WO2014145169A2

WO2014145169A2 - Systems, methods and apparatuses for a compact reactor with finned panels

Info

Publication number: WO2014145169A2
Application number: PCT/US2014/029886
Authority: WO
Inventors: John Hemmings
Original assignee: Gi-Gasification International (Luxembourg), S.A.
Priority date: 2013-03-15
Filing date: 2014-03-15
Publication date: 2014-09-18
Also published as: WO2014145169A3

Abstract

Herein disclosed is a reactor comprising: a multiplicity of elements wherein each element comprises at least two folded fins and at least two spacers, wherein the at least two folded fins and spacers are attached to each other and form a flow passage for a heat transfer medium; a containment structure configured to contain the multiplicity of elements, wherein space formed between the elements and the containment structure is configured to contain a granular catalyst placed in proximity to the elements and configured to allow passage of a process fluid; and a structure placed at the bottom of the multiplicity of elements configured to support the granular catalyst. Also disclosed herein is a method of carrying out a reaction.

Description

SYSTEMS, METHODS, AND APPARATUSES FOR A COMPACT REACTOR WITH

FINNED PANELS

[0001] Not applicable.

RELATED CASES

[0002] This application claims priority from US Provisional Patent Application No. 61/800,090 filed on March 15, 201 3, which is incorporated herein by reference in its entirety.

[0003] The assignee of this application filed the following related provisional patent applications on March 1 5, 2013 : (1 ) US Provisional Application No. 61/798,981 , entitled "Systems, Methods and Apparatuses for a Compact Reactor" and having assignee patent file number GI-0006-US-P01 ; (2) US Provisional Application No. 61/799,485, entitled "Systems, Methods and Apparatuses for Use of Organic Rankine Cycles" and having assignee patent file number GI-0007-US-P01 ; (3) US Provisional Application No. 61/799,825, entitled "Systems, Methods and Apparatuses for a Shaped-Finned Reactor" and having assignee patent file number GI-0008-US-P01 ; and (4) US Provisional Application No. 61 /800,376, entitled "Systems, Methods and Apparatuses for Fischer-Tropsch Catalyst Regeneration" and having assignee patent file number GI-0035-US-P01 , all of which are incorporated herein by reference in their entireties.

[0004] The assignee of this application is filing on even date herewith the following related

PCT patent applications: PCT Application No. _t entitled "Systems, Methods and

Apparatuses for Use of Organic Rankine Cycles" and having assignee patent file number GI- 0007-WO-01, and claiming priorit from the above-mentioned US Provisional Application

Nos. 61/799,485 and 61 /799,825); and PCT Application No. , entitled "Systems,

Methods and Apparatuses for Fischer-Tropsch Catalyst Regeneration" and having assignee patent file number G1-0035-WO-01 and claiming priority from the above-mentioned US Provisional Application No. 61 /800,376, all of which are incorporated herein by reference in their entireties.

BACKGROUND

[0005J The present disclosure relates to systems and apparatuses for a compact reactor and methods of use; specifically it relates to systems and apparatuses for a compact reactor for catalytic reactions and applications thereof, including without limitation Fischer-Tropsch reactions.

Background of the Invention

[0006] A great many processes involve catalytic reactions, in which the rate of a chemical reaction is changed (e.g., increased) due to the participation of a substance called a catalyst. Unlike reagents, a catalyst does not participate in the chemical reaction and is not consumed by the reaction itself. In addition, a catalyst may participate in multiple chemical transformations. Catalytic reactions have a lower rate-limiting free energy of activation than the corresponding un-catalyzed reaction, resulting in higher reaction rate at the same temperature.

[0007] However, the mechanistic explanation of catalysis is complex. Catalysts may affect the reaction environment favorably, or bind to the reagents to polarize bonds, e.g. acid catalysts for reactions of carbonyl compounds, or form specific intermediates that are not produced naturally, such as osmate esters in osmium ietroxide-catalyzed dihydroxylation of alkenes, or cause lysis of reagents to reactive forms, such as atomic hydrogen in catalytic hydrogenation.

|0008] Furthermore, many catalytic reactions are exothermic (heat-generating) or endothermie (heat-absorbing) and thus require thermal energy management utilizing, for example, a heat exchange medium.

[0009J The Fischer-Tropsch (or "Fischer Tropsch," "F-T" or "FT") process (or synthesis or conversion) involves a set of chemical reactions that convert a mixture of carbon monoxide and hydrogen (known as reformed gas. synthesis gas, or "syngas") into liquid hydrocarbons (called "liquid FT hydrocarbons" herein). The process was first developed by German chemists Franz Fischer and Hans Tropsch in the 1920's. The FT conversion is a catalytic and exothermic process. The FT process is utilized to produce petroleum substitutes, typically from carbon-containing energy sources such as coal, natural gas, biomass, or carbonaceous waste streams (such as municipal solid waste) that are suitable for use as synthetic fuels, waxes and/or lubrication oils. The carbon-containing energy source is first converted into a reformed gas (or synthetic gas or syngas), using a syngas preparation unit in what may be called a syngas conversion. Depending on the physical form of the carbon-containing energy source, syngas preparation may involve technologies such as steam methane reforming, gasification, carbon monoxide shift conversion, acid gas removal gas cleaning and conditioning. These steps convert the carbon source to simple molecules, predominantly carbon monoxide and hydrogen, which are the active ingredients of synthesis gas but inevitably also containing carbon dioxide, water vapor, methane, nitrogen, impurities deleterious to catalyst operation such as sulfur and nitrogen compounds are often present in trace amounts and are removed to very low concentrations as part of synthesis gas conditioning.

[0010] Once the syngas is created and conditioned, the syngas is used as an input to an FT reactor having an FT catalyst to make the liquid FT hydrocarbons in a Fischer-Tropsch synthesis (or FT synthesis or FT conversion). Depending on the type of FT reactor, the FT conversion of the syngas to liquid FT hydrocarbons takes place under appropriate operating conditions.

