Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
  • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
  • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

• the present invention is directed to the conversion of CO 2 -rich natural gases into liquid fuels.
• the invention is directed to reducing CO 2 levels in CO 2 -rich natural gases that are converted into liquid fuels.
• remote natural gas refers to a natural gas asset that cannot be economically shipped to a commercial market by pipeline.
• the Fischer-Tropsch and MTG processes both have advantages and disadvantages.
• the Fischer-Tropsch process has the advantage of forming products that are highly paraffinic. Highly paraffinic products are desirable because they exhibit excellent combustion and lubricating properties.
• a disadvantage of the Fischer-Tropsch process is that the Fischer-Tropsch process emits relatively large amounts of CO 2 during the conversion of natural gas assets into saleable products.
• An advantage of the MTG process is that the MTG process produces highly aromatic gasoline and LPG fractions (e.g., propane and butane).
• FIG. 1 A schematic of a conventional Fischer-Tropsch process is shown in Figure 1.
• a natural gas feed stream 11 comprising CH 4 and CO2
• enters a first separator 12 wherein an amount of CO 2 is removed in an exit stream 13.
• a natural gas feed stream 14, comprising CH 4 and CO 2 exits the first separator 12 and mixes with a stream 15 of O 2 and H 2 O.
• the feed stream 14 then enters a synthesis gas formation reactor 16.
• a synthesis gas stream 17, comprising CO, H 2 and CO 2 exits the synthesis gas formation reactor 16 and enters a Fischer-Tropsch reactor 18.
• a Fischer-Tropsch product stream 19 exits the Fischer- Tropsch reactor 18 and enters a second separator 20.
• the second separator 20 separates the Fischer-Tropsch product stream 19 into a hydrocarbon products stream 21, and an unreacted gas stream 22, comprising unreacted CO, H 2 and CO 2 .
• the unreacted gas stream 22 either recirculates in a recirculation stream 24 that mixes with the synthesis gas stream 17 before the synthesis gas stream enters the Fischer-Tropsch reactor 18, or exits the process in an exit stream 23 where the unreacted gases are used as a fuel.
• the Fischer-Tropsch process can be understood by examining the stoichiometry of the reaction that occurs during a Fischer-Tropsch process.
• synthesis gas i.e., a mixture including carbon monoxide and hydrogen
• Typical Fischer-Tropsch reaction products include paraffins and olefins, generally represented by the formula nCH 2 . While this formula accurately defines mono-olefin products, it only approximately defines C 5 + paraffin products.
• the value of n i.e., the average carbon number of the product
• the desired net synthesis gas stoichiometry for a Fischer-Tropsch reaction is independent of the average carbon number (n) of the product and is about 2.0, as determined by the following reaction equation:
• nCH 2 represents typical Fischer-Tropsch reaction products such as, for example, olefins and paraffins.
• the ratio of hydrogen to carbon monoxide produced by the above reactions is not always adequate for the desired Fischer-Tropsch conversion ratio of 2.0.
• all ratios are molar ratios, unless otherwise noted.
• the resulting ratio of hydrogen to carbon monoxide is 3.0, which is higher than the desired hydrogen to carbon monoxide ratio of 2.0 for a Fischer- Tropsch conversion.
• the resulting hydrogen to carbon monoxide ratio is 1.0, which is lower than the desired hydrogen to carbon monoxide ratio of 2.0 for a Fischer-Tropsch conversion.
• the above dry reforming reaction In addition to exhibiting a hydrogen to carbon monoxide ratio that is lower than the desired ratio for a Fischer- Tropsch conversion, the above dry reforming reaction also suffers from problems associated with rapid carbon deposition. Finally, because the above partial oxidation reaction provides a hydrogen to carbon monoxide ratio of 2.0, the partial oxidation reaction is the preferred reaction for Fischer-Tropsch conversions.
• Suitable adsorbents can include, for example, water, amines, caustic compounds, combinations thereof and the like.
• Suitable adsorbents can include, for example, ZnO, Cu, Ni, combinations thereof and the like. ZnO is a preferred adsorbent because it selectively removes sulfur species without removing CO 2 .
• CO 2 in the natural gas feedstock has a tendency to react in a dry reforming reaction, which suffers from the disadvantages of generating low hydrogen content synthesis gas and carbon deposits, only a limited amount of CO2 can be tolerated in the synthesis gas.
• the amount of CO 2 in the synthesis gas must be limited to a few percent, preferably about 5 mol% or less. In instances where the synthesis gas comprises greater than 5 mol%, excess CO 2 must be removed from the synthesis gas and destroyed.
• Suitable CO 2 disposal methods include, but are not limited to, venting, injection into an underground reservoir, conversion to solid carbonates or injection into a body of water. Unfortunately, each of these methods suffer from disadvantages. First, venting is undesirable because it increases a facility's greenhouse gas emissions. Also, while injection into an underground reservoir and conversion into solid carbonates avoid additional greenhouse gas emissions, these methods are extremely costly. Finally, the injection of CO 2 into a body of water, using conventional methods wherein CO 2 is recovered at near atmospheric pressure, is both expensive and unproven.
