WO2012106795A1 - Amélioration de procédé fischer-tropsch pour la formulation de combustible hydrocarboné - Google Patents

Amélioration de procédé fischer-tropsch pour la formulation de combustible hydrocarboné Download PDF

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WO2012106795A1
WO2012106795A1 PCT/CA2011/000151 CA2011000151W WO2012106795A1 WO 2012106795 A1 WO2012106795 A1 WO 2012106795A1 CA 2011000151 W CA2011000151 W CA 2011000151W WO 2012106795 A1 WO2012106795 A1 WO 2012106795A1
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Prior art keywords
hydrogen
stream
syngas
naphtha
fischer
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PCT/CA2011/000151
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English (en)
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Steve Kresnyak
Timothy W. Giles
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Steve Kresnyak
Giles Timothy W
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Application filed by Steve Kresnyak, Giles Timothy W filed Critical Steve Kresnyak
Priority to PCT/CA2011/000151 priority Critical patent/WO2012106795A1/fr
Priority to MX2013009296A priority patent/MX356953B/es
Priority to NZ614183A priority patent/NZ614183A/en
Priority to JP2013552800A priority patent/JP5801417B2/ja
Priority to BR112013020515A priority patent/BR112013020515A2/pt
Priority to MYPI2013002957A priority patent/MY163924A/en
Publication of WO2012106795A1 publication Critical patent/WO2012106795A1/fr

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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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    • C10G2300/42—Hydrogen of special source or of special composition
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    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
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    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
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    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
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    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • 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
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Definitions

  • the present invention relates to the modification of the Fischer-Tropsch sequence of operations including the Fischer-Tropsch process for the production of hydrocarbon fuels in an efficient manner.
  • the Fischer-Tropsch process converts hydrogen and carbon monoxide (commonly known as syngas) into liquid hydrocarbon fuels, examples of which include synthetic diesel, naphtha, kerosene, aviation or jet fuel and paraffinic wax.
  • syngas hydrogen and carbon monoxide
  • the coal, gas or biomass, etc. is thermally gasified using heat and pressure to produce the syngas which results in turning the feedstock into hydrogen and carbon monoxide.
  • the synthetic fuels are very appealing from an environmental point of view, since they are paraffinic in nature and substantially devoid of contamination.
  • the patent teaches a process for synthesizing hydrocarbons where initially, a synthesis gas stream is formulated in a syngas generator.
  • the synthesis gas stream comprises primarily hydrogen and carbon monoxide.
  • the process involves catalytically converting the synthesis gas stream in a synthesis reaction to produce hydrocarbons and water followed by the generation of hydrogen-rich stream in the hydrogen generator.
  • the process indicates that the hydrogen generator is separate from the syngas generator ⁇ supra) and that the syngas generator comprises either a process for converting hydrocarbons to olefins, a process for catalytically dehydrogenating hydrocarbons, or a process for refining petroleum, and a process for converting hydrocarbons to carbon filaments.
  • the final step in the process in its broadest sense, involves consumption of hydrogen from the hydrogen-rich stream produced in one or more processes that result and increase value of the hydrocarbons or the productivity of the conversion of the hydrocarbons from the earlier second mentioned step.
  • the liquid fuels begin with the organic material, typically biomass as a solid feedstock.
  • the process involves a stage for the gasification of the solid feedstock, a stage for purification of synthesis gas and subsequently a stage for transformation of the synthesis gas into a liquid fuel.
  • the solid feedstock is subjected to a gasification stage so as to convert said feedstock into synthesis gas comprising carbon monoxide and hydrogen,
  • purification treatment that comprises an adjustment for increasing the molar ratio of hydrogen to carbon monoxide, H2/CO, up to a predetermined value, preferably between 1.8 and 2.2,
  • stage b) the purified synthesis gas that is obtained in stage b) is subjected to a conversion stage that comprises the implementation of a Fischer- Tropsch-type synthesis so as to convert said synthesis gas into a liquid effluent and a gaseous effluent,
  • the liquid effluent that is obtained in stage c) is fractionated so as to obtain at least two fractions that are selected from the group that consists of: a gaseous fraction, a naphtha fraction, a kerosene fraction, and a gas oil fraction, and e) at least a portion of the naphtha fraction is recycled in gasification stage.”
