CA2911660C

CA2911660C - Conversion of synthesis gas into liquid hydrocarbons via fischer tropsch synthesis

Info

Publication number: CA2911660C
Application number: CA2911660A
Authority: CA
Inventors: Franciscus Johanna Arnoldus Martens
Original assignee: Nexen Energy ULC
Current assignee: CNOOC Petroleum North America ULC
Priority date: 2013-11-13
Filing date: 2014-11-13
Publication date: 2016-10-04
Anticipated expiration: 2034-11-13
Also published as: CA2911660A1; CA2938299A1; WO2015070332A1

Abstract

A process for converting at least one synthesis gas, having a molar H2 to CO ratio between about 0.25 and 1, into at least one hydrocarbon, via Fischer-Tropsch synthesis by contacting the at least one synthesis gas with at least one catalyst, forming at least one hydrocarbon, wherein said at least one catalyst has Water Gas Shift and Fischer-Tropsch synthesis activity.

Description

2 PCT/CA2014/000823 CONVERSION OF SYNTHESIS GAS INTO LIQUID HYDROCARBONS VIA
FISCHER TROPSCH SYNTHESIS
FIELD
[0001]
The present disclosure relates to improvements in the Fischer-Tropsch ("FT") synthesis and/or process for converting synthesis gas into liquid hydrocarbons suitable for use as liquid fuel or as chemical feedstock.
BACKGROUND
[0002] FT-synthesis is a collection of catalyzed chemical reactions that converts a mixture of carbon monoxide (CO) and hydrogen (H2) into hydrocarbons and water.
A variety of catalysts have been used, but the commercially viable catalysts are comprised of the transition metals: cobalt, iron, and ruthenium. In addition to the transition metal, the catalysts typically contain a number of promoters, including alkali metal oxides and copper. The products of FT-synthesis include alkanes (hydrocarbons with a C-C single straight bond) and alkenes (also called olefins (hydrocarbons having at least one unsaturated C=C
double bond)), which are both suitable for diesel fuel. Other FT-synthesis products include alcohol or other oxygenated hydrocarbons at times, which may be beneficial in some circumstances.

[0003] FT-synthesis has been undergoing development since the 1910's. Examples include the following: 1) BASF, German Patent DRP 293,787 (1913); 2) A.
Mittasch and C.
Schneider, US Patent 1,201,850 (1916); 3) Fischer and Tropsch, German Patent (1925); and 4) Kinetics of the Fischer-Tropsch Synthesis on Iron Catalysts (1964), Anderson, R.B. et al. Bulletin 614, Bureau of Mines, United States Department of the Interior.

[0004]
Current market development and new application is directed toward FT-synthesis using a Cobalt-based catalyst for high FT activity and maximizing the production of long chained alkanes.
Companies involved in Cobalt-based FT-synthesis include Shell (SMDS Bintulu, Pearl GTL Qatar) and Sasol (Oryx Qatar), as well as Velocys, BP-Davy, and Axens. When syngas feed is rich in 1-12 and at preferred temperature, the Cobalt-based FT-synthesis reaction forms mainly alkanes and water according to the overall reaction:

n CO + (2n+1) H2 4 CnH2n+2+ n H20

[0005] The product is mainly paraffinic oil (saturated hydrocarbons).
Consequently the overall molar H2 to CO consumption ratio is about (2n+1)/n 2. The typical Cobalt-based FT
reaction temperature is 220 - 230 degrees Celsius.

[0006] Natural gas ("NG") is the most desirable feedstock from the standpoint of the 1) chemical H2 demand, 2) the minimal cleaning steps required, and 3) the economics for stranded NG resources.

[0007] Liquid and solid based feedstocks have the drawback of shortage of H2 in the reaction scheme, as well as process steps required to remove a larger range of impurities being present at larger quantities (e.g. sulfur containing compounds, ammonia, hydrogen cyanide, metal carbonyls, metals as gas or trapped in compounds/ashes).

[0008] Cobalt-based catalysts' Water Gas Shift ("WGS") activity is too low to compensate, for shortage of H2.

[0009] Iron-based catalysts have both FT and WGS activity. The FT
reaction produces H20 (steam) (same as for the Cobalt-based catalyst), and at shortage of H2, the WGS reaction responds as follows:
CO + H20 (steam) - CO2 + H2

[0010] The typical FT reaction temperature currently practiced is 220-240 C (low-temperature-FT) or 330-360 C (high-temperature-FT).

[0011] With low H2 present and at preferred temperatures, the combined FT
and WGS
reactions form mainly alkenes and CO2 according to the overall reaction:
2n CO + n 112 4 CnH2n n CO2

[0012] The product is mainly olefinic oil (having at least one unsaturated C=C double bond). Consequently the overall molar H2 to CO consumption ratio is about n/2n = 1/2 . By practice we found that the overall consumption ratio is closer to 0.55 than 0.50

[0013] The following is an example of a current process configuration used in the field:

[0014] A refinery, producing a heavy residual feedstock (vacuum residue, visbroken residue, or de-asphalter residue), being in need of 110,000 Sm3/hr pure H2 to satisfy the Hydro-cracker H2 demand, and having the application of partial oxidation ("PDX") of the residual feedstock, requires the subsequent raw synthesis gas cleanup step at a rate of 19,300 kmol/hr followed by hydrogen extraction via a pressure swing absorber ("PSA"), with the PSA-offgas used as a fuel gas and/or as feed to a combined cycle unit producing electricity and superheated steam. The PDX synthesis gas has a molar H2 to CO ratio of 0.9, and the PSA-offgas has a molar H2 to CO ratio of 0.35.

[0015] The high value product is pure H2, while the high CO containing PSA-offgas is only getting the heating equivalent value of Natural Gas, which in many regions now is a fraction of that of liquid fuels.

[0016] The economics for conversion of the CO-containing gas to liquid hydrocarbons is very attractive, even with increased consumption of Natural Gas to compensate for the alternative use of the CO-containing gas.

[0017] Two currently practised schemes are now discussed below. Both schemes apply a Cobalt-based catalyst. This requires an increase of the PDX synthesis gas molar H2 to CO
ratio from 0.9 to about 1.8.

