JP4748939B2 - Fischer-Tropsch and oil-derived naphtha and distillate upgrades - Google Patents

Description

  The present invention relates to the conversion of distant natural gas into marketable transportation fuels and petroleum products. More particularly, the invention relates to Fischer-Tropsch and / or petroleum-derived naphtha and distillates for use in marketable transportation fuels and petroleum products, for example hydrotreating, hydrocracking. ) And hydrodewaxing, and related to upgrading.

  The Fischer-Tropsch reaction is a well-known reaction, and the catalysts and conditions for carrying out the Fischer-Tropsch reaction are well known to those skilled in the art and are described, for example, in EP 0 911 184 A1, The entire contents of the patent are incorporated herein. The Fischer-Tropsch process converts synthesis gas into linear hydrocarbons (n-paraffins, linear olefins and small amounts of fatty acids). Because of the linearity of such products, if they have undergone heteroatom removal or isomerization, they are not limited to jet fuel, diesel fuel, and petrochemical feedstock ( It is well suited for use in a variety of transportation fuels and other marketable petroleum products, including but not limited to benzene, toluene and xylene).

  However, light naphtha fractions are generally not well suited for use in ordinary gasoline because their linearity makes them exhibit a very low octane rating. In addition, naphtha can be used as a petrochemical feedstock for ethylene products, but naphtha is not suitable for transportation fuels. Moreover, even though naphtha is suitable as a fuel for fuel cell vehicles, fuel cell vehicles are not yet widely used, so there is still a way to convert naphtha for use in regular transportation fuels. is needed.

  In addition to the need to convert the naphtha fraction of the Fischer-Tropsch process, heavy boiling distillates from the Fischer-Tropsch process are allowed to be used in transportation fuels and other marketable petroleum products. There is also a need to upgrade to obtain (e.g. hydrorefining, hydrocracking or hydrodesulfurization).

  More specifically, the Fischer-Tropsch process product exhibits a boiling range with unacceptable levels of oxygenates (oxygenates) and olefins (alcohols and trace acids) in the final product. Also, because of the high content of linear hydrocarbons in such products, the resulting products are not limited, but unacceptable cold resistance including jet freezing point, diesel cloud point and lubricating oil based feed point pour point. Indicates. Traditionally, these products can be upgraded and sold by various methods including, but not limited to, hydrorefining, hydrocracking, hydrodesulfurization, combinations thereof, etc. And lube base stock can be obtained.

While such methods can upgrade Fischer-Tropsch products in response to the above challenges to obtain marketable transportation fuels and other petroleum products, the disadvantage of these methods is that they require hydrogen. . That is, in order to perform the above methods, hydrogen must be supplied separately during the application of these methods in order to successfully upgrade the Fischer-Tropsch product. Hydrogen can be obtained from synthesis gas, but hydrogen can only be obtained from synthesis gas by using an expensive separation process. Costly separation processes to ensure that hydrogen is separated from carbon oxides that would otherwise poison the catalysts used in hydrorefining, hydrocracking and hydrodewaxing processes is necessary. In addition, hydrogen can be supplied from a separate facility that reforms natural gas to hydrogen using a steam reforming process. Unfortunately, the construction and operation of a separate hydrogen production facility is extremely expensive. As a result, including, but not limited to, hydrorefining, hydrocracking and hydrodewaxing operations, the Fischer-Tropsch product can be cheaply upgraded to obtain a marketable product. There is an urgent need for a relatively low cost hydrogen source to be used in the upgrade process.

Another problem encountered during the upgrade of Fischer-Tropsch distillate is that the resulting feed contains oxygenate without sulfur. The cheapest catalysts for hydrorefining, hydrocracking and hydrodewaxing are sulfurized Group 6 and Group 8 metals (including but not limited to nickel, cobalt, molybdenum, tungsten, their Combination). Non-sulfurized catalysts for hydrorefining, hydrocracking and hydrodewaxing are available, but based on expensive noble metals including but not limited to platinum, palladium, combinations thereof, etc. ing. Unfortunately, when the sulfided catalyst is in the presence of oxygenate and in the absence of sulfur, the oxygen in the feed replaces the sulfur on the catalyst, leading to reduced catalyst performance. Decreased catalyst performance may appear in a variety of forms including, but not limited to, reduced activity, selectivity and / or stability. In order to prevent such performance degradation, manufacturers typically add sulfur compounds to ensure that the catalyst remains fully sulfided. Usually, the added sulfur compound is a pure chemical such as dimethyl disulfide. Unfortunately, pure chemicals are expensive to purchase and require special handling, which can lead to safety issues and generate additional costs. As a result, there is a need for a method of maintaining sulfurized catalysts in their active sulfurized state without the need for chemical use.