• the present invention satisfies the above objectives by providing a process that not only converts natural gas into liquid fuels, but also reduces CO 2 levels in the natural gases being converted.
• a process, according to the present invention, for converting CO 2 -rich natural gas into liquid fuel includes introducing a CO 2 -rich natural gas feed stream into a synthesis gas formation reactor and then forming a synthesis gas. At least a portion of the synthesis gas is then introduced into a Fischer-Tropsch reactor. A Fischer- Tropsch process is conducted generating a Fischer-Tropsch product. A naphtha is separated from the Fischer-Tropsch product and introduced into a naphtha reformer. Hydrogen by-product is generated by reforming the naphtha to obtain a C 6 -C ⁇ 0 product having a hydrogen to carbon ratio of less than about 2.0.
• At least a portion of the hydrogen by-product is recirculated and mixed with the CO 2 -rich natural gas feed stream.
• the hydrogen by-product mixes with the CO 2 -rich natural gas feedstream such that at least a portion of the CO 2 present in the CO 2 -rich natural gas feed stream is converted into additional CO by a reverse water gas shift reaction so that the synthesis gas derived from the feed stream contains a volume amount of CO 2 that is less than a volume amount of CO 2 present in the feed stream prior to mixing with the hydrogen byproduct.
• the additional CO is converted into hydrocarbons in the Fischer- Tropsch reactor.
• the present invention also provides a process for using the CO 2 in natural gas for preparing hydrocarbons.
• a process includes reforming a Fischer-Tropsch naphtha to obtain a C 6 -C ⁇ o product and a hydrogen byproduct.
• the process further includes reacting the hydrogen by-product with the CO 2 in a natural gas so that a reverse water gas shift reaction occurs converting the CO 2 into additional CO.
• the CO is then converted into hydrocarbons in a Fischer-Tropsch reactor. It is most preferred that the process is integrated so that the natural gas containing the CO 2 is used to create synthesis gas, from which the Fischer-Tropsch naphtha is prepared. This process thereby reduces the level of CO 2 in the natural gas while also making use of the generally inert C0 2 to obtain a valuable product, all preferably in an integrated process.
• the present invention reduces CO 2 levels in CO 2 -rich natural gases, including natural gases being converted into liquid fuel, by converting at least a portion of the CO 2 present in a natural gas into additional CO with subsequent conversion of the additional CO into hydrocarbons.
• the process of the present invention reduces CO 2 levels in natural gases by reacting hydrogen by-product, generated from Fischer-Tropsch naphtha reformation, with CO2 in a reverse water gas shift reaction to convert CO 2 into additional CO, and then converting the. additional CO into hydrocarbons in a Fischer-Tropsch reactor.
• one advantage of the present invention is that it avoids producing low-hydrogen-content synthesis gases and carbon deposits, often resulting from the dry reformation of excess CO 2 present in a natural gas, without having to employ costly, ineffective or environmentally hazardous CO 2 disposal techniques.
• Figure 1 is a schematic view of a conventional Fischer-Tropsch process.
• Figure 2 is a schematic view of a preferred embodiment of a Fischer-Tropsch process according to the present invention.
• CO 2 -rich is intended to refer to a gas comprising at least about 1 mole percent CO 2 , preferably at least 2 mole percent CO 2 , more preferably at least about 5 mole percent CO 2 and most preferably at least about 10 mole percent CO 2 .
• the conversion of CO 2 into additional CO requires an additional hydrogen source so that a reverse water gas shift reaction can occur.
• a suitable reverse water gas shift reaction is represented by the following general reaction:
• the hydrogen for the above reverse water gas shift reaction can be generated, for example, by converting at least a portion of a C 5 + Fischer-Tropsch product into aromatics to form hydrogen by-product.
• a typical C 8 paraffin reaction that demonstrates how hydrogen by-product can be generated by converting a Fischer-Tropsch product into aromatics is as follows:
• naphtha reforming processes Processes for converting paraffin-rich streams into aromatics are well known in the field. Commonly, such conversion processes are referred to as "naphtha reforming processes," and are divided into two classes.
• the first class of naphtha reforming processes are referred to as conventional reforming processes and use a catalyst comprising at least one of Pt, alumina, and a halogen (typically Cl), Re, Ir, combinations thereof and the like.
• the catalyst in conventional reforming processes is typically exposed to sulfur before being employed in the reaction.
• Those of ordinary skill in the art commonly expose conventional reforming catalysts to sulfur prior to use in a reforming reaction in order to obtain highly selective conversion of C 8 to Cio paraffins into aromatics.
• non- acidic zeolitic reforming processes
• non-acidic zeolitic reforming processes use a catalyst comprising at least one of Pt, a non-acidic zeolitic, typically an L-type zeolite, K, Ba, combinations thereof and the like.