  • an oxidizing agent such as water vapour and gaseous hydrocarbon feedstocks such as natural gas with the recycled naphtha
  • the process instructs the conversion of natural gas or other fossil fuels to higher hydrocarbons where the natural gas or the fossil fuels is reacted with steam and oxygenic gas in a reforming zone to produce synthesis gas which primarily contains hydrogen, carbon monoxide and carbon dioxide.
  • the synthesis gas is then passed into a Fischer-Tropsch reactor to produce a crude synthesis containing lower hydrocarbons, water and non-converted synthesis gas.
  • the crude synthesis stream is separated in a recovery zone into a crude product stream containing heavier hydrocarbons, a water stream and a tail gas stream containing the remaining constituents.
  • the tail gas stream is reformed in a separate steam reformer with steam and natural gas and then the sole reformed tail gas is introduced into the gas stream before being fed into the Fischer-Tropsch reactor.
  • the patentees primarily focused on the production of the high carbon content syngas in a GTL environment using an ATR as crude synthesis stream and reforming the synthesis tail gas in an SMR with natural gas addition to create optimum conditions that feed to the Fischer-Tropsch reactor.
  • this reference employs, as a cornerstone technology, catalytic gasification.
  • the present technology has applicability in the fuel synthesis art.
  • One object of the present invention is to provide an improved Fischer-Tropsch based synthesis process for synthesizing hydrocarbons with a substantially increased yield.
  • a further object of one embodiment of the present invention is to provide a process for synthesing hydrocarbons, comprising the steps of formulating a hydrogen lean syngas stream in a non-catalytic thermal partial oxidizing gasification reaction (POX); catalytically converting the syngas stream to produce naphtha; recycling produced naphtha as a feedstream to a hydrogen generator to formulate/synthesize a hydrogen rich stream; and combining the hydrogen rich stream with the hydrogen lean syngas stream of step (a) to enhance the conversion of hydrocarbons.
  • POX non-catalytic thermal partial oxidizing gasification reaction
  • the present technology provides a very elegant solution to ameliorate the shortcomings that have been clearly evinced in the prior art references.
  • the prior art in the form of patent publications, issued patents, and other academic publications, all recognize the usefulness of a Fischer-Tropsch process, steam methane reforming, autothermal reforming, biomass gasification, naphtha recycle, and other processes, the prior art when taken individually or when mosaiced is deficient a process that provides the synthesis of a hydrogen rich stream to augment a lean stream for passage into a Fischer-Tropsch or suitable reactor for the purpose of enhancing the production of, as one example, diesel fuel or aviation fuel.
  • the Fischer-Tropsch process is particularly useful since the resultant synthetic fuel is "clean" fuel and does not have the contamination level typically associated with the same petroleum based fuel.
  • the present invention amalgamates, in a previously unrecognized combination, a series of known unit operations into a much improved synthesis route for production of synthetic hydrocarbon fuels.
  • This process engages a counter-intuitive step, namely, the removal of a production fraction, namely the naphtha, which, despite being a refined product, is then effectively destroyed making use of the naphtha as a feedstock for a hydrogen generator and then recycled into the Fischer-Tropsch generator.
  • This keystone unit operation is propitious since it works in concert with all of the other precursor operations which, of their own right, are highly effective, namely the gasification, hydrogen generation, and Fischer-Tropsch synthesis operations.
  • the process may also include an autothermal reforming unit (ATR) operation.
  • ATR autothermal reforming unit
  • autothermal reforming employs carbon dioxide and oxygen, or steam, in a reaction with light hydrocarbon gases like natural gas to form syngas. This is an exothermic reaction in view of the oxidation procedure.
  • the hydrogen to carbon monoxide ratio produced is 1 : 1 and when the autothermal reformer uses steam, the ratio produced is approximately 2.5: 1.
  • an ATR may also be considered as a hydrogen generator, as described previously. It has been found that the addition of the ATR operation to the circuit in combination with the hydrogen generation circuit, shown in the example above as a steam methane reformer (SMR), has a significant effect on the hydrocarbon productivity from the overall process.