[0018] In the first scheme the desired ratio is achieved by mixing the H2-lean PDX
synthesis gas with enough H2-rich steam methane reformer ("SMR") synthesis gas having a molar H2 to CO ratio of about six (6). This requires the integration of two (2) world scale SMRs. In addition, the hydro-cracker H2 demand is to be satisfied via one additional world scale SMR + WGS + PSA combination. The FT hydrocarbon liquid production is between 21,000 and 29,000 bbl/day, depending on the design efficiency of the process (e.g. multiple reactors in series and/or FT-offgas recycle), and in the less efficient case, an even larger amount of FT-offgas is routed to the fuelgas pool. Although straightforward, the complexity added to the refinery is challenging.

[0019] In the second scheme, the desired ratio is achieved by applying WGS to one portion of the PDX synthesis gas, removing the CO2 by acid gas absorption, and mixing this synthesis gas portion with the other portion of the PDX synthesis gas. The FT
hydrocarbon liquid production is between 10,000 and 12,000 bbl/day, depending on the design efficiency of the process (e.g. multiple reactors in series and/or FT-offgas recycle).

[0020] Unavoidably, the hydro-cracker H2 demand needs to be satisfied, requiring the addition of one world scale SMR + WGS + PSA combination.

[0021] The FT reactions are exothermic, releasing some 15% of the chemical energy content of the synthesis gas, which typically is transferred via indirect heat exchange to raise saturated steam. The steam pressure controls the FT synthesis temperature. For a Cobalt-based FT catalyst, the synthesis is controlled below 230 degrees Celsius to prevent excessive CH4 production. As a consequence, the co-production of saturated steam is at a pressure of 1.7 to 2.0 MPa only, which is of low value to the refinery.

[0022] There is a need to reduce complexity in existing FT process technologies.

[0023] There is also a need to generate steam at a more useful (higher) pressure.
SUMMARY

[0024] In one aspect, there is provided a process for converting H2-lean syngas into one or more hydrocarbons, comprising:
supplying a H2-lean syngas, including H2 and CO in a molar ratio of less than 1.0, and adscititious H20 to the reaction zone such that a reaction mixture becomes disposed in sufficient proximity to a catalyst material within the reaction zone, the catalyst material having both water gas shift activity and Fischer-Tropsch synthetic activity, such that the conversion is effected.

[0025] In some implementations, for example, the H20 of the adscititious H20 is adscititious relative to any H20 that is produced during the conversion of the H2-lean syngas

[0026] In some implementations, for example, the effected conversion includes at least Fischer-Tropsch synthesis.

[0027] In some implementations, for example, the 1120 of the adscititious 1120 is adscititious relative to any H20 that is produced during the Fischer-Tropsch synthesis.

[0028] In some implementations, for example, the reaction mixture is generated by admixing of the H2-lean syngas and the adscititious 1120.

[0029] In some implementations, for example, the supplying of the adscititious 1120 to the reaction zone is effected independently of the supplying of the H2-lean syngas to the reaction zone.

[0030] In some implementations, for example, the H20 of the adscititious H20 is in the form of steam.

[0031] In some implementations, for example, the molar H2/C0 ratio is between 0.25 and 1.0, such as, for example, between 0.25 and 0.6, and such as, for example, between 0.25 and 0.5.

[0032] In some implementations, for example, the ratio of moles of H2 to moles of CO
within the supplied H2-lean syngas is less than 0.55, the ratio of moles of H2O of the supplied adscititious 1420 to moles of CO of the supplied H2-lean syngas is defined in accordance with the following formula:
H20/C0feed = A X (0.55 - 112/CO 1 feed) or, equivalently:
the ratio of moles of H20 of the supplied adscititious H20 to moles of CO of the supplied H2-lean syngas ¨
A x (0.55 ¨ (the ratio of moles of H2 of the H2-lean syngas to moles of CO of the H2-lean syngas);
wherein A is between 1.0 and 1.3

[0033] In some implementations, for example, prior to the supplying of the H2-lean syngas to the reaction zone, any treatment of the H2-lean syngas feedstock is such that no H2 enrichment of the H2-lean syngas is effected prior to the reaction zone.

[0034] In some implementations, for example, the catalyst material includes a Fe-based catalyst material.

[0035] In some implementations, for example, the catalyst material is activated.

[0036] In some implementations, for example, the catalyst material includes at least one promoter.

[0037] In some implementations, for example, the at least one promoter includes one or more metal oxides, and wherein the metal oxide is an oxide of any one of manganese, potassium, chromium, and copper.

[0038] In some implementations, for example, the reaction zone is disposed at a pressure of between 0.2 to 7 MPa, such as, for example, between 1.5 to 6 MPa, and such as, for example, between 1.5 to 3 MPa.

[0039] In some implementations, for example, the reaction zone is disposed at a temperature of between 240 degrees Celsius and 320 degrees Celsius, such as, for example, between 260 degrees Celsius and 300 degrees Celsius, and such as, for example, between 270 degrees Celsius and 290 degrees Celsius.

[0040] In some implementations, for example, at least one of the one or more hydrocarbons that are produced by the conversion is liquid at standard temperature and pressure conditions.

[0041] In some implementations, for example, the H2-lean syngas is derived from any one of bitumen, heavy oil, shale oil, heavy hydrocarbon residues from a heavy oil or bitumen upgrading process, natural gas, coal, biomass, organic waste.

[0042] In some implementations, for example, the heavy hydrocarbon residue includes a residual product from any one of atmospheric distillation, vacuum distillation, deasphalting, coking, visbreaking, thermal cracking, fluid catalytic cracking, resid fluid catalytic cracking, or any combination thereof.

[0043] In another aspect, there is provided a process for upgrading a hydrocarbon feed comprising:
converting the hydrocarbon feed to a first syngas;
separating the first syngas into at least a H2-rich stream and a H2-lean syngas, wherein the H2-lean syngas includes H2 and CO in a molar ratio of less than 1.0; and supplying the H2-lean syngas and adscititious H20 to the reaction zone such that a reaction mixture becomes disposed in sufficient proximity to a catalyst material within the reaction zone, the catalyst material having both water gas shift activity and Fischer-Tropsch synthetic activity, such that conversion of the H2-lean syngas to one or more hydrocarbons is effected.

