WO2015025225A2

WO2015025225A2 - A process for the production of hydrocarbons

Info

Publication number: WO2015025225A2
Application number: PCT/IB2014/002500
Authority: WO
Inventors: Shehzada Khurram; Mubarik Ali BASHIR; Khalid Karim; Faisal BAKSH; Mohammad Abdur RAKIB
Original assignee: Saudi Basic Industries Corporation
Priority date: 2013-08-21
Filing date: 2014-08-08
Publication date: 2015-02-26
Also published as: WO2015025225A3

Abstract

The present disclosures and inventions relate to a method comprising the steps of: a) providing a feedstream comprising syngas; b) contacting the feedstream with a catalyst comprising cobalt or iron, thereby producing a product stream comprising at least one hydrocarbon; and c) regenerating the catalyst using a reduction-oxidation process; wherein the method is essentially free of steam during the reduction- oxidation process.

Description

A PROCESS FOR THE PRODUCTION OF HYDROCARBONS

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This Application claims the benefit of U.S. Provisional Application No.

61/868,198, filed on August 21, 2013, which is incorporated herein by reference in its entirety.

BACKGROUND

[0002] Syngas (mixtures of hydrogen and carbon monoxide), also called synthesis gas or syn gas, can be readily produced from either coal or methane (natural gas) by methods well known in the art and widely commercially practiced around the world. A number of well- known industrial processes use syngas for producing various oxygenated organic chemicals. The Fischer-Tropsch catalytic process for catalytically producing hydrocarbons from syngas was initially discovered and developed in the 1920's, and was used in South Africa for many years to produce gasoline range hydrocarbons as automotive fuels. The catalysts typically comprised iron or cobalt supported on alumina or titania, and promoters, like rhenium, zirconium, manganese, and the like were sometimes used with cobalt catalysts, to improve various aspects of catalytic performance. The products were typically gasoline-range hydrocarbon liquids having six or more carbon atoms, along with heavier hydrocarbon products.

[0003] Accordingly, there remains a need for a method and apparatus for producing a hydrocarbon from syngas with improved results.

SUMMARY

[0004] In accordance with the purposes of the invention, as embodied and broadly described herein, the invention, in one aspect, relates to methods comprising the steps of:

a. providing a first feedstream comprising syngas;

b. contacting the first feedstream with a catalyst comprising cobalt or iron, thereby producing a product stream comprising at least one hydrocarbon; and c. regenerating the catalyst using a reduction-oxidation process;

wherein the method is essentially free of steam during the regeneration process.

_ i __ [0005] Disclosed are apparatuses, wherein the apparatus comprises: a. a heater for heating a gas, which is in fluid communication with the first conduit; b. a first conduit, wherein the first conduit transfers the gas from the heater to a reactor, which is in fluid communication with the reactor; c. the reactor comprising a shell side and a tube side, which is in fluid communication with the second conduit; and d. a second conduit, which is in fluid communication with the heater; wherein the second conduit recycles the gas from the reactor to the heater; wherein the apparatus produces at least one hydrocarbon.

[0006] Disclosed are methods that comprise using the apparatus; wherein the method comprises an activation and regeneration process for producing a hydrocarbon.

[0007] While aspects of the present invention can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only and one of skill in the art will understand that each aspect of the present invention can be described and claimed in any statutory class. Unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification. BRIEF DESCRIPTION OF THE FIGURES

[0008] The accompanying figure, which is incorporated in and constitute a part of this specification, illustrates several aspects and together with the description serve to explain the principles of the invention.

[0009] Figure 1 shows an apparatus for producing a hydrocarbon according to one aspect of the invention.

[0010] Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or can be learned by practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.

DESCRIPTION

[0011] The present invention can be understood more readily by reference to the following detailed description of the invention and the Examples included therein.

[0012] Before the present compounds, compositions, articles, systems, devices, and/or methods are disclosed and described, it is to be understood that they are not limited to specific synthetic methods unless otherwise specified, or to particular reagents unless otherwise specified, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, example methods and materials are now described.

[0013] All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited. The publications discussed herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the dates of publication provided herein can be different from the actual publication dates, which can require independent confirmation.

A. DEFINITIONS

[0014] As used herein, nomenclature for compounds, including organic compounds, can be given using common names, IUPAC, IUBMB, or CAS recommendations for

nomenclature. When one or more stereochemical features are present, Cahn-Ingold-Prelog rules for stereochemistry can be employed to designate stereochemical priority, EIZ specification, and the like. One of skill in the art can readily ascertain the structure of a compound if given a name, either by systemic reduction of the compound structure using naming conventions, or by commercially available software, such as CHEMDRAW™ (Cambridgesoft Corporation, U.S.A.).