• non-acidic zeolitic reforming catalysts are not exposed to sulfur prior to operation.
• non-acidic zeolitic reforming catalysts are highly ⁇ selective for the conversion of hexane and heptane in aromatics.
• the present invention can employ either or both of the above naphtha reforming processes.
• Aromatic products produced by the above reforming processes can be used in various applications. Suitable applications for such aromatic products include, but are not limited to, high octane blend components for gasoline, benzene for use as a chemical, especially for the production of cyclohexane, ethylbenzene and/or cumene, toluene for use as a chemical and xylene for use as a chemical, especially for the production of paraxylene.
• hydrogen can also be provided from alternative sources to supplement or replace hydrogen generated during naphtha reforming.
• the C 6 -C ⁇ o portion of the C 5 + hydrocarbon product will exhibit a lower hydrogen to carbon ratio than a hydrogen to carbon ratio of a C ⁇ 0 + portion of the product.
• the C 6 -C ⁇ o portion of the C 5 + hydrocarbon product will exhibit a hydrogen to carbon molar ratio that is preferably about 0.1 unit less, more preferably about 0.2 unit less, and most preferably about 0.25 unit less than the hydrogen to, carbon ratio of the C ⁇ 0 + portion of the product.
• At least a portion of the hydrogen from the formation of aromatics is used to react with at least a portion of the CO 2 present in the CO 2 -rich natural gas feed stream.
• the separation of CO 2 from other gases is well known in the industry and can be accomplished using any adsorbent or absorbent conventionally used to selectively separate CO 2 .
• adsorbent or absorbent conventionally used to selectively separate CO 2 .
• basic liquid amines are used to separate CO 2 from other gases but aqueous solutions of alkali metals with little or no amines can be used when the use of amines is undesirable.
• the CO 2 in the CO 2 -rich natural gas feed stream can be converted into additional CO by reacting the natural gas feed stream with hydrogen by-product so that the synthesis gas derived from the feed stream contains a volume amount of CO 2 that is less than a volume amount of CO2 present in the feed stream prior to reacting with the hydrogen by-product.
• the natural gas feed can either be reacted with hydrogen byproduct in a separate reactor before entering the synthesis gas formation reactor, or both the hydrogen by-product and the natural gas feed can be fed into the synthesis gas reactor. The latter is more preferable because it is less costly than reacting in a separate reactor.
• the synthesis gas, generated from the CO 2 -rich natural gas after reaction with the hydrogen by-product preferably contains about 5 mol% or less of CO 2 .
• Hydrogen produced in the naphtha reforming process often contains significant amounts of C 2 + hydrocarbons. These can cause coking in the methane reforming reactor, so it is preferable to process the hydrogen from the naphtha reforming reactor in a pre-reformer ahead of the main naphtha reformer. Likewise if there are significant C 2 + hydrocarbons in the methane feed to the reformer, it too .should be processed in the pre- reformer. The purpose of the pre-reformer is to convert C 2 + hydrocarbons into syngas, methane, and water and to thereby avoid the coking that would otherwise occur.
• Staged steam- methane reforming processes utilizing a pre-reformer typically includes an adiabatic pre- reforming reactor containing a highly active nickel catalyst, to reform heavier hydrocarbons in the feedstock (and a portion of the methane, if present) to yield a mixture of methane, hydrogen, carbon monoxide, carbon dioxide, and steam.
• This pre- reforming product is then further processed in a reformer to produce a raw synthesis gas product.
• staged reformer process utilizes a gas heated reformer (GHR) followed by an autothermal reformer.
• GHR is a type of heat exchange reformer in which the hot raw synthesis gas from the autothermal reformer furnishes the heat for the first reforming stage in the GHR.
• the hydrogen to carbon stoichiometric ratio of the resulting products can be determined by any number of methods including, but not limited to, chemical analysis such as Carlo-Erba combustion, Orsat chemical analysis, gas chromatography for identifying individual species, simple gas density, and NMR spectroscopy, combinations thereof, and the like. Generally, simple chemical analysis is preferred in order to minimize cost and to provide an accurate analysis.
• the product streams in the present invention are Fischer-Tropsch-derived products generally in the ranges of C1-C5, naphtha and C 1 0+, wherein each of the general ranges may comprise more than one product stream.
• each product stream can be a mixture, such as a synthetic crude, or may be individual streams such as LPG (C 3 's and C 's) condensates (Cs's and C 6 's), high octane blend components (Ce-Cio aromatic containing streams), jet fuel, diesel fuel, other distillate fuels, and lube blend stocks or lube blend stock feedstocks. Desired stoichiometric ratios specified in the present invention refer to the net product analysis.
• the C 6 -C ⁇ o naphtha product may be further described as "aromatic containing" meaning that the aromatic content is at least about 2 wt.%, preferably at least about 10 wt.% and most preferably at least about 25 wt.%, with analysis being done by GC or GC-MS.