[0044] Relative to the H2-lean syngas, the H2-rich stream includes a higher concentration of 142

[0045] In some implementations, for example, the 1120 of the adscititious 1120 is adscititious relative to any H20 that is produced during the conversion of the H2-lean syngas.

[0046] In some implementations, for example, the effected conversion includes at least Fischer-Tropsch synthesis.

[0047] In some implementations, for example, the H20 of the adscititious 1120 is adscititious relative to any H20 that is produced during the Fischer-Tropsch synthesis.

[0048] In some implementations, for example, the reaction mixture is generated by admixing of the 112-lean syngas and the adscititious H20.

[0049] In some implementations, for example, the supplying of the adscititious H20 to the reaction zone is effected independently of the supplying of the H2-lean syngas to the reaction zone.

[0050] In some implementations, for example, the H20 of the adscititious H20 is in the form of steam.

[0051] In some implementations, for example, the ratio of moles of H2 to moles of CO
within the H2-lean syngas is between 0.25 and 1.0, such as, for example, between 0.25 and 0.6, and such as, for example, between 0.25 and 0.5.

[0052] In some implementations, for example, the ratio of moles of H2 to moles of CO
within the supplied H2-lean syngas is less than 0.55, the ratio of moles of H20 of the supplied adscititious H20 to moles of CO of the supplied Hz-lean syngas is defined in accordance with the following formula:
H20/COreed = A x (0.55 - H2/C0feed) or, equivalently:
the ratio of moles of H20 of the supplied adscititious H20 to moles of CO of the supplied H2-lean syngas ¨
A x (0.55 ¨ (the ratio of moles of 112 of the H2-lean syngas to moles of CO of the H2-lean syngas);
wherein A is between 1.0 and 1.3

[0053] In some implementations, for example, prior to the supplying of the H2-lean syngas to the reaction zone, any treatment of the H2-lean syngas feedstock is such that no 112 enrichment of the H2-lean syngas is effected prior to the reaction zone.

[0054] In some implementations, for example, the catalyst material includes a Fe-based catalyst material.

[0055] In some implementations, for example, the catalyst material is activated.

[0056] In some implementations, for example, the catalyst material includes at least one promoter.

[0057] In some implementations, for example, the at least one promoter includes one or more metal oxides, and wherein the metal oxide is an oxide of any one of manganese, potassium, chromium, and copper.

[0058] In some implementations, for example, the reaction zone is disposed at a pressure of between 0.2 to 7 MPa, such as, for example, between 1.5 to 6 MPa, and such as, for example, between 1.5 to 3 MPa.

[0059] In some implementations, for example, the reaction zone is disposed at a temperature of between 240 degrees Celsius and 320 degrees Celsius, such as, for example, between 260 degrees Celsius and 300 degrees Celsius, and such as, for example, between 270 degrees Celsius and 290 degrees Celsius.

[0060] In some implementations, for example, at least one of the one or more hydrocarbons that are produced by the conversion is liquid at standard temperature and pressure conditions.

[0061] In some implementations, for example, the heavy hydrocarbon residue includes a residual product from any one of atmospheric distillation, vacuum distillation, deasphalting, coking, visbreaking, thermal cracking, fluid catalytic cracking, resid fluid catalytic cracking, or any combination thereof.

[0062] In some implementations, for example, the converting of hydrocarbon feed to a first syngas is effected by any one of gasification, partial oxidation, auto-thermal reforming, steam reforming, or any combination thereof

[0063] In some implementations, for example, the process further comprises effecting hydrocracking with the H2-rich stream separated from the first syngas.

[0064] In another aspect, there is provided a process for upgrading a hydrocarbon residue and producing bitumen (an oil based semi solid substance) via steam-assisted gravity drainage ("SAGD") using steam that is generated by at least the heat produced by the upgrading, comprising:
converting the heavy hydrocarbon residue to a syngas product;

converting the syngas product via at least Fischer-Tropsch synthesis, wherein the conversion is effected within a reaction zone disposed at a temperature of greater than 260 degrees Celsius;
transferring heat, from the converting, to a steam generator;
with the transferred heat, effecting generation of steam by the steam generator; and supplying steam to a hydrocarbon reservoir via a SAGD injection well to effect mobilization of bitumen within the hydrocarbon reservoir.

[0065] In some implementations, for example, the transferred heat is transferred from the reaction zone.

[0066] In some implementations, for example, the transferred heat is transferred from Fischer-Tropsch products generated by the converting.

[0067] In some implementations, for example, the temperature within the reaction zone is between 260 degrees Celsius and 300 degrees Celsius, such as, for example, between 270 degrees Celsius and 290 degrees Celsius.

[0068] In some implementations, for example, the reaction zone is disposed at a pressure of between 0.2MPa to 7 MPa, such as, for example, between 1.5 MPa to 6 MPa, and such as, for example, 1.5 MPa to 3 MPa.

[0069] In some implementations, for example, the conversion is effected by a catalyst material.

[0070] In some implementations, for example, the catalyst material is activated.

[0071] In some implementations, for example, the catalyst material includes a Fe-based catalyst material.

[0072] In some implementations, for example, the catalyst material includes at least one promoter.

[0073] In some implementations, for example, the at least one promoter includes one or more metal oxides, and wherein the metal oxide is an oxide of any one of manganese, potassium, chromium, and copper.

[0074] In some implementations, for example, at least one of the one or more hydrocarbons that are produced by the conversion by at least Fischer-Tropsch synthesis are liquid at standard temperature and pressure conditions.

[0075] In some implementations, for example, the converting of the heavy hydrocarbon residue includes:
converting the heavy hydrocarbon to a first syngas; and separating the first syngas into at least a H2-rich stream and a H2-lean syngas, wherein the H2-lean syngas defines the syngas product such that the conversion, by at least Fischer-Tropsch synthesis, is of the H2-lean syngas.