[0015] As used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a functional group," "an alkyl," or "a residue" includes mixtures of two or more such functional groups, alkyls, or residues, and the like.

[0016] Ranges can be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, a further aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms a further aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as "about" that particular value in addition to the value itself. For example, if the value "10" is disclosed, then "about 10" is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 1 1 , 12, 13, and 14 are also disclosed.

[0017] References in the specification and concluding claims to parts by weight of a particular element or component in a composition denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight component Y, X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.

[0018] A weight percent (wt. %) of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included.

[0019] As used herein, the terms "optional" or "optionally" means that the subsequently described event or circumstance can or can not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0020] As used herein, the term "essentially free" means that the reaction, method, and/or apparatus can include a small amount of the material in such a way that the material does not substantially contribute to the outcome of the reaction. As used herein, the material would not substantially contribute positively or adversely to the outcome of the reaction. Further, the material can be present in trace amounts or even more than trace amounts as long as the amount of material does not substantially contribute to the outcome of the reaction. For example, if a method or apparatus is essentially free of water, the method or apparatus can include a small amount of water in such a way that the water does not substantially contribute to the outcome of the reaction.

[0021] As used herein, the term "syngas" or "synthesis gas" refers to a mixture comprising hydrogen and carbon monoxide, which can be produced from, for example, coal or methane (natural gas).

[0022] Certain materials, compounds, compositions, and components disclosed herein can be obtained commercially or readily synthesized using techniques generally known to those of skill in the art. For example, the starting materials and reagents used in preparing the disclosed compounds and compositions are either available from commercial suppliers such as Aldrich Chemical Co., (Milwaukee, Wis.), Acros Organics (Morris Plains, N.J.), Fisher Scientific (Pittsburgh, Pa.), or Sigma (St. Louis, Mo.) or are prepared by methods known to those skilled in the art following procedures set forth in references such as Fieser and Fieser's Reagents for Organic Synthesis, Volumes 1 -17 (John Wiley and Sons, 1991); Rodd's Chemistry of Carbon Compounds, Volumes 1 -5 and Supplemental (Elsevier Science Publishers, 1989); Organic Reactions, Volumes 1-40 (John Wiley and Sons, 1991); March's Advanced Organic Chemistry, (John Wiley and Sons, 4th Edition); and Larock's

Comprehensive Organic Transformations (VCH Publishers Inc., 1989).

[0023] Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order.

Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including: matters of logic with respect to arrangement of steps or operational flow; plain meaning derived from grammatical organization or punctuation; and the number or type of embodiments described in the specification.

[0024] Disclosed are the components to be used to prepare the compositions of the invention as well as the compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds can not be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F and an example of a combination molecule, A-D is disclosed, then even if each is not individually recited each is individually and collectively contemplated meaning combinations, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are considered disclosed. Likewise, any subset or combination of these is also disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E would be considered disclosed. This concept applies to all aspects of this application including, but not limited to, steps in methods of making and using the compositions of the invention. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the methods of the invention.

[0025] It is understood that the compositions disclosed herein have certain functions. Disclosed herein are certain structural requirements for performing the disclosed functions, and it is understood that there are a variety of structures that can perforin the same function that are related to the disclosed structures, and that these structures will typically achieve the same result.

B. METHOD

[0026] In one aspect, the method comprises the steps of:

a. providing a first feedstream comprising syngas;

[0027] In one aspect, the method does not comprise using steam during the regeneration process. In another aspect, the method is essentially free of steam. In one aspect, the regeneration process step is free of steam. In a further aspect, the method is free of steam. For example, steam can be used during the conventional regeneration process of a Fischer Tropsch reaction as a steam/water regeneration to remove deactivating carbon. The steam can react with the carbon on the catalyst surface to form carbon monoxide and hydrogen, to clean the catalyst surface. Instead of using steam/water regeneration, the catalyst herein of the invention is regenerated using a reduction-oxidation process. Avoiding the use of steam can reduce the costs. In another aspect, since steam is not involved, the reduction-oxidation process can avoid using a high pressure vessel. In a further aspect, the steam is isolated from the reduction-oxidation process in the method. In an even further aspect, the method is less expensive and/or uses less time than other methods. In one aspect, the method comprises using a minimal amount of water during the regeneration process. In another aspect, the method comprises using essentially no water during the regeneration process. In another aspect, the method comprises not adding water during the regeneration process. In not using steam, it is intended throughout to mean not using steam as a process component. Steam can still be used as a heating medium as long as it is not a part of the actual process components.