[0011] Turning to the syngas conversion step, to create the syngas from natural gas, for example, methane in the natural gas reacts with steam and/or oxygen in a syngas preparation unit to create syngas. This syngas comprises principally carbon monoxide, hydrogen, carbon dioxide, water vapor and unconverted methane. When partial oxidation is used to produce the synthesis gas, typically it contains more carbon monoxide and less hydrogen than is optimal and consequently, the steam is added to the react with some of the carbon monoxide in a water-gas shift reaction. The water gas shift reaction can be described as:

CO + H₇0 ¾ H₂ + C0₂ (1 ) [0012] Thermodynamically, there is an equilibrium between the forward and the backward reactions. That equilibrium is determined by the concentration of the gases present,

[0013] The Fischer-Tropsch (FT) reactions for the FT conversion of the syngas to the liquid FT hydrocarbons may be simplistically expressed as:

(2n+ 1 ) H₂ + n CO→ C„H_2n+2 + n H₂0, (2) [0014] where 'n' is a positive integer.

[0015] The FT reaction is performed in the presence of a catalyst, called a Fischer-Tropsch catalyst ("FT catalyst"). Unlike a reagent, a catalyst does not participate in the chemical reaction and is not consumed by the reaction itself, in addition, a catalyst may participate in multiple chemical transformations. Catalytic reactions have a lower rate-limiting free energy of activation than the corresponding un-catalyzed reaction, resulting in higher reaction rate at the same temperature. However, the mechanistic explanation of catalysis is complex. Catalysts may affect the reaction environment favorably, or bind to the reagents to polarize bonds, e.g. acid catalysts for reactions of carbonyl compounds, or form specific intermediates that are not produced naturally, such as osmate esters in osmium tetroxide-catalyzed dihydroxylation of aikenes, or cause lysis of reagents to reactive forms, such as atomic hydrogen in catalytic hydrogenation. [0016] Furthermore, many catalytic reactions are exothermic (heat generating) or endothermic (heat absorbing) and thus require thermal energy management utilizing, for example, a heat exchange medium. The Fischer-Tropsch process is a highly exothermic process. It is known thai the FT process yields better products if it is operated at closer to isothermal conditions.

[0017] In addition to liquid FT hydrocarbons, the Fischer-Tropsch synthesis also commonly produces gases (called "FT tail gases" herein) and water (called "FT water" herein). The FT tail gases typically contain CO (carbon monoxide), C0₂ (carbon dioxide), H? (hydrogen), light hydrocarbon molecules, both saturated and unsaturated, typically having carbon values ranging from Q to C₄, and a small amount of light oxygenated hydrocarbon molecules such as methanol. Typically, FT tail gases are mixed in a facility's fuel gas system for use as fuel. The FT water will typically include dissolved oxygenated species, such as alcohols, and light hydrocarbons, which are typically removed prior to disposal of the FT water.

[0018] Therefore, there is a need to develop systems and methods that provide thermal energy management for catalytic reactions.

SUMMARY

[0019] Herein disclosed is a reactor comprising: a multiplicity of elements wherein each element comprises at least two folded fins and at least two spacers, wherein the at least two folded fins and spacers are attached to each other and form a flow passage for a heat transfer medium; a containment structure configured to contain the multiplicit of elements, wherein space formed between the elements and the containment structure is configured to contain a granular catalyst placed in proximity to the elements and configured to allow passage of a process fluid; and a structure placed at the bottom of the multiplicity of elements configured to support the granular catalyst.

[0020] In one or more embodiments of the present disclosure, the reactor further comprises a means to introduce the heat transfer medium to and remove the heat transfer medium from the flow passage formed by the folded fins and spacers, in one or more embodiments of the present disclosure, the reactor further comprises a means to introduce the process fluid and remove the process fluid from the space between the elements and the containment structure. In another embodiment, the reactor further comprises comprising inert solids placed between the multiplicity of elements and the catalyst support structure. In some cases, the inert solids are ceramic. [0021] In one or more embodiments of the present disclosure, the folded fins are made of a nieial selected from the group consisting of copper, brass, aluminum, and combinations thereof. In one or more embodiments of the present disciosure, the spacers are made of a metal selected from the group consisting of copper, aluminum, brass, and combinations thereof.

[0022] in one or more embodiments of the present disclosure, the heat transfer medium is an organic working fluid and comprises no water. In one or more embodiments of the present disclosure, the organic working fluid is a composition of Fischer Tropsch products. In one or more embodiments of the present disclosure, the granular catalyst is a Fischer-Tropsch catalyst. In one or more embodiments of the present disclosure, the process fluid is a Fischer- Tropsch process fluid.

[0023] In one or more embodiments of the present disclosure, at least a portion of the catalyst support structure is porous. In one or more embodiments of the present disclosure, the reactor is configured to product 0.3-3000 barrels/day of Fischer-Tropsch products. In one or more embodiments of the present disclosure, the reactor comprises more than one containment structure and a shell configured to house the more than one containment structure.

[0024] Herein disclosed is a reactor comprising: a multiplicity of elements wherein each element comprises a lower plenum, an upper plenum, and a channel made front folded fin comprising folds, wherein the lower plenum, upper plenum and one side of the folds are connected to form a flow passage for a heat transfer medium and the other side of the folds are configured to contain a catalyst and to allow passage of a process fluid; and a structure placed at the bottom of the multiplicity of elements configured to support the catalyst. In one or more embodiments of the present disclosure, the reactor further comprises a structure placed at the end and sides of the multiplicity of elements configured to contain the catalyst. In one or more embodiments of the present disclosure, at least a portion of the catalyst support structure is porous. In one or more embodiments of the present disclosure, the reactor further comprises a shell configured to contain the multiplicity of elements and the catalyst support structure. In some cases, the shell is a pressure vessel.

[0025] In one or more embodiments of the present disclosure, the folded fin is made from a material selected from the group consisting of aluminum, brass, copper, and stainless steel. In one or more embodiments of the present disclosure, the plenums are made from solid metal with grooves. In one or more embodiments of the present disclosure, the plenums have ports to allow the heat transfer medium to enter and leave the plenums. In one or more embodiments of the present disciosure, the elements are held together so that they are connected port to port. In one or more embodiments of the present disclosure, the distance between elements is suitable for installation of catalyst. In one or more embodiments of the present disclosure, the elements are approximately 1 mm to 4 mm apart at closest approach.