[0076] In some implementations, for example, the process further comprises effecting hydrocracking with the H2-rich stream separated from the first syngas.

[0077] In some implementations, for example, the H2-lean syngas includes H2 and CO
in a molar ratio of less than 1.0, and prior to the conversion, by at least Fischer-Tropsch synthesis, the process further comprises: supplying the H2-lean syngas and adscititious H20 to the reaction zone such that a reaction mixture becomes disposed in sufficient proximity to a catalyst material within the reaction zone, the catalyst material having both water gas shift activity and Fischer-Tropsch synthetic activity, such that the conversion, by at least Fischer-Tropsch synthesis, is effected.

[0078] In some implementations, for example, the H20 of the adscititious H2O is adscititious relative to any H20 that is produced during the conversion of the H2-lean syngas.

[0079] In some implementations, for example, the H20 of the adscititious H20 is adscititious relative to any H20 that is produced during the Fischer-Tropsch synthesis.

[0080] In some implementations, for example, the reaction mixture is generated by admixing of the H2-lean syngas and the adscititious H20.

[0081] In some implementations, for example, the supplying of the adscititious H20 to the reaction zone is effected independently of the supplying of the H2-lean syngas to the reaction zone.

[0082] In some implementations, for example, the H2O of the adscititious H20 is in the form of steam.

[0083] In some implementations, for example, the ratio of moles of H2 to moles of CO
within the supplied H2-lean syngas is between 0.25 and 1.0, such as, for example, between 0.25 and 0.6, and such as, for example, between 0.25 and 0.5.

[0084] In some implementations, for example, when the ratio of moles of H2 to moles of CO within the supplied H2-lean syngas is less than 0.55, the ratio of moles of H2O of the supplied adscititious H20 to moles of CO of the supplied H2-lean syngas is defined in accordance with the following formula:
H20/C0feed = A x (0.55 - H2/C0feed) or, equivalently:
the ratio of moles of H20 of the supplied adscititious H2O to moles of CO of the supplied H2-lean syngas ¨
A x (0.55 ¨ (the ratio of moles of H2 of the H2-lean syngas to moles of CO of the H2-lean syngas);
wherein A is between 1 and 1.3.

[0085] In some implementations, for example, prior to the supplying of the H2-lean syngas to the reaction zone, any treatment of the H2-lean syngas feedstock is such that no H2 enrichment of the H2-lean syngas is effected prior to the reaction zone.

[0086] In some implementations, for example, the heavy hydrocarbon residue includes a residual product from any one of atmospheric distillation, vacuum distillation, deasphalting, coking, visbreaking, thermal cracking, fluid catalytic cracking, resid fluid catalytic cracking, or any combination thereof BRIEF DESCRIPTION OF THE DRAWINGS

[0087] In the drawings, embodiments of the invention are illustrated by way of example. It is to be expressly understood that the description and drawings are only for the purpose of illustration and as an aid to understanding, and are not intended as a definition of the limits of the invention.

[0088] Embodiments will now be described, by way of example only, with reference to the attached figures, wherein:

[0089] Figure 1 is a flow diagram illustrating the processing of a synthesis gas via a Fischer-Tropsch synthesis;

[0090] Figure 2 is a flow diagram illustrating the processing of a synthesis gas, produced by a heavy oil or bitumen upgrading process, via a Fischer-Tropsch synthesis; and

[0091] Figure 3 is a flow diagram illustrating the processing of a synthesis gas via a Fischer-Tropsch synthesis, and using heat produced within the process for generating steam for use in a steam-assisted gravity drainage process.
DETAILED DESCRIPTION

[0092] Referring now to Figure 1, there is provided a configuration used in processing synthesis gas, according to one embodiment.

[0093] Synthesis gas (or "syngas") 10 is fed into a guard bed 20, to remove any catalyst poisons (such as H2S, COS, NH3, HCN) from the synthesis gas 10, prior to introduction into a Fisher-Tropsch ("FT") reactor 30 which includes an Iron-based catalyst 31. The FT process is effected within the FT reactor 30. The effluent from FT reactor 30 consists of two streams, a first stream being a wax product stream 40, and a second stream 50 that is cooled via a cooler 60 and further separated via a separator 70, into three streams, an aqueous product stream 41, an oil product stream 42 and a tail-gas stream 39. The tail-gas stream 39 is recovered via olefin oligomerization 80, resulting in an oil product stream 46 and a fuel gas stream that optionally is separated 81 into a hydrogen gas stream 44, which is sent to an upgrader, an LPG
product stream 43 for sales, and a residual fuel gas stream 45.