  • SMR steam methane reformer
  • refinery gas a feedstock to the ATR together with the naphtha recycle as feedstock to the SMR, which results in a significant increase in the volume of syndiesel fuel produced.
  • the process is capable of converting 100% of all the carbon introduced by the biomass feedstock to syndiesel with a 300% increase in production of syndiesel and synthetic jet fuel, as compared to conventional Fischer- Tropsch operation and without the production of any hydrocarbon byproducts. This obviously has significant economic benefits.
  • a further object of one embodiment of the present invention is to provide a process for synthesing hydrocarbons, comprising the steps of: (a) formulating a hydrogen lean syngas stream in a non-catalytic partial oxidation reformer (POX) reaction; (b) catalytically converting the syngas stream to produce hydrocarbon containing at least naphtha and fuel gas; (c) recycling the naphtha to a hydrogen generator to form a hydrogen rich stream; (d) recycling fuel gas from step (b) to a second syngas generator to form a supplemental syngas stream; and (e) combining the hydrogen rich stream and the supplemental syngas stream with the hydrogen lean stream of step (a) to enhance the conversion of hydrocarbons.
  • POX non-catalytic partial oxidation reformer
  • a system for synthesizing hydrocarbons comprising: (a) means for generating syngas lean in hydrogen content; (b) means for catalytically converting the syngas to produce hydrocarbon containing at least naphtha; (c) a hydrogen generator; (d) circuit means for recycling naphtha to the hydrogen generator to form a hydrogen rich stream; and (e) circuit means for combining the hydrogen rich stream with the syngas stream lean in hydrogen content to provide a blended and enriched hydrogen content stream for enhancing hydrocarbon production.
  • Figure 1 is a process flow diagram of methodology known in the prior art
  • Figure 2 is a process flow diagram similar to Figure 1, illustrating a first embodiment of the present invention
  • Figure 3 is a process flow diagram illustrating a further variation of the instant technology
  • Figure 4 is a process flow diagram illustrating yet another variation of the present invention.
  • Figure 5 is a process flow diagram of a still further embodiment of the present invention.
  • Figure 6 is a process flow diagram illustrating a still further variation of the present methodology.
  • FIG. 1 shown is a process flow diagram of a circuit for gasifying biomass with the result being the production of naphtha and syndiesel.
  • the process is generally denoted by numeral 10 and begins with a biomass feedstock 12, which feedstock has been described with examples herein previously.
  • the biomass is then treated in a gasifier 14 to which oxygen 16 may be added as required.
  • the gasifier may be any suitable gasifier, however, as an example, a gasifier that is useful in this process is that which has been patented by Choren Industries GmbH. Details of this gasifier and the process for using the gasifier are disclosed in United States Patent No. 7,776,114, issued August 17, 2010, to Ruger et al.
  • Choren gasification process and apparatus has been found to be effective in the methodology of the present invention to be discussed hereinafter.
  • Choren process the same effectively involves a low temperature pyrolysis stage which is followed by a high temperature gasification stage.
  • Choren gasifier is a highly eligible process and apparatus for carrying out the instant technology, it will be well appreciated by those skilled in the art that any other suitable gasifier can be integrated into the process without any compromise in performance.
  • Table 1 delineates gasifiers useful for syngas production.
  • Synthesis gas composition (%vol.) after gas cleaning
  • the number in the bracket for Carbo V gasifier is the synthesis gas composition, when air is used as gasification agent.
  • the gasifier is useful for synthesizing a hydrogen lean or deficient synthesis gas (syngas) stream in a non-catalytic partial oxidation reaction.
  • the so formed syngas is then subjected to cleaning operations 18 with subsequent removal of carbon dioxide at 20.
  • WGS water gas shift
  • the process uses the supplemental addition of hydrogen to maximize the conversion to syndiesel.
  • the raw syngas is treated in various steps of scrubbing units and guard units well known to those skilled in the art to create a relatively pure clean syngas suitable for use in a
  • the carbon dioxide removal may also include a compression step (not shown) which is optionally attributable to the other processes discussed in forthcoming Figures.