[0026] Also disclosed herein is a method of carrying out a reaction, comprising: providing a reactor comprising a multiplicity of elements wherein each element comprises at least two folded fins and at least two spacers, wherein the at least two folded fins and spacers are attached to each other and form a flow passage for a heat transfer medium; a containment structure configured to contain the multiplicity of elements, wherein space formed between the elements and the containment structure is configured to contain a granular catalyst placed in proximity to the elements and configured to allow passage of a process fluid; and a structure placed at the bottom of the multiplicity of elements configured to support the granular catalyst; and performing the reaction in the reactor.

0Θ27] In one or more embodiments of the present disclosure, the reaction is exothermic. In one or more embodiments of the present disclosure, the method is utilized for a Fischer- Tropsch process or a methanol synthesis process, in one or more embodiments of the present disclosure, the reactor produces 0.3-3000 barrels/day of Fischer- Tropsch products.

[0028] In one or more embodiments of the present disclosure, the heat exchange medium is an organic working fluid and comprises no water. In one or more embodiments of the present disclosure, the organic working fluid is a composition of Fischer Tropsch products.

[0029j In ^{0He or mo,}'^e embodiments of the present disclosure, the reactor comprises more than one containment structure and a shell configured to house the more than one containment structure and the method further comprises charging the containment structure and the elements contained therein with catalyst before placing the containment structure in the shell. In one or more embodiments of the present disclosure, the method comprises treating the catalyst-loaded containment structure so that the catalyst is evenly distributed. In one or more embodiments of the present disclosure, the method comprises vibrating the containment structure or randomizing the catalyst during catalyst loading.

[0030J Further disclosed is a method of carrying out a reaction, comprising: providing a reactor comprising a multiplicity of elements wherein each element comprises a lower plenum, an upper plenum, and a channel made from folded fin comprising folds, wherein the lower plenum, upper plenum and one side of the folds are connected to form a flow passage for a heat transfer medium and the other side of the folds are configured to contain a catalyst and to allow passage of a process fluid; and a structure placed at the bottom of the multiplicity of elements configured to support the catalyst; and performing the reaction in the reactor.

[0031] In one or more embodiments of the present disclosure, the reaction is exothermic, in one or more embodiments of the present disclosure, the method is utilized for a Fischer- Tropsch process or a methanol synthesis process, in one or inore embodiments of the present disclosure, the heat exchange medium is an organic working fluid and comprises no water. In one or more embodiments of the present disclosure, the organic working fluid is a composition of Fischer Tropsch products.

[0032] In one or more embodiments of the present disclosure, the method comprises charging the elements with the catalyst prior to placing the elements in a containment shell. In one or more embodiments of the present disclosure, the method comprises treating the catalyst- loaded elements so that the catalyst is evenly distributed.

[0033] These and other embodiments, features and advantages will be apparent in the following detailed description and drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

[0034] For a more detailed description of the present disclosure, reference will now be made to the accompanying drawings.

[0035] FIG. 1 is a side view of a reactor assembly, according to one or more embodiments of the present disclosure.

[0036J FIG. 2 is the cross-section viewed from the front of the reactor, which cross section is indicated by bold numeral "2" in FIG. 1.

[0037] FIGS. 3A and 3B are the cross-section views of inlet pipe manifold 23 and, similarly, the outlet pipe manifold 25that are depicted in FIG. 2. FlG. 4 is the cross-section viewed from the top of the reactor, which cross section is indicated by bold numeral "4" in FlG. 1.

[0038] FIG. 5 is the blow-up view of bold numeral "5" in FIG. 4.

[0039] FIG. 6 is the blow-up view of bold numeral "6" in FlG. 5,

[0040] FlG. 7 is an element header view (flat head) of a reactor, according to one or more embodiments of the present disclosure.

[0041 ] FIG. 8 is element header view (pipe header) of a reactor, according to one or more embodiments of the present disclosure.

DETAILED DESCRIPTION

V |0042] OVERVIEW. One or more embodiments of the finned panel reactor as described herein are suitable for a process that involves catalytic reactions (exothermic or endothermic). One or more embodiments of the finned panel reactor as described herein are also configured to provide heating for an endothermic reaction and to provide cooling for an exothermic reaction. The details of such a reactor, processes using such a. reactor and the uses thereof are described herein below.

[0043] In one or more embodiments of the present disclosure, an exothermic chemical reaction is carried out using a fine-grained heterogenous catalyst (50 to 200 micron equivalent diameter) contained within microchannels that are formed by a folded fin of a highly conductive material, such as copper or aluminum. In one or more embodiments of the present disclosure, the fin material is 0.1 - 0.3 mm thick and folded into corrugations that are 3 - 50 ram high and 0.6 - 2 mm across, in one or more embodiments of the present disclosure, the folded fin-stock is formed into panels, with coolant distribution below and coolant collection above in plenums.

[0044] In one or more embodiments of the present disclosure, the reactor comprises a number of heat removal elements, enclosed in a pressure vessel with a means to contain the finegrained catalyst such that catalyst is in intimate contact with the heat transfer element, as illustrated in FiGS. 1-6.

[0045] REACTOR. Turning first to FIG, 1, a side view of a reactor assembly, according to one or more embodiments of the present disclosure is illustrated. The reactor 100 includes a reactor shell 20, a coolant inlet 102 and a plurality of cooling elements 24. The reactor 100 also includes a process fluid inlet 103, a process fluid outlet 104, and a coolant outlet (not depicted in FIG. 1). The number of cooling elements 24 that are deployed in a single reactor 100 is limited by coolant side manifold pressure drop considerations, in one or more embodiments of the present disclosure, the reactor 100 is between 30 and 10,000 mm long with between 1 and 1 ,000 cooling element 24. In one or more embodiments of the present disclosure, the reactor 100 contains between 3 and 30,000 liters of catalyst, capable of 0.3 to 3,000 barrels per day (BPD) of production.