  Finally, there is also a need for a method for upgrading (eg, hydrorefining, hydrocracking or hydrodewaxing) petroleum-derived hydrocarbon products produced with natural gas. Petroleum-derived hydrocarbon products produced with natural gas can include condensates, naphthas and distillates. These products have a chemical composition similar to that of normal petroleum products and vary widely including but not limited to linear paraffins, isoparaffins, cycloparaffins, aromatic hydrocarbons, mixtures thereof, etc. A mixture of various hydrocarbons. They also contain sulfur and nitrogen impurities that must be removed to obtain a marketable product.

(Summary of Invention)
The method of the present invention addresses the above needs. The process of the present invention comprises a gasoline component, distillate that can be sold by, for example, hydrorefining, hydrocracking and hydrodewaxing (ie, upgrading) Fischer-Tropsch and / or petroleum-derived naphtha and distillate. At least one of an output fuel component and a lubricant-based feedstock component is produced.

The fuel component produced by the present invention has an octane number sufficient for use in conventional transportation fuels and petrochemical feedstocks. In addition, during naphtha reforming, the present invention produces hydrogen by-products that can be used in hydrorefining, hydrocracking and hydrodewaxing processes to inexpensively upgrade Fischer-Tropsch products. Thus, the present invention provides at least a portion of the hydrogen required for hydrorefining processes at low cost without the need for expensive separation processes or the use of a separate hydrogen production facility.

  In addition, the present invention can combine Fischer-Tropsch naphtha and distillate with petroleum-derived naphtha and distillate so as to obtain blended naphtha and distillate having a sulfur level of at least about 1 ppm. . Thus, the present invention ensures that the sulfurization catalyst used to hydrotreat naphtha and distillate maintains sufficient sulfur levels without the need for sulfur addition through the introduction of expensive pure chemicals. .

Finally, by combining Fischer-Tropsch naphtha and distillate with petroleum-derived naphtha and distillate, the present invention enables petroleum hydrocarbon products, including condensate, naphtha and distillate, to be sold gasoline components. And can be upgraded to obtain petroleum-derived feedstock products (eg, hydrorefining, hydrocracking or hydrodewaxing ).

  The method of the present invention for upgrading at least one of a Fischer-Tropsch naphtha and a Fischer-Tropsch distillate to produce at least one of a gasoline component, a distillate fuel component or a lubricant-based feedstock component Tropschnaphtha can be reformed to produce hydrogen by-products and gasoline components having a research octane rating of at least about 80. The hydrogen by-product is then used to upgrade the Fischer-Tropsch distillate to produce a distillate fuel component and / or a lubricant-based feed blending component.

  The method of the present invention for upgrading a Fischer-Tropsch naphtha can include hydropurifying the Fischer-Tropsch naphtha to remove oxygenates to produce a hydro-purified Fischer-Tropsch naphtha. The method can further include reforming the hydrofinished Fischer-Tropsch naphtha to produce hydrogen by-products and gasoline components having a research octane number of at least about 80. Finally, the hydrogen byproduct is recycled to hydrotreat the Fischer-Tropsch naphtha.

  Another method of the present invention for upgrading Fischer-Tropsch naphtha to obtain gasoline components mixes Fischer-Tropsch naphtha with petroleum-derived naphtha to obtain a blended naphtha having a sulfur level of at least about 1 ppm. Can be included. The blend naphtha is hydrorefined to produce a hydrorefined blend naphtha. Finally, the hydrorefined blend naphtha is reformed to produce hydrogen by-products and gasoline components having a research octane number of at least about 80.

  The method of the present invention for upgrading a Fischer-Tropsch distillate to produce at least one of a distillate fuel and a lube-based feedstock component comprises a Fischer-Tropsch distillate having a sulfur level of at least about 1 ppm. Mixing with petroleum-derived distillates can be included to obtain a blend distillate having The blend distillate is hydrorefined to produce a hydrofinished blend distillate. Finally, the hydrorefined blend distillate is upgraded to produce a distillate fuel component and / or a lubricant based feed blend component.