[0028] In another aspect, the method is essentially free of steam during the regeneration process. In a further aspect, the method does not have to be anhydrous to be essentially free of steam. In an even further aspect, even though the method is essentially free of steam, the method can comprise background levels of water vapor. The background levels of water vapor can be present due to the overall humidity conditions or due to the overall presence of water in the feed material.

[0029] In one aspect, the method does not comprise using steam. In another aspect, the method is essentially free of steam. For example, steam can be used in a conventional Fischer Tropsch reaction during steam reformation, which converts a methane feedstock into carbon monoxide and hydrogen. Further, for example, in a conventional process, steam can also be used to crack the methane into a hydrogen-carbon monoxide-methane mixture at high temperatures. Avoiding using steam by steam reforming or steam cracking herein in the invention can reduce costs. In not using steam, it is intended throughout to mean not using steam as a process component. Steam can still be used as a heating medium as long as it is not a part of the actual process components.

[0030] In one aspect, the method comprises a catalyst comprising cobalt. In another aspect, the catalyst comprising cobalt can also comprise a promoter. In a further aspect, the promoter comprises a group 1 alkali metal, copper, or an alkali metal oxide, or a combination thereof. In a further aspect, the catalyst comprises a support. In one aspect, the support comprises silica, alumina, or zeolite, or a combination thereof. In a further aspect, the catalyst comprising cobalt comprises any conventional promoter and/or any conventional support that does not hinder the catalyst's activity. In another aspect, the catalyst comprising cobalt can comprise any conventional particle size that does not hinder the catalyst's activity.

[0031] In one aspect, the method comprises a catalyst comprising iron. In another aspect, the catalyst comprising iron can also comprise a promoter. In a further aspect, the promoter comprises a group 1 alkali metal, copper, or an alkali metal oxide, or a combination thereof. In a further aspect, the catalyst comprises a support. In one aspect, the support comprises silica, alumina, or zeolite, or a combination thereof. In a further aspect, the catalyst comprising iron comprises any conventional promoter and/or any conventional support that does not hinder the catalyst's activity. In another aspect, the catalyst comprising iron can comprise any conventional particle size that does not hinder the catalyst's activity.

[0032] In another aspect, the hydrocarbon comprises carbons in an amount ranging from one carbon to ten carbons, including two carbons, three carbons, four carbons, five carbons, six carbons, seven carbons, eight carbons, and nine carbons. In one aspect, the hydrocarbon can be an alkane, alkene, or alkyne. In another aspect, the hydrocarbon can be a straight chain or a branched chain.

[0033] In one aspect, the method comprises, prior to step b, activating the catalyst in the catalyst's initially free state using a second feedstream comprising hydrogen. In another aspect, the activation does not comprise using steam. In one aspect, the activation is essentially free of steam. In a further aspect, the activation process step is free of steam. The catalyst's initially free state as used herein can also mean the fresh catalyst or the state of the catalyst prior to being used in the reaction.

[0034] In one aspect, the reduction-oxidation process comprises heating a reactor vessel to a temperature ranging from 200 °C to 400 °C, including exemplary values 210 °C, 230 °C, 250 °C, 270 °C, 290 °C, 300 °C, 310 °C, 330 °C, 350 °C, 370 °C, and 390 °C. In a further aspect, the range can be derived from any two exemplary values. For example, the reduction- oxidation process comprises heating a reactor vessel to a temperature ranging from 210 °C to 390 °C.

[0035] In one aspect, the method comprises regenerating the catalyst. In another aspect, the regenerating the catalyst step occurs in-situ. In another aspect, the method comprises multiple in-situ reduction-oxidations in the reactor. In a further aspect, the method comprises any suitable reaction conditions for the in-situ regeneration. In a yet further aspect, the in-situ process avoids the use of an additional reactor for ex-situ reduction. As such, this method can be cheaper than a method comprising the additional reactor for an ex-situ reduction.

[0036] In one aspect, the method comprises a single reactor for the reduction-oxidation process. In another aspect, the method comprises more than one reactor for the reduction- oxidation process. [0037] In one aspect, the method does not comprise using salt or oil during the reduction- oxidation process. In another aspect, the method does not comprise using salt or oil during the regeneration process. In another aspect, the method is essentially free of salt or oil during the reduction-oxidation process. In a further aspect, the method is essentially free of salt or oil during the regeneration process. In an even further aspect, the method is essentially free of salt. In a yet further aspect, the method is essentially free of oil.