[0094] Table 1 below provides the data when implementing the FT process using the system configuration of Figure 1 when the feed 10 is derived from partial oxidation ("PDX") synthesis gas. Table 2 below provides data when implementing the FT process using the system configuration of Figure 1 when the feed 10 is derived from a H2-lean syngas resulting from separating a PDX synthesis gas into at least a H2-rich stream and a H2-lean syngas, such as, for example, by way of a separation effected by pressure swing absorption.
Relative to the H2-lean syngas, the H2-rich stream includes a higher concentration of H2 TABLE 1 PDX synthesis gas (syngas) processed according Figure 1.
Mass balance Feed Mass balance FT-2 Tailgas !Olefin Oligo-calculations ,basismerization Mol Coumpounds weight [1] Syngas feed [30] FT feed [39] Tailgas from FT [43]+[44]+[45] [46] Oil from Oligo kg/lonol kmol/h kg/h kmol/h kg/h kmol/h kg/h ikmol/h kg/h Ikmol/h kg/h Water gas shift H2 2.02 8630 17396 8630 17396 2714 5470 2714 5470 CO 128.01 19967 279180 19967 279180 1864 52206 11864 52206 CO2 144.01 1585 25740 1586 25784 4204 185014 14204 185014 H2O 118.02 116 281 16 282 64 1155 164 1155 Inert gases ;0 0 ;
N2 28.01 42 1176 42 1176 42 1176 1176 Ar 39.95 44 1753 44 1753 44 1753 144 1753 Contaminants 0 0 H2S 34.08 1 10 1 0 0 COS 60.08 1 58 0 0 HCN 27.03 0 1 0 0 NH3 17.03 0 0 0 0 Hydrocarbons 1 0 0 CI-14, methane 16.04 62 987 62 987 1236 3790 236 C2H4, ethylene 28.05 12 326 8 228 C2H6, ethane 30.07 0 0 0 0 33 978 33 978 1 C3H6, propylene 42.08 89 3763 9 376 C3H8, propane ,44.10 i0 0 0 0 ,128 5644 128 5644 C4H8, butenes 56.11 1 ' 75 4182 7 418 C4H10, butanes 158.12 0 0 0 0 59 3422 59 3422 C5H10, pentenes 70.13 33 2318 3 232 C51-112, pentanes 172.15 10 0 0 0 47 3362 47 3362 C6H12, hexenes 184.16 0 0 0 0 15 C6H14, hexanes ,86.18 0 0 0 0 0 C7H14, heptenes 98.19 0 0 0 0 41 C7H16, heptanes 100.20 10 0 0 0 0 C8H16, octenes 112.21 0 0 0 0 21 C8HI8, octanes 1114.23 10 1 0 C9-C10 olefins 1 0 2019 C9-C10 paraffins CI 1-C14 olefins 1 0 467 CI I -C14 paraffins 1 0 0 C15-C22 olefins 0 CI5-C22 paraffins 0 1 C22+ olefins :
, 0 C22+ paraffins 0 Oxygenates C I -C4, alcohols , naphtha alcohols 1 0 distillate alcohols 0 1 wax alcohols 0 carboxylic acids , 1 :
, TOTAL: 1 119346 326574 19346 326559 9642 274560 9462 265225 67 9335 kg/h [40] Wax product 15993 [41] Aqueous prod. 16716 [42] Oil product 19289 TABLE 2 PSA-offgas (syngas) processed according Figure 1.
Mass balance calculations Coumpounds Mol weight [1] Syngas [30] FT-1 feed [39] Tailgas FT [43]+[44]+[45] [46] Oil from Oligo-feed Tailgas from mserization Oligomerization kg/lcmol kmol/ kg/h kmol kg/h kmol/ kg/h kmol/h kg/h kmol/h kg/h WGS compounds H2 2.02 3452 695 3452 6959 1001 2017 1001 2017 .
CO 28.01 9967 279 9967 27918 1515 42423 1515 42423 .
CO2 44.01 585 257 586 25784 5550 244250 5550 244250 H20 18.02 2016 363 2016 36312 58 1051 58 1051 ' Inert gases 0 0 N2 28.01 42 117 42 1176 42 1176 42 1176 Ar 39.95 44 175 44 1753 44 1753 , 44 1753 , Contaminants 0 0 H2S 34.08 0 1. 0 0 COS 60.08 1 58 . , 0 0 HCN 27.03 0 1. , 0 0 NH3 17.03 0 0, 0 0 Hydrocarbons 0 0 (aliphatic) CH4, methane 16.04 62 987 62 987 197 3168 197 3168 , C2H4, ethylene 28.05 9 254 6 177 C2H6, ethane 30.07 0 0 0 - 0 25 761 25 761 C3H6, propylene 42.08 70 2927 7 293 C3H8, propane 44.10 0 0 0 0 100 4390 100 4390 C4H8, butenes 56.11 58 3253 6 325 , C4 HIO, butanes 58.12 , 0 0 , 0 0 46 2661 46 2661 C5H10, pentenes 70.13 26 1803 3 180 C5H12, pentanes 72.15 0 0 0 0 36 2615 36 2615 C6H12, hexenes 84.16 0 0 0 0 4 336 , C6H14, hexanes 86.18 0 0 0 0 0 0 C71-l14, heptenes 98.19 0 0 0 0 32 , C7H16, heptanes 100.20 0 0 0 0 0 0 C8H I 6, octenes 112.21 0 0 10 0 C8H18, octanes 114.23 0 , 0 0 0 0 0 C9-C10 olefins 0 , 0 0 1571 C9-C10 paraffins 0 0 0 0 CII-C14 olefins 0 0 0 363 Cl 1-C14 paraffins 0 0 0 0 C15-C22 olefins 0 - 0 0 C15-C22 paraffins 0 0 0 .
C22+ olefins 0 , 0 0 C22+ paraffins 0 0 0 Oxygenates 0 0 C1-C4, alcohols 0 0 0 naphtha alcohols 0 - 0 0 distillate alcohols 0 0 0 wax alcohols' 0 0 0 carboxylic acids _ 0 0 .

TOTAL: 1616 352 1616 35215 8776 314500 8635 307240 52 7261 kg/h ..
[40] Wax product 1243 -[41] Aqueous pr 1020 [42] Oil product 1500 Table 3 below summarizes the two cases.

PSA-offgas Case PDX syngas + FT Steam Feed Total syngas & steam 16168 19346 kmol/hr CO 9967 9967 kmol/hr H2/C0 0.346 0.866 kmol/kmol H20/C0 0.202 0.002 kmol/kmol Total syngas & steam 8452 7838 ton/day Initial FT COreaction 1.0 1.53 normalized Rate Initial FT space velocity 1.0 1.20 normalized Initial FT COconv rate 1.0 1.28 normalized Usage, Consumption COfeed/C0cons 0.848 0.813 kmol/kmol H2cons/C0cons 0.290 0.730 kmol/kmol H2Ocons by reactions 601 -422 ton/day Output FT Hydrocarbon Liquid FT Wax 299 384 ton/day 360 463 ton/day Olefin 174 224 ton/day Liquid Hydrocarbon + +
Total Raw 833 1071 ton/day After Hydro-cracking 6979 8973 bbl/day Contaminated Water 245 401 ton/day Offgas post-Total flow 86359462 kmol/hr H2/C0 0.661 ' 1.456 kmol/kmol CO2 0.632 0.436 kmol/kmol Total flow , 7374 6365 ton/day 1-1V 4.40 7.72 MJ/kg HV 32.48 49.14 TJ/day

[0095] Referring now to Figure 2, there is depicted a process for FT
synthesis from a synthesis gas in a typical heavy oil or bitumen-processing scenario, according to another embodiment.
Step 1

[0096] A hydrocarbon stream 100 is generated from (a) a residual (reject) product from i) atmospheric distillation, ii) vacuum distillation, iii) de-asphalting, iv) visbreaking, v) coking, or (b) from concentrated biomass, such as via i) torrefaction or ii) liquefaction (hydrothermal, pyrolysis).
Step 2

[0097] A raw synthesis gas 120 is generated by partial oxidation (gasification) 110 of the hydrocarbon stream 100 obtained in step 1.

