herein, initiation ectric discharge is a critical on of suitable catalysts according to embodiments of the present invention. In addition to those shown in Table 6, rapid heating and ignition ofdielectric discharges were observed for copper wire, magnetite, and iron s in argon and air flows. 195246NZ AMENDED SPEC SEPT2016000.DOCX Dielectric discharge was observed from iron filings in separate experiments, even though no appreciable coal conversion or dielectric discharges were observed for the coal with Fe-filings in experiment IVtWPyOOS. A potential cause for this discrepancy is poor energy absorption. The lack of coal heating or dielectric discharges was hypothesized to be d to the distribution of the electromagnetic energy fields within the reactor's MW oven . Accordingly, in some embodiments, stainless steel wires can be inserted around the coal bed to enhance energy sion at and around the coal bed. After inserting the metal wires, a successful plasma ignition between the wires was observed and plasma-induced coal sion was sful, as shown for experiment M[WPy009 in Table 5.

In addition, the catalytic materials tested in Table 6 were re-evaluated for the potential ability to catalyze dielectric discharges and/or plasma ion when physically mixed with amorphous carbon. In all cases when the materials were packed in a manner in which there was a continuous bed of solids where all particles were touching, no dielectric rges or plasmas were observed. However, when the materials were dispersed slightly, dramatic discharges were observed ting that the use of any material that promotes dielectric discharges or plasmas can be used in the continuous flow process to enable plasma and dielectric discharge generation at pressures greater than 0.9 atm, thus enabling plasma and dielectric rge conversion of coal and other HFH to occur at pressures outside the traditional envelope ofhigh-vacuum plasma ations.

Conversion product yields from Pitt#8 coal in nitrogen flow were 10.1wt%(as rec'd) gas, 36.6wt°/o(as rec'd) THF soluble products, and 53.3wt%(as rec'd) char. The composition of the gas recovered from the MWPy009 experiment is presented in Table 7. 195246NZ AMENDED SPEC SEPT2016000.DOCX The total recovered tar/oil extracts (47.9 wt%) contained ~33wt% (as received) pentane soluble oil product, which would be ered material that can be upgraded to a JP-8 fuel.

Table ~. Surnm;n'y i)t' tlic cun][)o.sitinn nl'tlie ea.s rccoiercil t'rnm comcrsioi] of.M\\ P\ 009.

Gas Mole (%) I Gas Mole (%) N2 73.9 Ethane 0.97 02 1.0 Ethylene 1.3 H2 11.5 co 2.8 CH4 7.8 C02 0.63 Table 8 shows the products and repeatability ofMW-induced sion within the static coal reactor when stainless steel wires are inserted into the static coal bed. For each experiment nitrogen sweep gas was uously passed over the coal bed. The gas composition for MWPyOl 1 and MWPy012 is shown in Table 9. A significant amount of en gas is directly generated from the coal during MW-induced conversion, and the majority of the carbon-containing species were methane, ethane and ethylene with some CO and C02 formation due to liberation of oxygen from the coal.

Table 8. Product Distribution and Repeatability ofMW-Induced Coal Conversion with Stainless Steel Wires Inserted into a Static Coal Bed under Nitrogen Flow MW Coal Pentane Total Tar Yield CharYield Gas Yield PentaneSol. Mass Run ID: Coal Catalyst time Load Insol. (THFSol) Balance (min) JsL wt(g)| wt% wt(g)I wt% wt(g)| wt% wt (g)I wt% wt(g) I wt% MWPyOll Pitt steel wires 2.03 1.19 58.6% 0.285 14% 0.032 1.6% 0.53 26.0% 0.56 27.6% 100.2% MWPy012 Pitt steel wires 2.02 1.001 49.6% 0.131 6% 0.035 1.7% 0.70 34.7% 0.74 36.4% 92.4% 195246NZ AMENDED SPEC SEPT2016000.DOCX Table 9. Gas compositions resulting from the uced conversion ofPitt#8.