[0046] While the language in the preceding paragraph and in some subsequent paragraphs describe applications using cooling elements 24, in other embodiments heat transfer elements that are not cooling elements can be substituted for the cooling elements 24, with similar changes of substituting other heat transfer components being substituted for corresponding cooling components, for applications in which a heat transfer fluid other than a coolant is used. [0047] in one or more embodiments of the present disclosure, the reactor 100 is designed to utilize water as the coolant. In one or more embodiments of the present disclosure, the reactor 100 is designed to utilize boiling water as the coolant. In another embodiment, the reactor 100 utilizes an organic working fluid as the coolant (the "Organic Rankine Cycle" version), as further described in the previously mentioned, co-pending US Provisional Application No. 61/799,485, entitled "Systems, Methods arsd Apparatuses for Use of Organic Rankine Cycles" and having assignee patent file number GI-0007-US-P01. For the "Organic Rankine Cycle" version, the reactor system is designed to withstand a modest differential pressure, for example, less than 1 bar. The design of the reactor of this disclosure is straightforward and economic to fabricate, compared to alternative methods of fabricating microchannel reactors.

[0048] In one or more embodiments of the present disclosure, the cooling element 24 is 7 - 100 mm thick, 200 - 1800 mm wide, and 600 - 1800 mm high, in one or more embodiments of the present disclosure, a number of cooling elements 24 are assembled together with coolant supply and return from common headers. In one or more embodiments of the present disclosure, the cooling elements 24 are closely spaced together, e.g., with a spacing of 0.5 - 4 mm (approximately equal to the spacing between adjacent fins). In one or more embodiments of the present disclosure, each cooling element 24 consists of a channel for flow of coolant and has a volume of catalyst contained within the folds of the fins on the outside of the coolant channel and the distance from any point within the catalyst volume to the cooled surface is small, approximately half of the fin spacing. This arrangement leads to extremely efficient contact between catalyst and coolant.

[0049] In one or more embodiments of the present disclosure, the reactor 100 is arranged with nozzles to connect to the external coolan piping at one end of the vessel, in the head, so that the assembly is free to slide into the vessel, in one or more embodiments of the present disclosure, the reactor 100 of this disclosure is utilized for a FT process, in this case, the syngas inlet and process outlet nozzles may be placed in the shell (as shown in FIG. I),

[0050] FIG. 2 is a cross-section viewed from the front of the reactor 100, which cross-section is indicated by bold numeral "2" in FIG. 1. in FIG. 2, the shell 20 of the reactor 100 comprises a cylindrical pressure containment shell, having an upper chamber 29 and a lower chamber 30. Within the shell 20, the reactor 100 includes a reactor assembly that comprises a plurality of cooling elements 24, a coolant inlet flow channel 22, a coolant return flow channel 26, an inlet pipe manifold 23 ftuidly connecting the coolant inlet flow channel 22 with the cooling elements 24, and an outlet pipe manifold 25 fluidly connecting the cooling elements 24 with the coolant return flow channel 26. Placement of inert solids 18 are also depicted in FIG. 2. inside the shell 20 are channels 21 formed by attaching two strips of metal to the shell (by weiding) forming grooves which can engage with projections from the reactor assembly and therefore into which the reactor assembly is able to slide. In one or more embodiments, the channels 21 are U-shaped and are contain a sealant that conforms to the reactor assembly when the reactor assembly is slid into place within the reactor shell 20. An FT catalyst is contained in a bed between the elements, the bed formed by two side walls 27, and a porous catalyst support 28, for example a Johnson screen having inert solids above the screen. Process fluid enters the upper chamber 29 and leaves from the lower chamber 30. If a slice is taken through the fins and catalyst bed, there are three distinct layers of solid material - inert at bottom and top, catalyst in the middle. In one or more embodiments of the present disclosure, the catalyst in the middle is in between the fins, which are full of coolant.

[0051| The mechanical strength of the cooling element 24 is a function of the precise geometry in particular the thickness of the metal used for the fins, the depth and pitch of the fins, the number of spacers employed, the design of the inlet and outlet coolant plenums, such as the thickness of metal used for the flat head, the thickness of metal used in end strips and brazing or other joining technique used.

[0052] FIGS. 3A and 3B are the cross-section views of inlet pipe manifold 23 and, similarly, the outlet pipe manifold 25that are depicted in FIG. 2. In one or more embodiments of the present disclosure, a bottom pipe header at forms the inlet pipe manifold 23 and a top pipe header forms the outlet pipe manifold 25. The inlet pipe manifold 23 may have a pipe diameter of 13 mm at the far end, that is, away from where the inlet pipe manifold 23 connects with the coolant inlet flow channel 22, while having a pipe diameter of 50 mm high at the near end. The top pipe header might have the reverse dimensions. To achieve this effect, for the smaller diameter, the pipe header is cut at 90 degrees to the length of the cooling element, the end of the pipe that is cut will be circular as depicted in FIG. 3A and the diameter will be relatively small. In other cases, each pipe header is cut axially and triangular gussets are inserted, so that the end of the pipe cut will be ova! and the diameter will be relatively larger, as depicted in FlG. 38.

[0053] In one or more embodiments of the present disclosure, the 500 cooling elements 24 are fed from a manifold, such as a pipe, which is sized so that the manifold pressure drop is small compared to the pressure drop in the header. In one or more embodiments of the present disclosure, the pipe is between 300 mm and 900 mm in diameter with 500 cooling elements 24. In one or more embodiments of the present disclosure, coolant from the cooling elements 24 is collected as a manifold, such as a pipe, which is from 300 mm to 900 mm in diameter. In some embodiments, it is more convenient to employ a non-circular manifold, such as a flow channel defined between a flat plate and a curved plate formed in the arc of a cylinder, in such an embodiment, the flat plate may serve to contain the catalyst against the heating elements and the curved plate may be designed so that the entire assembly is able to slide easily into a containment shell of circular cross section. This concept is depicted in FIG. 2, which illustrates positioning of the shell 20, the coolant inlet flow channel 22, and the coolant return flow channel 26.

[0054] Referring again to FiG. 1, in one or more embodiments of the present disclosure, a finned panel reactor 100 of this disclosure comprises 500 cooling elements 24 and is capable of 800 BPD of FT products. As an example, it has 2,835 liters of catalyst contained within a box (7,000 mm long; 600 mm high; ! ,200 mm wide). In one or more embodiments of the present disclosure, the 500 cooling elements 24 are deployed 1 mm apart at the narrowest. In some eases, each element is made from a folded fin with a fin height of 5 mm, fin spacing 1 mm and the two folded fins that make up the element are deployed 3 mm apart, using 3 mm square bar spacers with 50 mm spacing.