[0038] In one aspect, the reduction-oxidation process comprises a reducing gas, wherein the reducing gas heats the reduction-oxidation process. In one aspect, the reducing gas is added to reduce and/or activate the catalyst at the start of a run. In another aspect, the reducing gas comprises hydrogen and an inert gas. In one aspect, the inert gas comprises argon, helium, neon, krypton, xenon, radon, or nitrogen, or a combination thereof. In a further aspect, the reducing gas comprises hydrogen and nitrogen. In an even further aspect, the reducing gas comprises hydrogen.

[0039] In one aspect, the reduction-oxidation process comprises an oxidizing gas. In a further aspect, the oxidizing gas is added to oxidize the catalyst at end of the catalyst life before the catalyst is discharged. In another aspect, the oxidizing gas comprises oxygen and an inert gas. In one aspect, the inert gas comprises argon, helium, neon, krypton, xenon, radon, or nitrogen, or a combination thereof. In a further aspect, the oxidizing gas comprises oxygen and nitrogen. In an even further aspect, the oxidizing gas comprises oxygen. In a further aspect, the oxidizing gas comprises more oxygen than the reducing gas. In an even further aspect, the oxidizing gas comprises air, oxygen, or water vapor, or a combination thereof. In a yet further aspect, the oxidizing gas comprises a dilute oxygen stream. In one aspect, the dilute oxygen stream is 20% oxygen in helium.

[0040] In one aspect, the catalyst can undergo a series of reduction and/or oxidation steps. In another aspect, the reducing gas and the oxidizing gas are added separately during the reduction-oxidation process. Thus, the term "reduction-oxidation process" as used herein, means (1) use of a reducing gas, (2) use of an oxidizing gas, or (3) use of both reduction and oxidation gases, typically in a series of steps. [0041] In another aspect, the method for a reduction-oxidation process does not comprise using steam. In a further aspect, the method for a reduction-oxidation process is essentially free of steam. In an even further aspect, even though the method for a reduction-oxidation process is essentially free of steam, the method can comprise background levels of water vapor. The background levels of water vapor can be present due to the overall humidity conditions or due to the overall presence of water in the feed material.

[0042] In another aspect, the method for a reduction process does not comprise using steam. In a further aspect, the method for a reduction process is essentially free of steam. In an even further aspect, even though the method for a reduction process is essentially free of steam, the method can comprise background levels of water vapor. The background levels of water vapor can be present due to the overall humidity conditions or due to the overall presence of water in the feed material.

[0043] In another aspect, the method for an oxidation process does not comprise using steam. In a further aspect, the method for an oxidation process is essentially free of steam. In an even further aspect, even though the method for an oxidation process is essentially free of steam, the method can comprise background levels of water vapor. The background levels of water vapor can be present due to the overall humidity conditions or due to the overall presence of water in the feed material.

[0044] In one aspect, the reducing gas consists of hydrogen and an inert gas in a molar ratio of 1 to 75 of hydrogen and 99 to 25 of inert gas. In another aspect, the reducing gas has a molar ratio of 20 to 30 of hydrogen and 80 to 70 of inert gas.

[0045] In one aspect, the oxidizing gas consists of oxygen and an inert gas in a molar ratio of 1 to 75 of oxygen and 99 to 25 of inert gas. In another aspect, the reducing gas has a molar ratio of 20 to 30 of oxygen and 80 to 70 of inert gas.

[0046] In one aspect, the reducing gas is added directly to a reactor tube or to a reactor shell side. In another aspect, the reducing gas can be added to both the reactor tube and the reactor shell side at the same time. The simultaneous addition of the reducing gas to both the reactor tube and the reactor shell side allows for the control of the inlet temperature of the reducing gas to the reactor tube. In another aspect, the reducing gas is added directly to a reactor tube. In a further aspect, the reducing gas is added directly to a reactor shell side. In a further aspect, being able to add the reducing gas to the reactor tube or to the reactor shell side shows the method to be more flexible than other methods. In one aspect, the reducing gas can be added either hot or cold. The oxidizing gas can be added in a way similar to the reducing gas.

[0047] In one aspect, the method comprises an isolated steam system. In another aspect, the method does not comprise steam because the method comprises an isolated steam system. In a further aspect, the method is essentially free of steam because the method comprises an isolated steam system.