Composition mole% MWPy01l|MWPy012 H2 16.76 7.173 C02 0.373 0.322 ethylene 0.905 0.545 ethane 0.337 0.523 AR/02 1.321 N2 71.089 85.639 CH4 6.913 4.552 co 2.302 1.246 The e soluble fraction's composition was analyzed by GCMS and is presented in Figure 2 for MWPyOl 1 and 12. Prior to pentane and THF removal (see "unconcentrated" in Figure 2), the majority the product signal is relatively weak due to saturation by pentane and THF, however the major compounds including benzene and toluene were observed. Removal of the solvent from the fraction allowed for more detailed analysis. The majority of the products were two- and three-ringed aromatics along with PCX species, which is very similar to the product distribution from thermal conversion of Pitt#8 coal. This indicates that during microwave-induced conversion the coal is undergoing conversion in a similar manner as thermally-induced conversion To improve the hydrogen content of the ts ofMW-induced conversion hydrogen and/or methane gas was used as a hydrogen source. Table 10. Effect of Nitrogen and Hydrogen Sweep Gas on t Yields during Static MW shows the effect of 90% hydrogen gas in 10% en as a sweep gas during static microwave-conversion ofPitt#8 coal without a catalyst. Introduction of hydrogen to the system reduced the overall liquid and gas product yield and resulted in plugging of the reactor tube within 6 s.

Furthermore the mass balance was reduced, which h later experimentation was shown to be a result of loss of lighter hydrocarbons and BTX components during solvent removal. 195246NZ AMENDED SPEC SEPT2016000.DOCX Although the yields were reduced there was a reduction in the phenols, cresols, and xylenols (PCX) content of the collected liquid products (as shown in Fig. 3) that were pentane soluble, which is consistent with the reduced mass balance as a result ofBTX and lighter hydrocarbon yields that were not collected or accounted for in the yield calculations.

Table 10. Effect of Nitrogen and Hydrogen Sweep Gas on Product Yields during Static MW Conversion Pe tane Pen- ane Total 1 ir(THF Cha Yield Gas ffeld Insc ubles Solu iles s. I) Purge MW time Coal Load Mass Run ID Gas Catalyst (min) wt(%) (%) -M- wt(g) wt(%) wt(g) wt(g) wt (%) wt(g) wt(g) wt(%) Balance MWPy017 N2 none 7 2.02 1.060 52.5% 0.179 8.9% 0.1 5.0% 0.29 14.4% 0.39 19.3% 80.6% MWPy018 90%H2 none 6 2.08 1.217 58.5% 0.1083 5.2% 0.062 3.0% 0.16 7.7% 0.222 10.7% 74.4% Table 11. Effect of N3, H2, and €N4 Sweep Gas on Product Yields during MW shows the products formed during microwave-induced conversion of a static Pitt#8 coal bed as a function of sweep gas used. For all tests the microwave heating time was 5 minutes, a total gas flow rate of200sccm, and 2g of coal was used. Under similar conditions as before (MWPy-011 and MWPy-012), the result of using a the modified microwave oven system (i.e., lower power ave source and addition of a water dummy load) reduced the overall product yield for experiment MWPy038.