[0098] The molar 1-12 to CO ratio of said synthesis gas 120 is optionally tuned by proper selection of (a) the gasification temperature and/or (b) moderator addition (e.g. water, steam or CO2), and/or (c) co-firing of a lighter hydrocarbon such as i) natural gas, ii) refinery gas, iii) FT-offgas, (d) off-spec or surplus of liquids such as FT-liquids, methanol etc.

Step 3

[0099] The raw synthesis gas 120 is cleaned and modified in any possible sequence and way, such as:
(a) washing or scrubbing with water (not shown) i) to remove solids, and/or ii) to remove gaseous component (NH3, RCN, COS, H2S), optionally in chilled water, and/or iii) to remove water vapor, optionally with chilled water (b) catalyst enhanced conversion COS and HCN hydrolysis 130, such as over an alumina bed, a ZnO bed or other oxide containing catalyst, prior to acid gas removal (c) acid gas removal 140 (H2S, CO2, COS, NH3, HCN, iron carbonyl, nickel carbonyl) using i) amine liquid (such as MBA, DEA, MDEA or DIPA process);
ii) alcoholic liquid (such as methanol with Rectisoirmprocess); or iii) glycol liquid (such as dimethyl ethers of polyethylene glycol with Selexorprocess) (d) absorption on guard-bed 150 (active carbon, zinc-oxide, zinc-copper) or sacrificial-bed 160 (catalyst, spent Iron-based FT catalyst) (e) modified by adding CO2 and/or steam at suitable temperature over suitable catalyst to modify the H2 to CO ratio of the synthesis gas (not shown).
(f) modified by extracting 142 170, such as via i) a PSA process, and/or ii) via a membrane, having the advantage that the CO rich gas remains at pressure (so no FT feedgas compressor required), and with minimum depressurization of the H2 pure gas (not shown).
Step 4

[00100]
The cleaned and modified synthesis gas, of any one of the processes in Step 3, is compressed or letdown to a suitable pressure and heated or cooled 180 as required for FT-synthesis.
(a) Advantageously with Step 3f, the compression of PSA tailgas results in a temperature increase, reducing the need for external heating.
(b) Advantageously with Step 3d, the removal of catalyst poison over a sacrificial catalyst, such as an Iron-based FT catalyst, results in a desirable temperature increase.
Step 5

[00101]
Optionally, if desired, the clean and conditioned synthesis gas of Step 4 may be treated for H2 to CO ratio by any of the following:
(a) addition of H2 190, such as from excess of H2 available (not needed by hydro-cracker 200), and/or (b) addition of a Hz-rich gas such as from i) a steam methane reformer ("SMR") with or without a downstream WGS
Converter, being dry (majority of the water condensed) or being wet (not shown);
ii) an auto thermal reformer (not shown);
iii) a partial oxidation process (115) using a light feedstock (such as natural gas, refinery gas, methanol, naphtha), requiring relatively few and easy cleaning steps;
(c) addition of steam (adscititious H20) 210, such as by admixing with the synthesis gas of Step 4, intended for increasing the H2 content of the synthesis gas (where the synthesis is a H2-lean synthesis gas, wherein the Hz-lean synthetis gas includes H2 and CO in a molar ratio of less 1.0, such as between 0.25 and 1.0, such as between 0.25 and 0.6, such as between 0.25 and 0.5) via the in-situ watergas shift ("WGS") occurring at the FT-catalyst;
and/or (d) no additional modification of the synthesis gas.
Step 6

[00102] The synthesis gas of Step 4 or 5 is processed in a FT reactor 220 over a FT-synthesis active catalyst that is also a WGS active catalyst.
In this embodiment, the FT reactor 220 is selected from:
(a) one single reactor, or multiple reactors in parallel having the inlets and outlets connected to a common inlet- and outlet-header respectively; recycling of part of the product gas stream from the reactor(s) to the feed synthesis gas stream to the reactor(s) is optional;
if recycle of product gas is applied, then, optionally, the recycle stream is treated, and there is further included, optionally:
i) removing some FT liquid product 230 and/or condensable water 240 by subsequent cooling, discharging and reheating, and/or ii) removing FT gases 250 that reduce the conversion rate and/or reaction selectivity, such as H20 and/or CO2; or (b) two or more reactors in series, with optional intermediate removal of some FT liquid product and/or condensable water by subsequent cooling, discharging and reheating, and/or with optional removing FT gases that reduce the conversion rate and/or reaction selectivity, such as 1420 and/or CO2.
Each reactor may be constructed from multiple reactors in parallel having the inlets and outlets connected to common inlet- and outlet-headers respectively.

[00103] FT-synthesis is an exothermal process, with FT hydrocarbon product distribution being very sensitive to the process temperature. The higher the temperature the more undesirable gases are produced (e.g. CH4) at higher temperatures. The FT
reaction temperature may be controlled by indirect exchange of the heat of reaction with water at boiling conditions, whereby the steam or water pressure is the regulating factor. For the FT

catalyst in a fixed bed configuration, the heat can be exchanged via a shell and tube heat exchanger with the catalyst at the tube side and the boiling water at the shell side. The reverse configuration can also be practiced. For the FT catalyst in a slurry the three phase (catalyst, hydrocarbon, gas) bubble column reactor is cooled via a submerged heat exchanger, such as cooling coils having boiling water as a coolant on coil side. In some embodiments, for example, the temperature within the reaction zone of the FT reactor is between 240 degrees Celsius and 320 degrees Celsius (such as, for example, between 260 degrees Celsius and 300 degrees Celsius, such as, for example, between 270 degrees Celsius and 290 degrees Celsius).
By providing such reaction zone temperature, boiling water may be produced at a pressure, such as 4.2 MPa which is suitable for application to steam-assisted gravity drainage ("SAGD"), without significantly increasing light gas production.