[0048] In one aspect, the reducing gas and/or oxidizing gas is heated to a temperature ranging from 200 °C to 400 °C before step c), including exemplary values 210 °C, 230 °C, 250 °C, 270 °C, 290 °C, 300 °C, 310 °C, 330 °C, 350 °C, 370 °C, and 390 °C. In a further aspect, the range can be derived from any two exemplary values. For example, reducing gas and/or oxidizing gas can be heated to a temperature ranging from 210 °C to 390 °C.

[0049] The methods disclosed herein can be performed by the apparatus disclosed herein.

C. APPARATUS

[0050] Also disclosed herein is an apparatus, wherein the apparatus comprises:

a. a heater for heating a gas, which is in fluid communication with the first conduit;

b. a first conduit, wherein the first conduit transfers the gas from the heater to a reactor, which is in fluid communication with the reactor;

c. the reactor comprising a shell side and a tube side, which is in fluid communication with a second conduit; and

d. the second conduit, which is in fluid communication with the heater; wherein the second conduit recycles the gas from the reactor to the heater;

wherein the apparatus is for producing at least one hydrocarbon. [0051] In one aspect, the gas is a reducing gas. In another aspect, the gas is an oxidizing gas. In a further aspect, the oxidizing gas comprises more oxygen than the reducing gas. In an even further aspect, the oxidizing gas comprises air, oxygen, or water vapor, or a combination thereof. In a yet further aspect, the oxidizing gas comprises a dilute oxygen stream. In one aspect, the dilute oxygen stream can be 20% oxygen in helium.

[0052] In one aspect, FIG. 1 shows an exemplary apparatus.

[0053] In one aspect, the apparatus comprises a heater (1) for heating a gas, which is in fluid communication with the first conduit (2). In another aspect, the heater (1) can be any heater suitable for heating a gas. In a further aspect, the heater (1) can be used for preheating the gas.

[0054] In one aspect, the apparatus comprises a first conduit (2), wherein the first conduit transfers the gas from the heater (1) to a reactor (3), which is in fluid communication with the reactor (3). In another aspect, the first conduit (2) can be made of any material suitable for a fischer-tropsch reaction. In a further aspect, the first conduit (2) can be any size suitable for the method.

[0055] In one aspect, the reactor (3) comprises a shell side and a tube side, which is in fluid communication with the second conduit (4). In another aspect, the hot reducing gas can be fed to the tube side of the reactor (3).

[0056] In a further aspect, the reactor can be loaded with a cobalt-based or an iron-based catalyst. In an even further aspect, the cobalt-based or the iron-based catalyst can be any catalyst suitable for use in a fischer-tropsch reaction.

[0057] In one aspect, the apparatus comprises a second conduit (4), which is in fluid communication with the heater (1); wherein the second conduit (4) recycles the gas from the reactor to the heater (1). In another aspect, the second conduit (4) can be made of any material suitable for a fischer-tropsch reaction. In a further aspect, the second conduit (4) can be any size suitable for the method.

[0058] In one aspect, the second conduit (4) further comprises a gas/gas heat exchanger (5); wherein the second conduit (4) transfers the reducing gas from the reactor (3) to the gas/gas exchanger (5). In another aspect, the second conduit (4) is in fluid communication with the gas/gas heat exchanger (5). In a further aspect, the gas/gas heat exchanger (5) can be any gas/gas heat exchanger suitable for a fischer-tropsch apparatus.

[0059] In one aspect, the second conduit (4) further comprises a condenser (6); wherein the second conduit (4) transfers the reducing gas from the reactor (3) to the condenser (6). In another aspect, the condenser (6) exchanges heat with the low temperature gas coming from the condenser (6). In a further aspect, the condenser (6) can be any condenser suitable for a fischer-tropsch apparatus. In a yet further aspect, the cooled gas can enter the condenser (6) for further cooling to remove the water. In an even further aspect, the water, which is removed, is produced during the reduction process. In one aspect, the reducing gas is dried by the condenser (6). In a further aspect, the condenser (6) recovers heat from the gas/gas heat exchanger (5). The heat is recovered in the gas/gas exchanger (5) by the dried reducing gas. This recovery reduces the heat load on the heater (1) and is a feature of heat economy.

[0060] In one aspect, the second conduit (4) further comprises a blower (7); wherein the second conduit (4) transfers the reducing gas from the reactor (3) to the blower (7). In a further aspect, the blower (7) can be any blower suitable for a fischer-tropsch apparatus.

[0061] In one aspect, the second conduit (4) transfers the reducing gas from the reactor (3), first to the gas/gas heat exchanger (5), then to the condenser (6), then to the blower (7), and then back to the reactor (3).