[0055] FiG. 4 is a horizontal cross-section viewed from the top of the reactor, which cross section is indicated by bold numeral "4" in FiG. I. in FIG. 4, a containing wall 10 for providing a boundary for a catalyst 12 and for the cooling elements 24 may comprise a pressure boundary, suitably reinforced; or alternatively may comprise a thin walled containment, intended to be housed within a pressure vessel. The catalyst 12 may comprise a granular catalyst deployed between the cooling elements 24. A passage J 1 is formed within each cooling element 24 to allow flow of the coolant within the cooling element 24.

[0056] FIG. S is a detailed view of bold numeral "5" in FiG. 4 and depicts details of each cooling element 24. Each cooling element 24 comprises a plurality of folded fin panels 1, an end plate 2 at either end, and spacers 3. The spacers 3 hold the folded fin panels I apart. The plurality of folded fin panels 1, an end plate 2 at either end, and spacers 3 may be brazed together. In various embodiments, the folded fin panels 1 are formed from copper, or aluminum sheet as described herein, the end plates 2 are made of copper or brass in case of copper fins, or aluminum in case of aluminum fins. In some embodiments, the spacers 3 are made of square, rectangular or round sections of copper, brass or aluminum as applicable. The spacers 3 add strength to the assembly of cooling elements 24 and improve the ability to withstand a pressure differentia! between coolant and process sides, |00S7] FlG, 6 is the blow-up view of bold numeral "6" in FIG, 5. Two folded fin panels 1 are joined together to form a cooling element 24. The folded fin material is as shown in FiG. 6, when viewed from the top, i.e. viewed in a plane orthogonal to the direction of process How.

[0058] The coolant flow may be understood with reference to FIGS. 1, 2 and 5. In FiG. 1, a coolant enters the coolant inlet 102 shown on Fro. 1 and leaves by means of the coolant outlet. (The coolant outlet is not depicted on FIG. J , as the coolant outlet would be behind the coolant inlet in that view.) The coolant inlet 102 and the coolant outlet may comprise similar nozzles. The coolant inlet 102 opens into a coolant inlet flow channel 22, as shown in FiG. 2. The coolant flows along the coolant inlet flow channel 22 and enters the inlet pipe manifold 23 fluidly connecting the coolant inlet flow channel 22 with the elements 24. The coolant then flows upwards in the space formed between the folded fin panels 1 and contained by end plates 2, as depicted by FiG, 5. The coolant may undergo partial phase change as it flows upwards in the cooling elements 24 and enters the outlet pipe manifold 25 in FiG. 2 and then flows along the coolant return flow channel 26 to the coolant outlet.

[0059] In one or more embodiments of the present disclosure, the active reactor itself is 1,200 mm wide by 7,000 long by 600 mm high. In one or more embodiments of the present disclosure, the catalyst is contained at the sides by plates 1,000 ram high that slide into "U" shaped channels inside the top and bottom of a pressure containment shell. In some cases, the U shaped channels are packed with a material such as ceramic fiber or are filled with an appropriate caulking material from external holes (tapped and plugged) to minimize the leakage around the reactor.

[00601 to ^{or!e or} raj ore embodiments of the present disclosure, an organic coolant compatible with the process fluid is utilized, operating at similar pressures, the requirement for sealing between the coolant and the process in this case is less than what is needed for a water-cooled system.

[0061] in one or more embodiments of the present disclosure, the coolant manifolds are segments of a circle in cross section and are defined by the side plates and arcs of a circle welded to the side plates, such that the assembly is able to slide into a circular shell. In one or more embodiments of the present disclosure, the coolant elements 24 are 1200 mm wide, 600 mm high and 13 mm thick, with wave-forms that may be 5 mm high by 1 mm pitch. In one or more embodiments of the present disclosure, the catalyst bed contains approximately 5.7 liters of catalyst per element, capable of producing 1 .6 BPD per element. In one or more embodiments of the present disclosure, an installation consists of ί to 500 such cooling elements, therefore such an installation would have an overall length of from 14 to 7.000 mm, and would be capable of producing 1.6 to 800 BPD of FT products when the reactor is utilized for a FT process.

[0062] Referring again to FIG. 2, the inlet pipe manifold 23 and the outlet pipe manifold 25 are designed so that the pressure drop is reasonable. This requires an increase in How area towards the inlet of the inlet pipe manifold 23 and the outlet of the outlet pipe manifold 25 Thus, if a pipe header is used, it would preferably need to change from circular cross section at the far end, as depicted in FIG. 3.4, to a cross section with higher surface at the near end. This, for example, is accomplished by cutting the pipe axial iy and inserting triangular gussets so that the cross section is as shown in FIG. 3B.

[0063] In one or more embodiments of the present disclosure, the header at the near end is welded or brazed into an axial header that has sufficient cross sectional area to take all of the flow from all of the elements.

[0064] There are several alternative embodiments for the coolant inlet manifold 23 and the coolant outlet manifold 25. FIGS. 7 and 8 show alternative details for the top headers. In various embodiments, the bottom headers are the same as the top headers.

[006S] Turning first to FlG. 7, instead of a spacer 3, one or more alternative embodiments employ a modified spacer 5 at the top and bottom of the device. The modified spacer 5 may be hollow or "U" shaped and serves to collect fluid. The modified spacer 5 is preferably sealed by attaching an end plate 6 made from brass, copper or aluminum and formed with indentations matching the corrugations of the fin. The end plate 6 may affixed to the fins, for example, by brazing or welding, in one or more embodiments of the present disclosure, the end plate 6 comprises a plate that has been cut out (for example, using a laser cutting machine) to look exactly like the cross section of the folded fins and is the right size to fit inside the folded fins, as depicted in FIG. 7. In various embodiments, large quantities of indented end plates 6 are produced, for example using laser profile cutting equipment. For the outlet header, coolant flows upwards between the fm 1 and the U-shaped spacer 5 and then along the U-shaped spacer 5 towards the sides of the cooling element 24 In one or more embodiments of the present disclosure, the coolant is then directed into a nozzle that is welded or brazed to the end strip of the cooling element 24. The inlet header is the reverse, fluid flows in through a nozzle and is distributed along the finned cooling element 24 using a U-shaped channel that also serves as a modified spacer 5.