Table 11. Effect of N2, Hz, and CR} Sweep Gas on Product Yields during MW Conversion Oil •ield Per :ane Tar 'ield mass Sweep net gas formed Ch w (penta ie sol.) Insolu 3le0il (THF Sol.) balance Run ID Gas Catalyst wt(g) wt% wt(g) wt% wt(g) wt% wt(g) wt% wt(g) wt% % MWPy038 N2 none 0.158 10.5 0.950 62.9 0.302 20.0 0.06 4.0 0,362 24.0 97.4% MWPyOBG 90%H2 none 0.035 2.1 1.360 83.4 0.088 5.4 0,13 8.0 0.218 13.4 98.9% MWPy035 90%CH4 none 0.061 4.1 0.860 57.3 0.274 18.3 0.14 9.3 0.414 27.6 89.0% Referring to Fig. 4, a continuous reactor is ed through which a continuous feed sing HFH (e.g., coal) 404 and a s gas is continuously fed h a region 406 irradiated by radio frequency or microwave energy. The reactor ses a feed tube 401, through which the coal ned in a reactive gas enters the reaction zone 406, within 195246NZ AMENDED SPEC SEPT2016000.DOCX an outer tube 405 through which the additional s gas 402 flows. The RF or ave source 407 irradiates a region composing a reaction zone 406. In some instances, a plasma 408 forms in, or near, the reaction zone. An exemplary outer tube can se a quartz tube. An exemplary feed tube can comprise an alumina tube. A ow distributor disk 403 can be placed upstream from the reaction zone. In an applied process, microwave or RF energy can be introduced dicularly (as shown in Fig. 4) to the reaction zone. Alternatively, the microwave or RF energy can be co-introduced co-currently or counter-currently (i.e., parallel) to the flow ofHFH and the process gas(es). This also enables the reactor and process reactor materials to be constructed of a wide-range of materials including, but not limited to steels, ceramics, and other engineered materials.

Fig. 5 is a schematic diagram depicting the process of continuous conversion of HFH according to embodiments of the present invention. A continuous feed, which ses HFH and a process gas, and a HFHTL catalyst are flowed 501 to the reaction zone 504, which has a pressure greater than 0.9 atm. The HFH can be between 0.1% and 100% by weight of the continuous feed. In some embodiments, the HFH can be between 0.5wt% and 95wt% of the continuous feed, between 4wt% and 93wt% of the continuous feed, or between 8wt% and 93wt% of the continuous feed. Generally, the HFH concentration in the process gas should be as high as possible to ensure maximum efficiency and product generation. At that same time, the concentration of the process gas should be sufficiently high to increase the hydrogen-to-carbon ratio of the final products and to ensure stable r performance.

In at least the reaction zone, the HFH and HFHTL catalyst are contacted 505. ave or RF energy is emitted 502 into the on zone from a source. Dielectric 195246NZ AMENDED SPEC SEPT2016000.DOCX discharging 506 occurs in at least the reaction zone to e conversion of the HFH.

Products and waste flow out 503 of the reaction zone. The HFH and HFHTL catalyst have a nce time of less than 30 seconds in the reaction zone.

Table 12 summarizes the product yields from microwave conversion ofPitt #8 coal under various ions in a continuous flow-reactor such as the one depicted by Fig. 4 and/or according to methods described in Fig. 5. Without catalyst addition, the oil yield is ~20wt% (daf) under both nitrogen and hydrogen (25% hydrogen in nitrogen) flow entrainment. Under the same conditions and coal feed rate, the addition of the Fe-powder CTL catalyst significantly enhanced the oil yield to nearly 42wt% (daf). Included in the oil product distribution was a substantial increase in the formation of light hydrocarbons, mainly benzene and other mono-aromatic and cyclo-paraffm compounds, as shown in Table 13. In some embodiments, the microwave power can range between 0.1 and 100 MW-hr per ton ofHFH. Relatively lower microwave powers can help reduce the intensity of the plasma formed and increase the relative degree ofdielectric discharging between coal particles. By increasing dielectric discharges and reducing the plasma intensity, the oil yield sed relative to the BTX yield, which was reduced more dramatically. gh the net oil yield was reduced, the yield ofnon-BTX compounds within the distillate fuel boiling ranges remained consistent (30 wt%), ting that BTX yield can be sed or decreased by adjusting the relative degree of plasma energy intensity ing in a higher number of plasma ions reacting directly with the coal (and volatilized products) to form ene, which then undergoes oligomerization and other polymerization reactions. Accordingly, in some embodiments, at least a n of the residual char is further reacted with a reactive plasma, such as hydrogen, to yield acetylene and other chemicals that could be used to 195246NZ AMENDED SPEC SEPT 2016000.DOCX increase distillate fuels production and/or help offset production costs through production of value-added als (such as acetylene, BTX, styrene, ethyl-benzene, aromatics, olefins, and LPG) from the char.