• the hydrogen by-product generated during naphtha reforming can also be used for other processes, such as hydrotreating a portion of the C$ + product to remove olefins, oxygenates and other trace heteroatoms.
• a CO 2 -rich natural gas feed stream 11 comprising CH and CO 2 , enters a first separator 12 wherein an amount of CO 2 is removed in an exit stream 13.
• a first separator 12 While the embodiment in Figure 2 is depicted as including a first separator 12, it is also suitable to use a liquid adsorber (not shown) using a solution including water, caustic amines, combinations thereof and the like. In addition to removing CO 2 , such a liquid adsorber would also remove as much sulfur as possible.
• the feed stream 14 then enters a synthesis gas formation reactor 16.
• the natural gas feed stream 14 is depicted as mixing with stream 15 before entering the reactor 16, it is equally suitable for the natural gas feed stream 14 to mix with the O2- and H2 ⁇ -containing stream 15 after entering the reactor 16.
• Reactor 16 may contain a pre-reforming section to convert C 2 + hydrocarbons. A description of a pre-reformer and its use in the present process is described in copending U.S. Application Serial No. , docket number 005950-709, the entire disclosure of which is incorporated herein by reference for all purposes.
• a synthesis gas stream 17, comprising CO, H2 and CO 2 exits the synthesis gas formation reactor 16 and enters a Fischer-Tropsch reactor 18. Additionally, water can be removed, for example, by condensation using equipment not shown.
• a Fischer-Tropsch product stream 19 exits the Fischer-Tropsch reactor 18 and enters a second separator 20.
• the second separator 20 separates the Fischer-Tropsch product stream 19 into a hydrocarbon products stream 21, and an unreacted gas stream 22, comprising unreacted CO, H 2 and CO 2 .
• Second separator 20 is shown as a separate vessel from Fischer-Tropsch reactor 18.
• the separation of the Fischer-Tropsch product stream 19 may also be conducted within Fischer-Tropsch reactor 18, so that second separator 20 is an integral part, or coincident with, Fischer- Tropsch reactor 18.
• Hydrocarbon product stream 21 is a C ⁇ + stream, indicating that the stream contains a range of hydrocarbon products. Ci hydrocarbons are generally present, but are not required.
• the C5+ components (i.e. those hydrocarbons having carbon numbers of 5 and higher) of the hydrocarbon products may be separated into a naphtha stream 28 and a C 10 + product stream 26.
• the unreacted gas stream 22 either recirculates in a recirculation stream 24 that mixes with the synthesis gas stream 17 before the synthesis gas stream enters the Fischer-Tropsch reactor 18, or exits the process in an exit stream 23 where the unreacted gases are used as a fuel.
• the hydrocarbon products stream 21 exits the second separator 20 and enters a third separator 25.
• the third separator 25 separates the hydrocarbon products stream 21 into a C 1 -C 5 product stream 27, wherein the C 1 -C 5 product has a hydrogen to carbon ratio of at least about 2.0, a naphtha stream 28 and a C ⁇ 0 + product stream 26, wherein the C ⁇ 0 + product has a hydrogen to carbon ratio of about 2.0. Water produced in the Fischer Tropsch reaction is also removed in this separation stage.
• the naphtha stream 28 enters a naphtha reformer 29. It is important to note that the sulfur content of mixed gas being fed to the reformer 29 should be about lppm or less. If sulfur removal is needed, it can be performed using equipment (not shown) such as, for example, adsorbent beds employing selective H 2 S liquid adsorption systems and solid adsorbents typically using ZnO. ZnO adsorption is preferred because it can selectively remove sulfur without removing a substantial amount of CO 2 .
• the naphtha reformer 29 reforms the naphtha stream 28 generating a C 6 -C ⁇ 0 product stream 30, wherein the C 6 -C ⁇ 0 product has a hydrogen to carbon ratio of less than about 2.0, and a hydrogen by-product stream 31.
• the C 6 -C ⁇ o product can be described as "aromatic containing" meaning that the aromatic content is at least about 2 wt.%, preferably at least about 10 wt.% and most preferably at least about 25 wt.%, with analysis being done by GC or GC-MS.
• the hydrogen by-product stream 31 recirculates so that the hydrogen by-product reacts with CO 2 present in the natural gas feed stream 14 before the feed stream 14 enters the synthesis gas formation reactor 16.
• the hydrogen by-product stream 31 is depicted as mixing with the feed stream 14 before entering the synthesis gas formation reactor 16, the hydrogen by-product stream 31 can also mix with the feed stream 14 during and/or after the feed stream 14 enters the formation reactor 16 instead of, or in addition to mixing with the feed stream 14 before entering the synthesis gas formation reactor 16.
• the hydrogen in the hydrogen by-product stream 31 reacts with CO 2 in the natural gas product stream 14 in a reverse water gas shift reaction to prepare additional CO, which is then converted into additional hydrocarbons. Accordingly, the volume amount of CO 2 in the synthesis gas stream 17 exiting synthesis gas formation reactor 16 is substantially less than the volume amount of CO 2 in the natural gas feed stream 14 prior to mixing with the hydrogen by-product stream 13.