[0066J Turning now to FlG. 8, in one or more embodiments, the coolant inlet manifold 23 and/or the coolant outlet manifold 25 comprise a so-called "pipe-header." A pipe header is

3 3 formed of a pipe or tube with an outside diameter equal to the width of the cooler element 24. The pipe header has slots cut across its axis and along its axis to accommodate the folds of the finned sheets that make up the folded fin panels 1. The header pipe is joined to the cooler element 24 by brazing. The general concept is depicted in FIG. 8, which depicts the pipe header 4, the spacer 3 and the folded fin panels 1.

[0067] There are further alternative designs, for example, the top and bottom flat heads may be replaced by a casting which is shaped to fit inside the fin form and attach by welding and transitions into a plenum in which flow is essentially vertical and directed into a nozzle or nozzles.

[0068J Regardless of the method of attachment of headers to the cooling elements, the general principle is to arrange an assembly of cooling elements so that they are 0.5 to 4 mm apart at the closest approach, and to fill the volume between elements with granular catalyst. The catalyst requires a support, which may take various forms, depending on the header design. With pipe headers, the process flow may enter and leave the catalyst bed through a rather narrow slot between adjacent pipes. In the fiat end plate version, process flow enters and leaves across essentially the same cross section as the bulk catalyst.

[0069] Catalyst Support. In one or more embodiments of the present disclosure, the catalyst support comprises a Johnson screen or sintered metal plate 5 to 25 mm below the elements with a layer of inert ceramic material, too large to enter the elements, between the bottom of the cooling elements and the top of the Johnson screen or sintered plate. In one or more embodiments of the present disclosure, the catalyst bed, in the vicinity of the cooling elements, is packed with fine grained inert material and catalyst, in a further embodiment, a layer of inert material is employed at the bottom of the cooling elements where heat transfer may be compromised (in particular in the vicinity of the headers).

{0070] Shell. In one or more embodiments of the present disclosure, the reactor shell 20 is made of a metal selected from the group consisting of stainless steel, carbon steel, 1SO-4948 alloy steels (e.g., steel alloys containing various amounts of alloying elements such as Chromium, Molybdenum, and Vanadium), combinations thereof, and other metals commonly used for pressure vessels.

[0071] Flos, in some embodiments, the folded fins 1 are made of a metal selected from the group consisting of copper, aluminum, brass, and high thermal conductivity alloys, in this disclosure, high thermal conductivity material is generally considered to possess a thermal conductivity of 100 W/m-K or higher, including copper, aluminum, and certain copper alloys. [0072] METHOD OF USE. The reactor disclosed herein may be used in many processes. In one or more embodiments of the present disclosure, the reactor is used in a FT process, In another embodiment, the reactor is used in methanol synthesis process.

[0073] FT Process,

[0074] For exothermic reactions, such as FT processes, the reactor in one or more embodiments of the present disclosure may be configured so that heat generated by the reactions is taken away by the heat exchange medium. In some cases, sufficient heat is taken away by the heat exchange medium so that the reactions within the reactor take place at close to isothermal conditions. For endothermic reactions, the heat exchange medium provides the necessary thermal energy for the suitable reactions to take place inside the reactor.

[0075] In one or more embodiments of the present disclosure, the operation temperature of the reactor is in the range of from about i 60 °C to about 260 °C; or alternatively from about 180 °C to about 240 °C; or alternatively from about 200 °C to about 230 °C. In some embodiments, the allowed temperature deviation from isothermal operation is in the range of from about 1 °C to about 10 °C; or alternatively from about 1 °C to about 5 °C; or alternatively from about 1 °C to about 2 " . in one or more embodiments of the present disclosure, the operation pressure of the reactor is in the range of from about 5 bar to about 40 bar; or alternatively from about 10 bar to about 30 bar; or alternatively from about 20 bar to about 30 bar. In one or more embodiments of the present disclosure, the processing capacity of the reactor is in the range of from about 0.3 barrels/day to about 3000 barrels/day.

[0076] In one or more embodiments of the present disclosure, the CO-io~]¾ ratio is in the range of from about 1.2 to about 2,2; or alternatively from about 1.4 to about 2; or alternatively from about 3.6 to about 1.8. In one or more embodiments of the present disclosure, the CO-to-H₂ ratio depends on the catalyst chosen to be used in the process, as well as on other details of the configuration and arrangement of reactors,

[0077] FT Catalyst In various embodiments, any known FT catalyst may be used in the reactor of this disclosure. Some examples are transition metal catalysts, such as nickel catalysts, cobalt catalysts, iron catalysts, and ruthenium catalysts. In some embodiments, the catalysts also have one or more suitable promoters, such as alkali metal oxides, copper, platinum group metals. In embodiments, these catalysts are supported on high-surface-area binders or supports, such as silica, alumina, zirconia, titania or zeolites.

[0078] In one or more embodiments of the present disclosure, the reactor is assembled without catalyst for purpose of pressure testing during fabrication. In one or more embodiments of the present disclosure, the assembly comprising heat transfer elements and containment is charged with catalyst prior to installation in the pressure vessel shell, in one or more embodiments of the present disclosure, the catalyst-loaded assembly is treated to ensure even catalyst distribution, such as vibrating the assembly during catalyst loading and/or using a spinning riffler or another suitable device to randomize the catalyst material as it enters the bundle.

[0079] In one or more embodiments of the present disclosure, removal of the catalyst requires vibration as a minimum - and may require more vigorous methods, depending on the details of the top and bottom headers and consequently on the free space available. In one or more embodiments of the present disclosure, the porous catalyst support is detachable, for example by attaching to side walls 27 (depicted in FIG. 2) by means of brackets and screws. This enables the catalyst side of the reactor to be serviced, for example to remove used catalyst using water or air. Once the spent catalyst has been removed, the assembly of elements may be pressure tested and leak tested and any elements requiring servicing may be repaired or replaced.