During plasma conversion the reactive plasma ions can react directly with the coal or HFH to form acetylene that then polymerizes to yield benzene, styrene, and other polymeric products. The increased BTX compounds can be a result ofplasma-induced ringopening reactions ofhydroaromatics, which are formed during catalytic hydrogenation of naphthalenes and other omatic species, followed by side-chain ge. The intensity of the plasma and the relative concentration of the reactive plasma ions can be controlled to maximize the yield ofdistillates and/or to minimize acetylene formation and over-cracking of the d oils.

T.ible 12 I'rrtliK't Melds t'ri)in CHntinudii'. .Micrn^aM' Cotncr-.ion nt'l'itt ( D;il Total wtCoal wt% Char Tar Yield total Oil Total Liquid Yield Total Mass Feed (g) Fed (daf) (wt%) (wt%, daf) (wt%, daf) Balance 16, N2/no-cat 4 2.8 58.4 2.0 19.7 21.7 84.4 MWPy-120, H2/no cat 4 2.9 58.4 2.7 20.6 23,3 85.6 26, 25%H2/Fe Powder/lOOOW 15 11,6 18.8 3.0 41.9 44.9 71.6 MWPy-134, 25%H2/Fe Powder/GOOW 18 13.8 26.9 9.1 33.1 42.2 75.8 MWPy-142, Fe Powder/GOOW 4 2.9 35.6 2.1 30.9 33.0 75.5 Table 13 C'onversion nfl'itt C'onl to H^(lri)c;irl)0lis heluvi the ,IP-<S Bdilini: R;inye Light Ends (wt%, daf) MWPy-126, Fe Powder/lOOOW 13.86 MWPy-134, 25%H2/Fe Powder/GOOW 5.61 MWPy-142,10%H2/Fe Powder/GOOW 0.54 In some embodiments, methane and HFH such as coal can be olyzed.

Methane conversion can lead to extensive carbon coating of the reactor walls. In one particular instance, an argon plasma can be pre-formed within the microwave zone to reduce 195246NZ AMENDED SPEC SEPT2016000.DOCX the detrimental carbon build up. An inner feed tube supplying methane and coal was lowered to a position near the exit of the waveguide, thus preventing methane or coal conversion within the microwave zone. In the instant configuration, the coal and methane were introduced into the pre-formed Ar plasma and only in lower ns of the reactor was a methane/coal/Ar plasma observed. While carbon buildup was reduced within the microwave waveguide, the ed oil yields were relatively low, as shown in Table 14 Product Yields from version of e and Coal in a Microwave . Without the addition of hydrogen to the feed, the oil yield was only 14.8wt% (total tar 26.6 wt%).

Addition of a small amount of hydrogen increased the oil yield to 22.3wt% but the total tar yield remained low at 24.5wt%. Accordingly, in some embodiments, hydrogen can be uced to aid in the conversion of tenes to soluble oils without influencing the deconstruction of the coal into oils but rather promoting the formation ofacetylene and gaseous hydrocarbons from methane and coal. Under the same conditions (1 atm pressure, no preheating, 18%CH4/1.5%H2 in Ar process gas, and coal feed rate of~5g/hr) the addition of a hydrotreating catalyst (CoMo/A1203) can improve the oil and tar yields to 29.7 and 38wt%, respectively. During these tests the coal itself was not generating rapid dielectric discharges, which is likely due to little to no exposure to microwave irradiation prior to entering the preformed plasma.