  • the syngas is then transferred to a Fischer-Tropsch reactor 22 to produce the hydrocarbons and water.
  • the so formed hydrocarbons are then passed on to a hydrocarbon cracking stage 24, a product fractionating stage 26 with naphtha being produced at 28 as a fraction, as well as diesel 30 as an additional product.
  • the diesel 30 formulated in this process is commonly known as syndiesel.
  • this process results in the formulation of 701 barrels per day (bbl/day) based on 20 tonnes per hour of forestry biomass.
  • an external source of hydrogen 32 is to be supplemented to the Fischer- Tropsch unit 22 and hydrocarbon cracking unit 24 denoted as streams 36 and 34 respectively.
  • energy 35 from the gasifier typically in the form of steam, may be used to generate power and this is equally true of the Fischer-Tropsch reactor 22 creating energy 40.
  • Table 2 establishes a comparison between FT diesel and conventional petroleum based diesel.
  • Naphtha can be generally defined as a distilled fraction of the Fischer-Tropsch FT hydrocarbon liquids, categorized by way of example with a typical boiling range of 30°C to 200°C, and more preferred 30°C to 105°C.
  • the specific naphtha specification will be optimized for each application to maximize syndiesel production and partially or fully eliminate the naphtha byproduct.
  • Suitable examples of FT reactors include fixed bed reactors and slurry-bubble reactors such as tubular reactors, and multiphase reactors with a stationary catalyst phase.
  • the FT catalyst particles are suspended in a liquid, e.g., molten hydrocarbon wax, by the motion of bubbles of syngas sparged into the bottom of the reactor.
  • a liquid e.g., molten hydrocarbon wax
  • the syngas is absorbed into the liquid and diffuses to the catalyst for conversion to hydrocarbons.
  • Gaseous products and unconverted syngas enter the gas bubbles and are collected at the top of the reactor. Liquid products are recovered from the suspending liquid using different techniques such as separators, filtration, settling, hydrocyclones, and magnetic techniques.
  • Cooling coils immersed in the slurry remove heat generated by the reaction.
  • the FT catalyst In a fixed bed reactor, the FT catalyst is held in a fixed bed contained in tubes or vessels within the reactor vessel. The syngas flowing through the reactor vessel contacts the FT catalyst contained in the fixed bed. The reaction heat is removed by passing a cooling medium around the tubes or vessels that contain the fixed bed.
  • H 2 and CO combine via polymerization to form hydrocarbon compounds having varying numbers of carbon atoms. Typically 70% conversion of syngas to FT liquids takes place in a single pass of the FT unit. It is also common practice to arrange the FT reactors in series and parallel to achieve conversion levels of 90+%.
  • the FT liquids After the FT separation stage to divert the unconverted syngas and light hydrocarbons, the FT liquids are directed to the hydrocarbon upgrader unit denoted as 27.
  • the upgrader unit typically contains a hydrocracking step 24 and a fractionation step 26.
  • Hydrocracking denoted as 24 used herein is referencing the splitting an organic molecule and adding hydrogen to the resulting molecular fragments to form multiple smaller hydrocarbons (e.g., C 10 H 22 + H 2 ⁇ C H 10 and skeletal isomers + C 6 H 14 ). Since a hydrocracking catalyst may be active in hydroisomerization, skeletal isomerization can occur during the hydrocracking step. Accordingly, isomers of the smaller hydrocarbons may be formed.
  • Hydrocracking a hydrocarbon stream derived from Fischer-Tropsch synthesis preferably takes place over a hydrocracking catalyst comprising a noble metal or at least one base metal, such as platinum, cobalt- molybdenum, cobalt-tungsten, nickel-molybdenum, or nickel-tungsten, at a temperature of from about 550°F to about 750°F (from about 288°C to about 400°C) and at a hydrogen partial pressure of about 500 psia to about 1,500 psia (about 3,400 kPa to about 10,400 kPa).
  • a hydrocracking catalyst comprising a noble metal or at least one base metal, such as platinum, cobalt- molybdenum, cobalt-tungsten, nickel-molybdenum, or nickel-tungsten, at a temperature of from about 550°F to about 750°F (from about 288°C to about 400°C) and at a hydrogen partial pressure of about 500 psia to about 1,500
  • the hydrocarbons recovered from the hydrocracker are further fractionated 26 and refined to contain materials that can be used as components of mixtures known in the art such as naphtha, diesel, kerosene, jet fuel, lube oil, and wax.