[0062] In one aspect, the second conduit (4) transfers the reducing gas from the reactor (3), first to the gas/gas heat exchanger (5), then to the condenser (6), then to the blower (7), then to the heater (1), and then back to the reactor (3).

[0063] In one aspect, the apparatus comprises a steam system (9) that is isolated from the apparatus. In another aspect, the apparatus does not comprise a steam system. In a further aspect, the apparatus is essentially free of steam. In an even further aspect, even though the apparatus is essentially free of steam, the apparatus can comprise background levels of water vapor. The background levels of water vapor can be present due to the overall humidity conditions or due to the overall presence of water in the feed material. [0064] In another aspect, the apparatus comprises a third conduit (8), wherein the third conduit recycles the gas to the reactor (3). In another aspect, the third conduit (8) can be made of any material suitable for a fischer-tropsch reaction. In a further aspect, the third conduit (8) can be any size suitable for the method.

[0065] In a further aspect, the third conduit (8) bypasses the heater (1). In one aspect, the third conduit (8) transfers the unheated gas to the reactor (3). In another aspect, the apparatus avoids an undesired temperature rise during the oxidation or reduction by bypassing the heater (1).

[0066] In one aspect, the apparatus comprises bypassing the gas/gas heat exchanger (5). In another aspect, the apparatus comprises transferring the gas from the reactor (3) to the condenser (6).

[0067] In one aspect, the apparatus comprises transferring an unheated gas to the reactor (3).

[0068] The apparatuses disclosed herein can use the methods disclosed herein.

D. METHOD USING THE APPARATUS

[0069] In one aspect, the method comprises using the apparatus according to the apparatus disclosed herein; wherein the method comprises an activation and regeneration process for producing a hydrocarbon.

[0070] In another aspect, the method for an activation and regeneration process does not comprise using steam. In one aspect, the method is essentially free of steam. In a further aspect, the method for an activation and/or regeneration process is essentially free of steam. In an even further aspect, even though the method for an activation and/or regeneration process is essentially free of steam, the method can comprise background levels of water vapor. The background levels of water vapor can be present due to the overall humidity conditions or due to the overall presence of water in the feed material. [0071] In one aspect, the method comprises using the apparatus according to the apparatus disclosed herein; wherein the method comprises an oxidation process for producing a hydrocarbon.

[0072] In another aspect, the method for an oxidation process does not comprise using steam. In a further aspect, the method for an oxidation process is essentially free of steam. In an even further aspect, even though the method for an oxidation process is essentially free of steam, the method can comprise background levels of water vapor. The background levels of water vapor can be present due to the overall humidity conditions or due to the overall presence of water in the feed material.

[0073] The methods using the apparatus disclosed herein can use the apparatuses disclosed herein and the methods disclosed herein.

E. ASPECTS

[0074] The disclosed methods and apparatuses include at least the following aspects.

[0075] Aspect 1 : A method comprising the steps of:

a. providing a first feedstream comprising syngas;

[0076] Aspect 2: The method according to aspect 1 , wherein, prior to step b, activating the catalyst in the catalyst's initially free state using a second feedstream comprising hydrogen.

[0077] Aspect 3: The method according to aspect 2, wherein the activation is essentially free of steam. [0078] Aspect 4: The method according to any of aspects 1-3, wherein the method is essentially free of steam.

[0079] Aspect 5: The method according to any of aspects 1-4, wherein the reduction- oxidation process comprises heating a reactor vessel to a temperature ranging from 200°C to 400°C.

[0080] Aspect 6: The method according to any of aspects 1-5, wherein the regenerating the catalyst step occurs in-situ.

[0081] Aspect 7: The method according to any of aspects 1-6, wherein the method comprises a single reactor for the reduction-oxidation process.

[0082] Aspect 8: The method according to any of aspects 1-7, wherein the method comprises multiple reactors for the reduction-oxidation process.

[0083] Aspect 9: The method according to any of aspects 1-8, wherein the method does not comprise using salt or oil during the reduction-oxidation process.

[0084] Aspect 10: The method according to any of aspects 1-9, wherein the reduction- oxidation process comprises a reducing gas, wherein the reducing gas heats the reduction- oxidation process.

[0085] Aspect 1 1 : The method according to aspect 10, wherein the reducing gas is added directly to a reactor tube or to a reactor shell side.

[0086] Aspect 12: The method according to aspects 10-1 1, wherein the reducing gas comprises hydrogen.

[0087] Aspect 13: The method according to any of aspects 1-12, wherein the method comprises an isolated steam system.

[0088] Aspect 14: The method according to any of aspects 1-13, wherein the reducing gas is heated to a temperature ranging from 200°C to 400°C before step c).