[00104] In some embodiments, for example, the reactor zone of the FT
reactor is disposed at a pressure of between 0.2 and 7 MPa, such as between 1.5 and 6MPa, such as between 1.5 and 3MPa.

[00105] It has been found that the FT synthesis activation energy increases when lowering the H2 to CO ratio of the synthesis gas. Thus, for given temperature, the FT
conversion rate reduces when lowering the H2 to CO ratio of the synthesis gas.
For the application of synthesis gas with low H2 to CO ratio the increase of the FT-reaction temperature from the typical 220-240 degrees Celsius to 270-290 degrees Celsius range or above is advantageous, as it increases the conversion rate.

[00106] In comparison to the Cobalt-based catalysts, the Iron-based catalyst advantageously supports the higher FT-reactor temperature without producing relatively undesirable high quantities of CH4, versus the Cobalt-based catalyst. For the higher FT-reactor temperature application, one or more promoters, such as one or more oxides of the elements manganese and/or potassium and/or chromium and/or copper are contained in the Iron-based catalyst formulation to improve stability and performance.

[00107] The Iron-based catalyst supports the WGS reaction, while the Cobalt based catalyst does not.

[00108] For the Iron-based catalyst, and for a synthesis gas having, at the FT reactor inlet, a molar H2 to CO ratio below the overall consumption ratio of 0.55, the total CO
consumption rate per reactor pass is high, as the CO consumption occurs from both the FT-synthesis and the WGS reaction. Effective utilization of the CO and H2 can be achieved in one reactor pass without the need for FT-offgas recycling.

[00109] A further benefit of the described process is, that by employing a low H2 to CO
ratio synthesis gas, the water partial pressure in the FT reactor remains low, which sustains long catalytic service. Namely, oxidation of the Iron-based catalyst by water is a much more important deactivation mechanism than the deactivation mechanism by CO2.

[00110] Another benefit of the described process is that in employing a more CO rich synthesis gas, the H2 availability is lower which suppressing termination of the hydrocarbon chain growth (resulting in more heavy waxes) and suppressing methane formation.
Step 7

[00111] Treatment or refining of the FT-products.
(a) Light olefin recovery 225.
With the Iron-based catalyst and at the higher FT-reactor temperature, some more light alkenes (olefins) are produced. In principle this reduces the yield of the liquid hydrocarbons (C5-C22).
The light products can largely be recovered by the polymerization of the light (C2-05) olefins over an appropriate catalyst that is known in the art.
In some embodiments, for example, the conversion is over an acidic catalyst.
In some embodiments, for example, by processing the reagents over a solid phosphoric acid catalyst (for example, UOP CatPoly process), a high-octane olefinic motor gasoline and some distillate may be yielded.

In some embodiments, for example, processing the reagents over an acidic MFI-type zeolite catalyst (for example, PetroSA Conversion of Olefins to Distillate process), yielding some olefinie naphtha and distillate.
In all cases the products can be used as is, separated in appropriate fractions, and/or further refined (e.g. by hydro-processing).
(b) Suitable use of FT-offgas 250 as a fuelgas The remainder of the FT-offgas is made suitable as a fuelgas for firing in boilers 256 by:
i) condensing of the majority of the water vapor and removal of the water, ii) condensing and removal of the hydrocarbon (e.g. paraffins, that may solidify and block feed lines upon further cool down, iii) optional scrubbing of the offgas to remove CO2 255 (acid gas removal such as via amine or SelexolTm), with the objective to increase the fuelgas heating value and/or for CO2 production and/or purification (e.g. for carbon capture).
(c) Distillation 260 of FT liquid hydrocarbons Naphtha is a desirable product, as it is in high demand as a diluent in the bitumen mining. The boiling range is between 30 and 200 degrees Celsius, with carbon number between five (5) and twelve (12). By distillation this fraction is removed, and the remainder is used as a chemical feedstock or treated in a hydro-cracker.
(d) Hydro-cracking or Thermal-cracking The bottom product of the distiller is fed to the hydro-cracker 200, which is to produce lighter products by i) breaking alkane (paraffinic) chains, and/or ii) to saturate the C=C double bond of the alkenes (olefins) and/or to break-down oxygenates.
Alternatively the bottom product can be co-processed with the de-asphalted oil in a thermal cracker.
(e) The hydrocarbon products, oxygenates and water-soluble oxygenates can be processed in various other ways as described in the art (e.g. De Klerk, A. Fischer¨Tropsch refining; Wiley-VCH: Weinheim, 2011; ISBN 978-3-527-32605-1).

[00112] In some embodiments, for example, heat, at between 260 degrees Celsius and 300 degrees Celsius (such as, for example, between 270 degrees Celsius and 290 degrees Celsius), is transferred from the process to effect steam generation at 4.2 MPa. In this respect, and referring to Figure 3, there is provided a process upgrading a hydrocarbon residue and producing bitumen via steam-assisted gravity drainage ("SAGD") using steam that is generated by at least the heat produced by the upgrading. The process includes:
(a) converting the heavy hydrocarbon residue 500 (such as, for example, resulting from processing of bitumen or heavy oil) to a syngas product 502, such as, for example, in a gasifier 504;
(b) converting the syngas product 502 to one or more hydrocarbons 508 via at least Fischer-Tropsch synthesis within a reactor 506, wherein the conversion is effected within a reaction zone disposed at a temperature of greater than 260 degrees Celsius;
(c) transferring heat, from the converting, to a steam generator 510;
(d) with the transferred heat, effecting generation of steam 512 by the steam generator from water 511; and (e) supplying steam to a hydrocarbon reservoir via an injection well 514 (of a SAGD well pair including the injection well 514 and the production well 516) to effect mobilization of bitumen within the hydrocarbon reservoir.