Table 14 Product Virltls t'roni oDM'r.sion hiinc ;ni(l C'oal in a Microna^c 1'lasina Overall Total Char Yield Char Yield Tar Yield Oil Yield (wt% total Liquid Net Gas Mass (wt% daf) (wt% daf) (wt% daf) daf) Yield (wt% daf) Yield (wt%) Balance (%) MWPy-169, 5%Fe Catalyst, 6%CH4inAr 85.63 64.05 11.79 14.80 26.59 -5.51 92.82 MWPy-201,5%Fe Catalyst, 18%CH4/1.5%HZin Ar 73.61 55.72 2.26 22.32 24.58 -0.67 99.26 MWPy-203, 5%Fe Catalyst+5% Hydrotreating Catalyst, 18%CH4/1.5%H2inAr 68.88 32.82 8.28 29.72 38.01 -2.61 97.22 195246NZ AMENDED SPEC SEPT2016000.DOCX To enhance dielectric discharges between coal particles, the reactor can be further modified to increase the exposure of coal to microwave energy by increasing the outer Ar sheath gas flow to avoid carbon coating on the wall of the reactor and/or by employing a modified flow distributor disk having a structure that resulted in higher gas velocity along the walls of the reactor. This enabled the inner feed tube to be raised above the main reaction zone, thus increasing the exposure time of the entrained coal to microwave irradiation. Alternative designs can be considered as part of the current embodiment that can include ative methods to introduce coal, HFH, gases, and microwave/RF energies.

In some embodiments, the coal feed rate is greater than 5 g/hr. For example, increasing the coal feed rate from ~5g/hr to 30g/hr dramatically improved tric discharging between coal les, likely due to increased proximity and uneven charging of coal particles ng corona discharging between particles. As a result of higher coal feed rates, the gas flow also can be increased from 4L/min to 12L/min to avoid reactor plugging due to coal swelling, which further improved dielectric rges between coal particles.

The sed flow rates results in a reduction of the residence time in the ave zone from 126 to 75 msec. Increasing the coal feed-rate, from 5 to 30g/hr, significantly increased the observation ofdielectric discharging between coal particles (run MWPy-215 in Table 15 Product Yields from Co-Conversion of Methane, Hydrogen, and Coal in a Microwave Plasma). This increase in the tric discharging between coal particles ed in a significant increase in oil yield to 35wt% (daf), despite the reduced residence time. This indicates that operational parameters such as coal (or HFH) particle proximity, concentration, exposure time to ave/RF irradiation, reactor configurations, wt% coal 195246NZ AMENDED SPEC SEPT 2016000.DOCX feed in the process gas, relative plasma position and energy density, and net residence time can all be adjusted and controlled to improve reactor performance, alter product distributions, increase product yields and reduce operational costs. Unlike the static bed tests, an entrained or fluidized coal bed can significantly enhance yields and performance by buting the coal, catalyst, or dilution media within the process gas allowing for uneven electric charge buildup, whereas when les are in direct contact the ability to generate uneven charge build up between particles is limited, thus reducing the degree ofdielectric discharging between entrained particles.

Table 15 Product ^ ifltls from C o-Cmnersion of Methane. Ihdroaen. ;nnl (. D;il in a MicrimaM' PI.I.MH.I Total Oil Total LIquic Net Gas BTO/Light Mass CH4 H2 CharYield Tar Yield Yield Yield Yield HC Yield Balance Conversion Conversion (wt% daf) (wt% daf) (wt% daf] (wt% daf) (wt%) (wt%, daf) (%) (%) (%) MWPy-211, 5%Fe Catalyst, 59.70 0.85 24.36 25.23 7.47 10.86 96.61 3.90 -7.88 3 Coal:H2:CH4 (wt ratio) - 700W MWPy-215, 5%Fe Catalyst, 45.60 7.13 34.87 41.99 0.46 17.85 89.17 11.25 -17.30 43:6:51 Coal:H2:CH4 (wt ratio) - 700W MWPy-219, 5%Fe Catalyst, 37.40 3.71 58.49 62.19 1.90 23.98 98.90 9.37 79:21 Coal:H2 (wt ratio) - 700W n.a.