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Hydrogen, Water And Hydrids (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=22376116

Family Applications (1)

Country Status (8)

Cited By (4)

Families Citing this family (14)

Citations (8)

Family Cites Families (15)

• 2002
  • 2002-04-09 US US10/118,029 patent/US6846404B2/en not_active Expired - Lifetime
• 2003
  • 2003-03-25 AU AU2003226025A patent/AU2003226025A1/en not_active Abandoned
  • 2003-03-25 WO PCT/US2003/009331 patent/WO2003087271A1/en not_active Ceased
  • 2003-03-25 JP JP2003584215A patent/JP4231415B2/ja not_active Expired - Fee Related
  • 2003-03-25 BR BR0308635-6A patent/BR0308635A/pt not_active IP Right Cessation
  • 2003-03-31 GB GB0307420A patent/GB2388118B/en not_active Expired - Fee Related
  • 2003-04-02 AU AU2003203438A patent/AU2003203438B2/en not_active Ceased
  • 2003-04-07 ZA ZA200302688A patent/ZA200302688B/xx unknown
  • 2003-04-09 NL NL1023135A patent/NL1023135C2/nl not_active IP Right Cessation
• 2004
  • 2004-09-27 US US10/949,340 patent/US20050043417A1/en not_active Abandoned

Patent Citations (8)

Also Published As

Similar Documents

Legal Events