[0080] Organic Working Fluid, in one or more embodiments of the present disclosure, the heat transfer medium (i.e., working fluid) is a mixture of appropriate organic chemicals, compatible with process fluids and designed to boil at a temperature and pressure desired for the reaction. The use of organic working fluid for such applications is disclosed in the previously mentioned, co-pending US Provisional Patent Application No. US Provisional Application No. 61/799,485. In the case of one or more embodiments of the present disclosure, for "low temperature" Fischer Tropsch reaction conditions, the heat transfer medium is a light naphtha which is essentially a mixture of n-pentane, n-hexane and n- heptane, which may be obtained by distillation from the FT reaction product. The precise composition of the n-pentane - n-hexane - n-heptane mixture depends on the desired operating pressure and temperature. Typically, the Fischer Tropsch reaction itself is carried out a¹ a pressure between 10 and 40 bar and at a temperature between 170 °C and 230 °C. Thus, the mixture composition varies from 70% n-hexane, 30% n-heptane to boil at 1 75 °C and 10 bar through 80% n-pentane, 20% n-hexane at typical conditions ί 90 °C and 27 bar.

[0081] Sub-Critical assd S per-Critical Operations. As described in the previously mentioned co-pending US Provisional Patent Application No. US Provisional Application No. 61/799,485, the organic working fluid may be used at subcritical or supercritical conditions.

[0082] In one or more embodiments of the present disclosure, the operation temperature of the reactor 101 (depicted in FIGS. 11 and 12) is in the range of from about 160 °C to about 260 °C; or alternatively from about 1 80 °C to about 240 °C; or alternatively from about 200 °C to about 230 °C. In some embodiments, the allowed temperature deviation from isothermal operation is in the range of from about 1 °C to about 10 °C; or alternatively from about 1 °C to about 5 °C; or alternatively from about 1 °C to about 2 °C. in one or more embodiments of the present disclosure, the operation pressure of the reactor is in the range of from about 5 bar to about 40 bar; or alternatively from about 10 bar to about 30 bar; or alternatively from about 20 bar to about 30 bar. In one or more embodiments of the present disclosure, the processing capacity of the reactor is in the range of from about 100 barrels/day to about 2000 barrels/day; or alternatively from about 100 barrels/day to about 1000 barrels/day; or alternatively from about 100 barrels/day to about 500 barrels/day,

[Θ083] In one or more embodiments of the present disclosure, the CO-to-H? ratio is in the range of from about 1.2 to about 2.2; or alternatively from about 1.4 to about 2; or alternatively from about 1.6 to about 1.8. In one or more embodiments of the present disclosure, the CO-to-¾ ratio depends on the catalyst chosen to be used in the process, as well as on other details of the configuration and arrangement of reactors.

[0084] Operation Mode, in various embodiments, the reactor of this disclosure may be used in parallel or in series or in combination thereof. In one or more embodiments of the present disclosure, the reactor of this disclosure is used in a continuous process, in some embodiments, the reactor is used in a semi-continuous fashion, e.g., for certain reactions where coke formation takes place and coke removal is subsequently necessary.

[0085] While other means to achieve similar performance objectives have been proposed, such as the designs of Velocys, CompaetGTL, and Heatric, the present configuration offers significant economic advantages over these.

[0086] Other Processes. Other exothermic or endothermic processes may use the reactor of this disclosure in the same fashion. For example, methanol synthesis is an exothermic process: CO + 2H₂ = CH₃OH - 90.97 kJ/moL By utilizing the disclosed reactor, the reaction heat is efficiently removed and a more uniform temperature profile is maintained, in some embodiments, multi-pass operaiion (e.g., reactor connected in series) is performed to obtain desired conversion rates of the reactants/feed stream (syngas).

[0087] Operatio&s. In various embodiments, the reactor of this disclosure may be used in parallel or in series or in combination thereof, in one or more embodiments of the present disclosure, the reactor of this disclosure is used in a continuous process.

EXAMPLES 0088] Examples of reactors consisting of from 1 to 100 elements are shown in Table 1 ;

Table 1

Unit Demo 25 BPD 500 Bf

Number of elements 1 10 100

Depth of fins mm 25 25 25

Pitch of fins - catalyst side mm 1.6 1.6 1.6

Pitch of f ns - coolant side mm 1.6 1.6 1.6

Width of finned panel m 250 600 1,200

Fin Thickness mm 0.2 0.2 0.2

Spacer thickness mm 6 6 6

Gap between elements mm 2 2 2

Length of Element Pack mm 58 580 5,800

Flow area - coolant side m 0.0071 0.1693 3.3867

Flow area - catalyst side m" 0.0061 0.1453 2.9067

Length of Process Channels mm 600 600 600

Volume Available for Catalyst Liter 4 87 1,744

BPD at STD Conditions* (3.5

liter/BPD) 1 25 498

Typical Heat Load (at 20 kW/BPD) kW 2 50 997

Flow of Coolant based on Heat Load I Kg/h 222 5,332 106,63:

Coolant Mass Velocity g/h/m² 31,486 31 ,486 31 ,486

Inlet Density Kg/m³ 326 326 326

Outlet Density Kg/m³ 201 201 201

Infet Velocity m/s 0.0269 0.0269 0.0269

Outlet Velocity m/s 0.0435 0.0435 0.0435 inlet header velocity m/s 2 2

Outlet header velocity m/s 2 2

inlet header diameter mm 1 1 54 241

Outlet header diameter_. mm 14 68 306

STD* Conditions (Standard conditions): 21 °C, 2.0: 1 H2/CO at inlet, 30 bar, 20% inerts at i let for the catalyst

[0089] The examples provided above utilize an organic working fluid as the cooling fluid. The organic working fluid comprises a Fischer Tropsch liquid containing mainly pentane and fiexane. It should be noted that the commercial scale reactor, 500 BPD consists of a pack of 100 elements and has an overall length of 6,000 mm and a width of 1,200 mm. This is housed in a pressure vessel 1,400 mm in diameter and 6,000 mm tangent to tangent. Such a reactor delivers comparable performance to a tubular reactor 3,500 mm in diameter and 9,000 mm in tube length.

[0090] While preferred embodiments of the invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the invention. The embodiments described herein are exemplary only, and are not intended to be limiting. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention. Where numerical ranges or limitations are expressly stated, such express ranges or limitations should be understood to include iterative ranges or limitations of like magnitude falling within the expressly stated ranges or limitations. The use of the term "optionally" with respect to any element of a claim is intended to mean that the subject element is required, or alternatively, is not required. Both alternatives are intended to be within the scope of the claim. Use of broader terms such as comprises, includes, having, etc. should be understood to provide support for narrower terms such as consisting of, consisting essentially of, comprised substantially of, and the like.