In some embodiments, hydrogen and coal are co-fed. To compare directly the effect ofco-feeding methane versus co-feeding hydrogen, experiment MWPy-219 was performed and the results are shown in Table 15 t Yields from Co-Conversion of Methane, en, and Coal in a Microwave . By co-feeding hydrogen rather than e during sion significantly increased the oil yield to 58.5wt% (daf) and the overall liquid yield was 62wt% (daf). This increase is directly related to the need for increasing the plasma -density required for ient methane conversion during plasma conversion. During tests without co-feed of coal, methane conversions as high as 75% per pass were observed and when coal is co-fed the methane conversion observed is . This is due to the need for methane to be exposed to a plasma having relatively 195246NZ AMENDED SPEC SEPT2016000.DOCX higher energy y, which can be efficiently and readily generated in a plasma torch. If coal is pyrolyzed in a plasma torch reactor (or similarly a thermal ), the main product of coal conversion is acetylene and acetylene polymers and conversion is limited by mass er of the ions within the plasma to the surface of the coal. Testing performed indicates that a yield of oil under such operation leads to ~20-25wt% (daf) and the product selectivity is ~80-85% BTX with only minimal sion to distillate fuel boiling range compounds.

However, by vely increasing the intensity and occurrences of dielectric discharges the oil yield can be improved, but the lower-energy plasma is not sufficient for high methane conversions. Preferably, a natural gas sion unit is segregated and en, rather than methane, is co-fed with the coal. In such instances, an oil yield of58.5wt% has been demonstrated. Due to the differences in the "mode" of operation required for optimal methane conversions and high oil yields from coal, preferred embodiments segregate the two processes and use RF or barrier discharge rs for methane conversion and continue to use microwave energy for conversion of coal ned in hydrogen (and other product gases from methane conversion).

Alternative tic materials can be used to help lower the energy requirements associated with co-feeding methane and coal, while improving overall methane conversions.

An example of including a reduced nickel catalyst into the reaction zone is illustrated in Table 16 where NiSAT® catalyst (commercial Nickel-based catalyst Sud-Chemie) was added to the coal feed mix. In this particular example when hydrogen was co-fed with the coal the overall liquid yield was 46.16 wt%, indicating the Ni is also aiding in increasing the hydrogen transfer reaction thus increasing the oil yield when compared to the case without Ni catalyst. When methane is co-fed with the hydrogen and coal (with the Ni catalyst) the 195246NZ AMENDED SPEC SEPT2016000.DOCX liquid yield further increased to 62wt% and 34% of the methane was ted into other ts, including hydrogen as indicated by the negative hydrogen conversion number (indicates more hydrogen is exiting the reactor than entering the reactor). This demonstrates one method in which energy required for methane decomposition can be lowered by variations in catalytic materials that can help promote hydro genation, methane decomposition, and hydrogen formation.

Table 16. .Summnn of results nhcn M*>.\ I ' c;it;i^.st is ;ultle(l to the cu.il tt'ed mix fur niifr<ni;i\t' ciniM'r.'.inn Total Oil Total Uquic Net Gas BTX/Ught Mass CH4 HZ Char Yield TarYleld Yield Yield Yield HCYield Balance Conversion sion (wt% daf) (wt% daf) (wt%daf) (wt% daf) (wt%) (wt%, daf) (%) (%) (%) MWPy-263: PittffS + 5%Fe Catalyst +5% NISAT 50.07 5.67 40.49 46.16 5.84 18.70 100.02 n.a. 16.94 6:1 Coal:H2, 29.4g/hrcoal feed rate 700W microwave power 600W ic MWPy-265: Pltt#8+5%Fe Catalyst+5% NiSAT 8:1:8 Coal:H2:CH4, hrcoal feed rate 55.43 8.80 53.32 62.12 -16.14 17.06 99.71 34.18 -9.70 700W microwave powerGOOW ic While a number of embodiments of the present invention have been shown and described, it will be apparent to those skilled in the art that many changes and modifications may be made t departing from the invention in its broader s. The appended claims, therefore, are intended to cover all such changes and modifications as they fall within the true spirit and scope of the invention. 195246NZ AMENDED SPEC SEPT2016000.DOCX

Claims (30)

Claims We claim:

1. A method for continuous flash conversion of heavy fossil hydrocarbons (HFH), the method comprising: flowing a continuous feed comprising HFH and a process gas through a reaction zone having a pressure greater than 0.9 atm; contacting the HFH and a HFH-to-liquids catalyst in at least the reaction zone; concentrating microwave or RF energy in the reaction zone using a microwave or RF energy source; and generating dielectric discharges within the on zone; wherein the HFH and the catalyst have a residence time in the reaction zone of less than 30 seconds.