  • the combined unit consisting of the hydrocracker 24 and hydrocarbon fractionator 26 are commonly known as the hydrocarbon upgrader 27.
  • the hydrocarbon products are essentially free of sulfur.
  • the diesel may be used to produce environmentally friendly, sulfur-free fuel and/or blending stock for diesel fuels by using as is or blending with higher sulfur fuels created from petroleum sources.
  • useable energy commonly generated as steam from the gasification stage may be used to generate electric power 38.
  • useable energy that can be drawn from the Fischer-Tropsch unit owing to the fact that the reaction is very exothermic and this represents a useable source of energy. This is denoted by numeral 40.
  • FIG 2 shown is a preliminary embodiment of the technology of the instant invention. As is evinced from Figure 2, many of the preliminary steps are common with that which is shown in Figure 1.
  • Table 4 lists a series of biomass species with calorific values for the purposes of examples.
  • Table 5 sets forth component analysis of examples of biomass.
  • the initial feedstock to the gasifier may be any one of coal, biomass, petroleum resids, municipal waste, plastics, wood, demetallized tire scrap, forestry waste, waste water byproduct, sewage biomass, livestock waste products, agricultural byproduct and waste, carbonaceous material and mixtures thereof.
  • the hydrogen to carbon monoxide ratio of the clean syngas leaving the biomass gasifier stage once it has passed the cleanup stage 18, is generally 1 : 1.
  • the carbon dioxide removal stage 20 at least a portion of the carbon dioxide 42 may be reintroduced into the gasifier 14 for purposes of controlling the reaction therein.
  • the procedure follows the unit operations as identified in Figure 1.
  • one of the most effective procedures in the instant technology relates to the fact that once the product fractionation stage has been completed and the naphtha 28 formulated, it has been found that by inclusion of the hydrogen generator using naphtha as the primary source, significant results can be achieved in the production of the synthetic diesel.
  • the steam reformer may contain any suitable catalyst and be operated at any suitable conditions to promote the conversion of the naphtha hydrocarbon to hydrogen H 2 and carbon monoxide.
  • the addition of steam and natural gas may be optimized to suit the desired production of hydrogen and carbon monoxide.
  • natural gas or any other suitable fuel can be used to provide energy to the SMR reaction furnace.
  • the catalyst employed for the steam reforming process may include one or more catalytically active components such as palladium, platinum, rhodium, iridium, osmium, ruthenium, nickel, chromium, cobalt, cerium, lanthanum, or mixtures thereof.
  • the catalytically active component may be supported on a ceramic pellet or a refractory metal oxide. Other forms will be readily apparent to those skilled.
  • the steam methane reformer may be augmented in terms of the hydrogen using natural gas 46, or using refinery gas 48 from the Fischer-Tropsch reactor 22 and the hydrocarbon upgrader 27. Energy recovered from the SMR 46 in the form of steam may be distributed via line 50 for production of electric power 38.
  • the hydrogen rich stream 52 has been formulated in the SMR, the same is introduced into the syngas stream exiting syngas clean-up stage 18.
  • a hydrogen rich stream from the SMR unit is combined at an optimal rate with a relatively lean hydrogen gas stream to generate the optimal Fischer-Tropsch syngas feed.
  • This commingled or mixed stream is subject to the carbon dioxide removal and acts as a feedstock to the Fischer-Tropsch reactor 22.
  • the stream has a hydrogen to carbon monoxide ratio of approximately 1 : 1 to 5 : 1 , preferably 2 : 1 as indicated by numeral 53.
  • a portion 54 of the hydrogen rich stream 52 may bypass the C0 2 removal unit and feed the Fischer-Tropsch unit directly at 53.
  • the hydrogen to carbon monoxide ratio is approximately 2 and is then subsequently introduced into the Fischer-Tropsch reactor 22 and subjected to the same steps that have been discussed with respect to Figure 1.