[0091] Accordingly, the scope of protection is not limited by the description set out above but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an embodiment of the present disclosure. Thus, the claims are a further description and are an addition to the preferred embodiments of the present disclosure. The inclusion or discussion of a reference is not an admission that it is prior art to the present disclosure, especially any reference that may have a publication date after the priority date of this application. The disclosures of ail patents, patent applications, and publications cited herein are hereby incorporated by reference, to the extent they provide background knowledge; or exemplary, procedural or other details supplementary to those set forth herein.

Claims

CLAIMS What is claimed is:

1. A reactor comprising:

a multiplicity of elements wherein each element comprises at least two folded fins and at least two spacers, wherein the at least two folded fins and spacers are attached to each other and form a flow passage for a heat transfer medium;

a containment structure configured to contain the multiplicity of elements, wherein space formed between the elements and the containment structure is configured to contain a catalyst placed in proximity to the the elements and configured to allow passage of a process fluid; and

a structure placed at the bottom of the multiplicity of elements configured to support the catalyst.

2. The reactor of claim 1 further comprising a means to introduce the heat transfer medium to and remove the heat transfer medium from the flow passage formed by the folded fins and spacers.

3. The reactor of claim 1 further comprising a means to introduce the process fluid and remove the process fluid from the space between the elements and the containment structure.

4. Ine reactor of claim 1 further comprising inert solids placed between the multiplicity of elements and the catalyst support structure.

5. The reactor of claim 4 wherein the inert solids are ceramic,

6. The reactor of claim 1 wherein the folded fins are made of a metal selected from the group consisting of copper, brass, aluminum, and combinations thereof.

7. The reactor of claim 1 wherein the spacers are made of a metal selected from the group consisting of copper, aluminum, brass, and combinations thereof.

8. The reactor of claim 1 wherein the heat transfer medium is an organic working fluid and comprises no water.

9. The reactor of claim 8 wherein the organic working fluid is a composition of Fischer Tropsch products.

10. The reactor of claim 1 wherein the catalyst is a granular catalyst.

11. The reactor of claim 1 wherein the catalyst is a Fischer-Tropsch catalyst.

12. The reactor of claim 1 wherein the process fluid is a Fischer-Tropsch process fluid,

13. The reactor of claim 1 wherein at least a portion of the catalyst support structure is porous.

14. The reactor of claim 1 wherein the reactor is configured to product 0.3-3000 barrels/day of Fischer-Tropsch products.

15. The reactor of claim 1 comprising more than one containment structure and a shell configured to house the more than one containment structure.

16. A reactor comprising:

a multiplicity of elements wherein each element comprises a lower inlet channel, an upper outlet channei, and a channel made from folded fin comprising folds, wherein the lower inlet channel, upper outlet channel and one side of the folds are connected to form a flow passage for a heat transfer medium and the other side of the folds are configured to contain a catalyst and to allow passage of a process fluid; and

17. The reactor of claims 16 further comprising a structure placed at the end and sides of the multiplicity of elements configured to contain the catalyst,

18. The reactor of claim 16 wherein at least a portion of the catalyst support structure is porous.

19. The reactor of claim 16 further comprising a shell configured to contain the multiplicity of elements and the catalyst support structure.

20. The reactor of claim 19 wherein the shell is a pressure vessel.

21. The reactor of claim 16 whereirs the folded fin is made from a material selected from the group consisting of aluminum, brass, copper, and stainless steel.

22. The reactor of claim 16 wherein the plenums are made from solid metal with grooves.

23. The reactor of claim 16 wherein the plenums have ports to allow the heat transfer medium to enter and leave the plenums.

24. The reactor of claim 16 wherein the elements are held together so that they are connected port to port.

25. The reactor of claim 16 wherein the distance between elements is suitable for installation of catalyst.

26. The reactor of claim 16 wherein the elements are approximately 1 mm to 4 mm apart at closest approach.

27. A method of carrying out a reaction, comprising:

providing a reactor comprising

a containment structure configured to contain the multiplicity of elements, wherein space formed between the elements and the containment structure is configured to contain a granular catalyst placed in proximity to the the elements and configured to allow passage of a process fluid; and

a structure placed at the bottom of the multiplicity of elements configured to support the granular catalyst; and

performing the reaction in the reactor.

28. The method of claim 27 wherein the reaction is exothermic,

29. The method of claim 27 wherein the method is utilized for a Fischer-Tropsch process or a methanol synthesis process.

30. The method of claim 27 wherein the reactor produces 0.3-3000 barrels/day of Fischer- Tropsch products.

31. The method of claim 27 wherein the heat exchange medium is an organic working fluid and comprises no water.

32. The method of claim 31 wherein the organic working fluid is a composition of Fischer Tropsch products.

33. The method of claim 27 wherein the reactor comprises more than one containment structure and a shell configured to house the more than one containment structure and the method further comprises charging the containment structure and the elements contained therein with catalyst before placing the containment structure in the shell.

34. The method of claim 33 comprising treating the catalyst-loaded containment structure so that the catalyst is evenly distributed.

35. The method of claim 34 comprising vibrating the containment structure or randomizing the catalyst during catalyst loading.

36. A method of carrying out a reaction, comprising:

providing a reactor comprising

a multiplicity of elements wherein each element comprises a lower plenum, an upper plenum, and a channel made from folded fin comprising folds, wherein the lower plenum, upper plenum and one side of the folds are connected to form a flow passage for a heat transfer medium and the other side of the folds are configured to contain a catalyst and to allow passage of a process fluid; and a structure placed at the bottom of the multiplicity of elements configured to support the catalyst; and

performing the reaction in the reactor.

37. The method of claim 36 wherein the reaction is exothermic.

38. The method of claim 36 wherein the method is utilized for a Fischer-Tropsch process or a methanol synthesis process.

39. The method of claim 36 wherein the heat exchange medium is an organic working fluid and comprises no water.

40. The method of claim 39 wherein the organic working fluid is a composition of Fischer Tropsch products.

41. The method of claim 36 comprising charging the elements with the catalyst prior to placing the elements in a containment shell.

42. The method of claim 41 comprising treating the catalyst-loaded elements so that the catalyst is evenly distributed.