2. The method of Claim 1, wherein the process gas ses a hydrogen-containing gas.

3. The method of Claim 1, wherein the st comprises iron.

4. The method of Claim 1, wherein the catalyst comprises char.

5. The method of Claim 1, wherein the catalyst comprises a promoter of dielectric discharge.

6. The method of Claim 1, wherein the HFH and the catalyst are admixed.

7. The method of Claim 1, further comprising ting a plasma in or near the on zone.

8. The method of Claim 1, wherein the pressure in the reaction zone is up to 7 atm. 195246NZ AMENDED SPEC SEPT2016000.DOCX

9. The method of Claim 1, wherein the residence time is greater than or equal to 5 milliseconds.

10. The method of Claim 1, wherein said concentrating comprises emitting ave or RF energy from a source into the reaction zone in a direction el to the continuous feed through the on zone.

11. A system for continuous flash conversion of heavy fossil hydrocarbons (HFH) comprising: a reaction zone having a pressure greater than 0.9 atm; a source emitting microwave or RF energy concentrated in the reaction zone; a source of a continuous feed comprising HFH and a process gas, the continuous feed passing through the reaction zone; a HFH-to-liquids catalyst contacting the HFH in at least the reaction zone; and dielectric discharges within the reaction zone; n, the HFH and the catalyst have a residence time in the reaction zone of less than 30 seconds, when this system is operated.

12. The system of Claim 11, wherein the process gas comprises a hydrogen-containing gas.

13. The system of Claim 1 1, wherein the s gas is selected from a group consisting of nitrogen, carbon dioxide, methane, natural gas, recycle gas, carbon de, argon, water, oxygen, and combinations thereof.

14. The system of Claim 1 1, wherein the HFH concentration in the s gas is between 0.1 wt% and 100 wt%. 195246NZ AMENDED SPEC SEPT2016000.DOCX

15. The system of Claim 11, wherein the system comprises a fluidized bed reactor, an entrained flow reactor, a free fall reactor, or a moving bed reactor.

16. The system of Claim 1 1, n the catalyst comprises iron.

17. The system of Claim 11, wherein the catalyst comprises char.

18. The system of Claim 11, n the catalyst is selected from the group consisting of nickel, cobalt, molybdenum, , copper, alumina, , oxygen and combinations thereof.

19. The system of Claim 11, wherein the st comprises a promoter of hydrogenation.

20. The system of Claim 11, wherein the catalyst comprises a promoter of electrical discharge.

21. The system of Claim 11, wherein the catalyst comprises a promoter of hydrogen formation.

22. The system of Claim 11, wherein the catalyst is a dilution material.

23. The system of Claim 1 1, wherein the catalyst and the HFH are admixed.

24. The system of Claim 11, further comprising a plasma in or near the reaction zone.

25. The system of Claim 11, wherein the pressure in the reaction zone is up to 7 atmospheres.

26. The system of Claim 11, n the residence time is greater than or equal to 5 milliseconds.

27. The system of Claim 11, wherein the catalyst has a concentration n 0.5 and 10 wt% relative to the HFH. 195246NZ AMENDED SPEC SEPT2016000.DOCX

28. The system of Claim 1 1, further comprising a on material and the continuous feed at a concentration between 0 and 30 wt%.

29. The system of Claim 1 1, wherein the microwave or RF energy is emitted in a parallel direction to the continuous feed through the reaction zone.

30. The system of Claim 11, wherein the dielectric discharges are generated in the reaction zone when the system is ed.