  • the results are quite substantial, providing the naphtha recirculation route and particularly using the naphtha as a feedstock to generate a hydrogen rich stream, the result is syndiesel production in great excess to that which is discussed in Figure 1.
  • the syndiesel production by following the methodology of Figure 2 results in a 977 barrel per day (bbl/day) production based on a 20 tonnes per hour biomass feed.
  • a small portion of the hydrogen rich stream 52 may be removed and treated on by a common hydrogen purification unit, a typical example is a Pressure Swing Adsorption unit (PSA) 55, to create a high quality hydrogen stream 56 for use in the hydrocarbon upgrader unit 27.
  • PSA Pressure Swing Adsorption unit
  • Figure 3 sets forth a further interesting variation on the overall process that is set forth in Figure 2.
  • the process results in the formulation of not only diesel, but also jet fuel or aviation fuel.
  • the operations common with Figure 2 are denoted with similar numerals.
  • a split product is made between the jet fuel and diesel fuel.
  • the split may be 25%:75% between jet fuel and diesel production from the firactionator 26.
  • jet fuel as indicated by numeral 59 in Figure 3 requires modification of the fractionation unit operation 26.
  • the fractionation unit operation can be modified for the jet fuel recovery by adding a suitable side stripper as part of the fractionation unit operation 26.
  • a hydrotreater step 57 should be considered for the hydrocarbon cracking unit.
  • the hydrotreater is a method to ensure the stability of the refined products by addition and saturation of the product with hydrogen.
  • the jet fuel produced is unique in that it will be of very high purity and free of sulfur compounds, thus wished as a "Clean Green" aviation fuel.
  • FIG. 4 A further variation of the overall process embraced by the technology discussed herein is shown in Figure 4.
  • the process flow of unit operations shown in Figure 4 is an amplification of the process as shown in Figure 2 and essentially augments further utilization of carbon and hydrogen to provide an alternate stream for introduction into the Fischer-Tropsch reactor 22. This has dramatic consequences on the production of syndiesel.
  • the similarly denoted unit operations are common in Figure 4. From the flow diagram, it is evident that the SMR unit operation 44 Figure 2 is absent in this flow diagram. This unit operation has been replaced with an ATR (Autothermal Reformer) unit operation, denoted by numeral 60. Both the naphtha and the refinery gas, 62 and 64, respectively, may be combined or separately transformed in the ATR unit 60.
  • ATR Automatic Reformer
  • Utility heating for the ATR may be provided by natural gas 66.
  • Oxygen may be introduced at 70.
  • the ATR is useful to produce some hydrogen and carbon monoxide syngas which is, of course, useful to introduce into and further enhance the Fischer-Tropsch reactor 22.
  • External hydrogen may be used for the hydrocarbon upgrader 27 requirement.
  • the formed syngas from the ATR is denoted by line 68 and is introduced in advance of the carbon dioxide removal stage 20. Alternatively, a portion of 68 or the entire stream 68 may be introduced after the C0 2 removal unit 20. Additional carbon dioxide 69 may also be provided to the ATR to optimize the augmented syngas composition to the Fischer-Tropsch unit 22.
  • the refinery gas 64, oxygen 70, natural gas 66 and carbon dioxide 69 are commingled in optimized proportions and processed through the ATR 60 and blended with the SMR 44 hydrogen rich syngas to achieve the optimum syngas for combining with stream 53 to the FT unit 22.
  • the Fischer- Tropsch reactor is effectively fed with the hydrogen rich stream generated from the SMR as well as the supplemental syngas stream generated from the ATR.
  • the SMR stream and ATR stream are commingled with the hydrogen lean syngas stream exiting cleanup unit operation 18 and subsequently introduced into the Fischer-Tropsch reactor 22.
  • FIG 6 shown is a further variation of the overall process which is similar to that which is shown in Figure 5, with the exception of the absence of gasifier 14 and syngas cleanup operation 18.
  • Other significant features of the present technology can be realized with the following.
  • step (b) naphtha is generated in addition to heavier
  • the process further includes the step of separating at least a portion of the naphtha from the heavier and lighter hydrocarbons.
  • the hydrogen rich stream of step (b) is introduced into the Fischer-Tropsch reactor for reaction.