[0089] Aspect 15: The method according to any of aspects 1-14, wherein the hydrocarbon comprises carbons in an amount ranging from one carbon to ten carbons. [0090] Aspect 16: The method according to any of aspects 1-15, wherein the reduction- oxidation process comprises an oxidizing gas.

[0091] Aspect 17: The method according to any of aspects 1-16, wherein the oxidizing gas comprises oxygen.

[0092] Aspect 18: An apparatus comprising: a. a heater for heating a gas, which is in fluid communication with the first conduit;

d. the second conduit, which is in fluid communication with the heater; wherein the second conduit recycles the gas from the reactor to the heater; wherein the apparatus is for producing at least one hydrocarbon.

[0093] Aspect 19: The apparatus according to aspect 18, wherein the second conduit further comprises a gas/gas heat exchanger; wherein the second conduit transfers the reducing gas from the reactor to the gas/gas heat exchanger.

[0094] Aspect 20: The apparatus according to any of aspects 18-19, wherein the second conduit further comprises a condenser; wherein the second conduit transfers the reducing gas from the reactor to the condenser.

[0095] Aspect 21 : The apparatus according to any of aspects 18-20, wherein the second conduit further comprises a blower; wherein the second conduit transfers the reducing gas from the reactor to the blower.

[0096] Aspect 22: The apparatus according to any of aspects 18-21 , wherein the second conduit recycles the reducing gas back to the reactor, bypassing the heater.

[0097] Aspect 23: The apparatus according to any of aspects 18-22, wherein the second conduit transfers the reducing gas from the reactor, first to the gas/gas exchanger, then to the condenser, then to the blower, and then back to the reactor. [0098] Aspect 24: The apparatus according to any of aspects 18-22, wherein the second conduit transfers the reducing gas from the reactor, first to the gas/gas exchanger, then to the condenser, then to the blower, then to the heater, and then back to the reactor.

[0099] Aspect 25: The apparatus according to any of aspects 18-24, wherein the apparatus comprises a steam system that is isolated from the apparatus.

[00100] Aspect 26: The apparatus according to any of aspects 18-25, wherein the gas is a reducing gas.

[00101] Aspect 27: The apparatus according to any of aspects 18-26, wherein the apparatus comprises a third conduit, wherein the third conduit recycles the gas to the reactor.

[00102] Aspect 28: The apparatus according to any of aspects 18-27, wherein the third conduit bypasses the heater.

[00103] Aspect 29: The apparatus according to any of aspects 18-28, wherein the gas is an oxidizing gas.

[00104] Aspect 30: The apparatus according to aspect 29, the oxidizing gas comprises more oxygen than the reducing gas.

[00105] Aspect 31 : The apparatus according to any of aspects 18-30, wherein the apparatus comprises bypassing the gas/gas heat exchanger.

[00106] Aspect 32: The apparatus according to any of aspects 18-31 , wherein the apparatus comprises transferring an unheated gas to the reactor.

[00107] Aspect 33: A method comprising using the apparatus according to any of aspects 18-32; wherein the method comprises an activation and regeneration process for producing a hydrocarbon.

[00108] Aspect 34: A method comprising using the apparatus according to any of aspects 18-33; wherein the method comprises an oxidation process for producing a hydrocarbon.

[00109] Aspect 35: The method of aspect 33, wherein the method is essentially free of steam. [00110] Aspect 36: The method of aspect 34, wherein the method is essentially free of steam.

[00111] Aspect 37: The method of aspect 1, wherein the regeneration process step is free of steam.

[00112] Aspect 38: The method of aspect 3, wherein the activation process step is free of steam.

[00113] Aspect 39: The method of aspect 4, wherein the method is free of steam.

[00114] Aspect 40: The method of aspect 35, wherein the method is free of steam.

[00115] Aspect 41 : The method of aspect 36, wherein the method is free of steam.

Claims

CLAIMS What is claimed is:

1. A method comprising the steps of: a. providing a first feedstream comprising syngas; b. contacting the first feedstream with a catalyst comprising cobalt or iron, thereby producing a product stream comprising at least one hydrocarbon; and c. regenerating the catalyst using a reduction-oxidation process; wherein the method is essentially free of steam during the regeneration process.

2. The method according to claim 1 , wherein, prior to step b, the method further

comprises activating the catalyst in the catalyst's initially free state using a second feedstream comprising hydrogen.