[00113]
The appended claims define distinctly and in explicit terms the subject matter of the invention for which an exclusive privilege or property is claimed.

Claims

1. A process for upgrading a hydrocarbon residue and producing bitumen (oil based semi solid substance) via steam-assisted gravity drainage ("SAGD") using steam that is generated by at least the heat produced by the upgrading, comprising:
converting the hydrocarbon residue to a syngas product;
converting the syngas product via at least Fischer-Tropsch synthesis, wherein the conversion is effected within a reaction zone disposed at a temperature of greater than 260 degrees Celsius;
transferring heat, from the converting, to a steam generator;
with at least the transferred heat, effecting generation of steam by the steam generator; and injecting the steam into a hydrocarbon reservoir to effect mobilization of bitumen within the hydrocarbon reservoir.

2. The process as claimed in claim 1;
wherein the transferred heat is transferred from the reaction zone.

3. The process as claimed in claim 1 or 2;
wherein the transferred heat is transferred from Fischer-Tropsch products generated by the converting.

4. The process as claimed in any one of claims 1 to 3;
wherein the temperature within the reaction zone is between 260 degrees Celsius and 320 degrees Celsius.

5. The process as claimed in any one of claims 1 to 3;
wherein the temperature within the reaction zone is between 270 degrees Celsius and 290 degrees Celsius.

6. The process as claimed in any one of claims 1 to 5;

wherein the reaction zone is disposed at a pressure of between 0.2MPa to 7 MPa.

7. The process as claimed in any one of claims 1 to 5;
wherein the reaction zone is disposed at a pressure of between 1.5 MPa to 6 MPa.

8. The process as claimed in any one of claims 1 to 5;
wherein the reaction zone is disposed at a pressure of between 1.5 MPa to 3 MPa.

9. The process as claimed in any one of claims 1 to 8;
wherein the conversion is effected by a catalyst material.

10. The process as claimed in claim 9;
wherein the catalyst material include a Fe-based catalyst material.

11. The process as claimed in claim 9 or 10;
wherein the catalyst material includes at least one promoter.

12. The process as claimed in claim 1 1;
wherein the at least one promoter includes one or more metal oxides, and wherein the metal oxide is an oxide of any one of manganese, potassium, chromium, and copper.

13. The process as claimed in any one of claims 1 to 12;
wherein the converted syngas comprises at least one hydrocarbon that is liquid at standard temperature and pressure conditions.

14. The process as claimed in any one of claims 1 to 13;
wherein the converting of the hydrocarbon residue includes:
converting the hydrocarbon residue to a first syngas; and separating the first syngas into at least a H2-rich stream and a H2-lean syngas, wherein the H2-lean syngas defines the syngas product such that the conversion, by at least Fischer-Tropsch synthesis, is of the the H2-lean syngas.

15. The process as claimed in claim 14, further comprising:
effecting hydrocracking with the H2-rich stream.

16. The process as claimed in claim 14 or 15;
wherein the H2-lean syngas includes H2 and CO in a molar ratio of less than 1.0;
and wherein, prior to the conversion, by at least Fischer-Tropsch synthesis, the process further comprises:
supplying the H2-lean syngas and adscititious H2O to the reaction zone such that a reaction mixture becomes disposed in sufficient proximity to a catalyst material within the reaction zone, the catalyst material having both water gas shift activity and Fischer-Tropsch synthetic activity, such that the conversion, by at least Fischer-Tropsch synthesis, is effected.

17. The process as claimed in claim 16;
wherein the H2O of the adscititious H2O is adscititious relative to any H2O
that is produced during the conversion of the H2-lean syngas

18. The process as claimed in claim 16 or 17;
wherein the H2O of the adscititious H2O is adscititious relative to any H2O
that is produced during the Fischer-Tropsch synthesis.

19. The process as claimed in any one of claims 16 to 18;
wherein the reaction mixture is generated by admixing of the H2-lean syngas and the adscititious H2O.

20. The process as claimed in any one of claims 16 to 19;
wherein the supplying of the adscititious H2O to the reaction zone is effected independently of the supplying of the H2-lean syngas to the reaction zone.

21. The process as claimed in any one of claims 16 to 20;
wherein the H2O of the adscititious H2O is in the form of steam.

22. The process as claimed in any one of claims 16 to 21;
wherein the ratio of moles of H2 to moles of CO within the supplied H2-lean syngas is between 0.25 and 1Ø

23. The process as claimed in any one of claims 16 to 21;
wherein the ratio of moles of H2 to moles of CO within the supplied H2-lean syngas is between 0.25 and 0.6.

24. The process as claimed in any one of claims 16 to 21;
wherein the ratio of moles of H2 to moles of CO within the supplied H2-lean syngas is between 0.25 and 0.5.

25. The process as claimed in any one of claims 16 to 24;
wherein, when the ratio of moles of H2 to moles of CO within the supplied H2-lean syngas is less than 0.55, the ratio of moles of H2O of the supplied adscititious H2O to moles of CO of the supplied H2-lean syngas is defined in accordance with the following formula:
the ratio of moles of H2O of the supplied adscititious H2O to moles of CO of the supplied H2-lean syngas ¨
A x (0.55 ¨ (the ratio of moles of 1-1, of the H2-lean syngas to moles of CO
of the H2-lean syngas));
wherein A is between 1 and 1.3.

26. The process as claimed in any one of claims 16 to 25;
wherein, prior to the supplying of the H2-lean syngas to the reaction zone, any treatment of the H2-lean syngas feedstock is such that no H2 enrichment of the H2-lean syngas is effected prior to the reaction zone.

27. The process as claimed in any one of claims 16 to 26;
wherein the hydrocarbon residue includes a residual product from atmospheric distillation, vacuum distillation, deasphalting, coking, visbreaking, thermal cracking, fluid catalytic cracking, resid fluid catalytic cracking, or any combination thereof.

28. The process as claimed in any one of claims 1 to 27;
wherein the hydrocarbon residue is a heavy hydrocarbon residue.

29. The process as claimed in any one of claims 1 to 28;
wherein the steam injection into the hydrocarbon reservoir is for a SAGD
injection well.