  • an auxiliary source of hydrogen may be added to the hydrogen generator.
  • the auxiliary source may comprise natural gas or refinery gas, as examples.
  • the converted hydrocarbons comprise at least one of aviation fuel and diesel fuel and in preparation of the fuel, the process may include a series of unit operations between steps (a) through (d) for optimizing conversion of hydrocarbons, including as examples, cleansing syngas by removal of carbon dioxide prior to synthesis of the hydrocarbons.
  • the syngas cleansing includes at least one of a caustic wash to halide removal, an acid wash for ammonia removal, and an activated charcoal treatment for hydrogen sulfide removal.
  • the carbon dioxide removal may be achieved by at least one of drying and compression and removal of the carbon dioxide as a product.
  • this is formed in a thermal gasifier, where the gasifier gasifies a member selected from the group consisting of coal, biomass, petroleum resids, petcoke, municipal waste, plastics, wood waste, demetallized tire scrap, forestry waste material, wastewater biomass, sewage biomass, agricultural waste, agricultural byproducts, carbonaceous material and mixtures thereof.
  • the fraction of naphtha may be generated in addition to heavier hydrocarbons and at least a portion of the heavier hydrocarbons may be separated from the naphtha.
  • the hydrogen generator in step (c) comprises a steam methane reformer (SMR).
  • SMR steam methane reformer
  • the hydrogen rich stream of step (d) is introduced into the Fischer-Tropsch reactor.
  • the process in a variation, further includes the step of adding an auxiliary source of hydrogen to the hydrogen generator and a second hydrogen generator.
  • the circuit means for recycling naphtha to the hydrogen generator comprises a recycle loop and the hydrogen generator comprises a member selected from the group consisting of a steam methane reformer and a autothermal reformer or a combination thereof.
  • the circuit means for recycling naphtha to the hydrogen generator may comprise a recycle loop for recycling naphtha into at least one of the steam methane reformer, the autothermal reformer or a combination thereof.

Abstract

L'invention porte sur un procédé Fischer-Tropsch amélioré pour la synthèse de combustibles hydrocarbonés verts sans soufre et brûlant proprement, dont les exemples comprennent le diesel de synthèse et le carburant aviation. Le naphta est décomposé dans un générateur d'hydrogène et recyclé comme charge de départ vers un réacteur de production de gaz de synthèse (FT) afin d'accroître la production de diesel de synthèse provenant du réacteur. Une autre variante intègre un second générateur d'hydrogène prenant des hydrocarbures gazeux légers pour leur conversion en hydrogène et en monoxyde de carbone qui apportent un complément au réacteur de Fischer-Tropsch. Il en résulte une augmentation importante du volume de diesel de synthèse formulé. L'invention porte également sur un système pour la mise en œuvre du procédé.
PCT/CA2011/000151 2011-02-11 2011-02-11 Amélioration de procédé fischer-tropsch pour la formulation de combustible hydrocarboné WO2012106795A1 (fr)

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PCT/CA2011/000151 WO2012106795A1 (fr) 2011-02-11 2011-02-11 Amélioration de procédé fischer-tropsch pour la formulation de combustible hydrocarboné
MX2013009296A MX356953B (es) 2011-02-11 2011-02-11 Mejoramiento del proceso de fischer-tropsch para la formulación de combustible de hidrocarburo.
NZ614183A NZ614183A (en) 2011-02-11 2011-02-11 Enhancement of fischer-tropsch process for hydrocarbon fuel formulation
JP2013552800A JP5801417B2 (ja) 2011-02-11 2011-02-11 炭化水素燃料調製のためのフィッシャートロプシュ法の強化
BR112013020515A BR112013020515A2 (pt) 2011-02-11 2011-02-11 aprimoramento do processo de fischer-tropsch para a formulação de combustível de hidrocarboneto
MYPI2013002957A MY163924A (en) 2011-02-11 2011-08-11 Enhancement of fischer-tropsch process for hydrocarbon fuel formulation

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JP2023011306A (ja) * 2021-07-12 2023-01-24 東洋エンジニアリング株式会社 合成燃料の製造方法
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