3. The method according to claim 2, wherein the activation is essentially free of steam.

4. The method according to any of claims 1-3, wherein the method is essentially free of steam.

5. The method according to any of claims 1-4, wherein the reduction-oxidation process comprises heating a reactor vessel to a temperature ranging from 200°C to 400°C.

6. The method according to any of claims 1-5, wherein the regenerating the catalyst step occurs in-situ.

7. The method according to any of claims 1-6, wherein the method comprises a single reactor for the reduction-oxidation process.

8. The method according to any of claims 1 -7, wherein the method comprises multiple reactors for the reduction-oxidation process.

9. The method according to any of claims 1-8, wherein the method does not comprise using salt or oil during the reduction-oxidation process.

10. The method according to any of claims 1-9, wherein the reduction-oxidation process comprises a reducing gas, wherein the reducing gas heats the reduction-oxidation process.

1 1. The method according to claim 10, wherein the reducing gas is added directly to a reactor tube or to a reactor shell side.

12. The method according to claims 10-1 1, wherein the reducing gas comprises hydrogen.

13. The method according to any of claims 1-12, wherein the method comprises an

isolated steam system.

14. The method according to any of claims 1-13, wherein the reducing gas is heated to a temperature ranging from 200°C to 400°C before step c).

15. The method according to any of claims 1-14, wherein the hydrocarbon comprises carbons in an amount ranging from one carbon to ten carbons.

16. The method according to any of claims 1-15, wherein the reduction-oxidation process comprises an oxidizing gas.

17. The method according to claim 16, wherein the oxidizing gas comprises oxygen.

18. An apparatus comprising: a. a heater for heating a gas, which is in fluid communication with the first

conduit; b. a first conduit, wherein the first conduit transfers the gas from the heater to a reactor, which is in fluid communication with the reactor; c. the reactor comprising a shell side and a tube side, which is in fluid

communication with a second conduit; and d. the second conduit, which is in fluid communication with the heater; wherein the second conduit recycles the gas from the reactor to the heater wherein the apparatus is for producing at least one hydrocarbon.

19. The apparatus according to claim 18, wherein the second conduit further comprises a gas/gas heat exchanger; wherein the second conduit transfers the reducing gas from the reactor to the gas/gas heat exchanger.

20. The apparatus according to any of claims 18-19, wherein the second conduit further comprises a condenser; wherein the second conduit transfers the reducing gas from the reactor to the condenser.

21. The apparatus according to any of claims 18-20, wherein the second conduit further comprises a blower; wherein the second conduit transfers the reducing gas from the reactor to the blower.

22. The apparatus according to any of claims 18-21 , wherein the second conduit recycles the reducing gas back to the reactor, bypassing the heater.

23. The apparatus according to any of claims 18-22, wherein the second conduit transfers the reducing gas from the reactor, first to the gas/gas heat exchanger, then to the condenser, then to the blower, and then back to the reactor.

24. The apparatus according to any of claims 18-22, wherein the second conduit transfers the reducing gas from the reactor, first to the gas/gas heat exchanger, then to the condenser, then to the blower, then to the heater, and then back to the reactor.

25. The apparatus according to any of claims 18-24, wherein the apparatus comprises a steam system that is isolated from the apparatus.

26. The apparatus according to any of claims 18-25, wherein the gas is a reducing gas.

27. The apparatus according to any of claims 18-26, wherein the apparatus comprises a third conduit, wherein the third conduit recycles the gas to the reactor.

28. The apparatus according to any of claims 18-27, wherein the third conduit bypasses the heater.

29. The apparatus according to any of claims 18-28, wherein the gas is an oxidizing gas.

30. The apparatus according to claim 29, the oxidizing gas comprises more oxygen than the reducing gas.

31. The apparatus according to any of claims 18-30, wherein the apparatus comprises bypassing the gas/gas heat exchanger.

32. The apparatus according to any of claims 18-31, wherein the apparatus comprises transferring an unheated gas to the reactor.

33. A method comprising using the apparatus according to any of claims 18-32; wherein the method comprises an activation and regeneration process for producing a hydrocarbon.

34. A method comprising using the apparatus according to any of claims 18-33; wherein the method comprises an oxidation process for producing a hydrocarbon.

35. The method of claim 33, wherein the method is essentially free of steam.

36. The method of claim 34, wherein the method is essentially free of steam.

37. The method of claim 1, wherein the regeneration process step is free of steam.

38. The method of claim 3, wherein the activation process step is free of steam.

39. The method of claim 4, wherein the method is free of steam.

40. The method of claim 35, wherein the method is free of steam.

41. The method of claim 36, wherein the method is free of steam.