  Finally, the plant of the present invention for upgrading at least one of Fischer-Tropsch naphtha and Fischer-Tropsch distillate to obtain at least one of a gasoline component, distillate fuel or lubricant-based feedstock component ( plant) can include a hydrocarbon source that provides hydrocarbons. The separator separates hydrocarbon gas, hydrocarbon condensate, and crude oil from the hydrocarbon. Syngas from hydrocarbon gas. Fischer-Tropsch naphtha and Fischer-Tropsch distillate are obtained by performing a Fischer-Tropsch process on the synthesis gas in a Fischer-Tropsch reactor located downstream of the synthesis gas generator. The Fischer-Tropsch naphtha is hydrorefined by a naphtha hydrotreating reactor located downstream of the Fischer-Tropsch reactor. The hydrorefined naphtha is reformed by a naphtha reformer downstream of the hydrorefining reactor to obtain hydrogen by-products and gasoline components containing at least about 10% aromatic hydrocarbons. The Fischer-Tropsch distillate is hydrorefined by a distillate hydrotreating reactor downstream of the Fischer-Tropsch reactor. Finally, the distillate upgrader is downstream of the distillate hydrotreating reactor and the hydrogen by-product from the reformer is recycled to the upgrader to the naphtha reformer. In place, the hydrorefined distillate can be upgraded by an upgrader to produce distillate fuel and / or lube-based feedstock components.

(Preferred embodiment)
Using the present invention, Fischer-Tropsch naphtha and optionally petroleum-derived naphtha can be modified to produce aromatic hydrocarbons and hydrogen by-products. The resulting aromatic hydrocarbons can increase the naphtha octane number to allow naphtha to be used as normal gasoline or as a blend feed in normal gasoline. The resulting aromatic hydrocarbons can also be sold as beneficial petrochemicals including but not limited to benzene, toluene and xylene.

  There are two types of reforming methods, catalytic reforming and AROMAX® reforming. The process of the present invention can use either catalytic reforming or Aromax® reforming or both to convert Fischer Tropsch naphtha to aromatic hydrocarbons. Catalytic reforming is described, for example, by D.M. Little, PennWell Books (1985) and is a well-known method. Similarly, Aromax® modifications are well known, such as Petroleum & Petrochemical International, Volume 12, No. 12, pp 65-68, and US Pat. No. 4,456, Buss et al. No. 527. For both of these reforming processes, the feed should have very low levels of heteroatoms (eg, sulfur, nitrogen and oxygen). Fischer-Tropsch naphtha generally has very low levels of sulfur and nitrogen, but often has significant levels of oxygen in the alcohol form and in trace amounts of acids and other oxygenates. These heteroatoms can be removed by use of a hydrotreater. Preferred hydrorefining catalysts use inexpensive non-noble metals from Groups 6 and 8, including but not limited to nickel, cobalt, molybdenum, tungsten, combinations thereof, and the like. These non-noble metals are active when they are in the sulfided state. To prevent sulfur from the sulfurized hydrorefining catalyst from migrating to the reforming catalyst (which can poison the reforming catalyst), strip the product to hydrogen sulfide and other The light sulfur compounds are removed and optionally treated with a sulfur adsorbent. Examples of using adsorbents (guard beds) to protect the reforming catalyst are described in US Pat. Nos. 5,601,698 and 5,322,615. .

Hydrogen by-products from the reformer is used, for example, to upgrade the distillate by use of a hydrotreating, hydrocracking and hydrogen consumption of the process, including hydrogen Kada' wax. By using hydrogen by-products from naphtha reforming, the present invention eliminates the need for expensive separation processes or separate hydrogen production facilities to replenish the added hydrogen required to upgrade the distillate. Is avoiding.

  Although the process of the present invention can produce hydrogen by-products for use in upgrade processes that consume hydrogen, it will be necessary for the process of the present invention to provide hydrogen at least initially. In particular, the hydrogen produced in the reformer can be used for other operations including naphtha and / or hydrorefining of distillate, so provision will be required to provide hydrogen at start-up. There are several solutions to this problem, including but not limited to providing a separate hydrogen source, for example from a high pressure vessel, producing hydrogen from an electrolysis unit, or low sulfur hydrogen to the reformer for starting. Providing a source of purified naphtha. In addition, it will be appreciated that in the process of the present invention where no hydrogen by-product has yet been produced, hydrogen is provided, for example, for hydrotreating and / or upgrading processes. Further, for example, if the amount of hydrogen by-product produced during the process of the present invention is not sufficient to carry out the hydrorefining and / or upgrade process, the hydrogen by-product to be consumed by the process It will be appreciated that additional hydrogen may be added to replenish.

  In a preferred embodiment, Fischer-Tropsch naphtha is mixed with petroleum-derived naphtha to obtain a blended naphtha having a sulfur level above about 1 ppm, preferably above about 10 ppm. This blend naphtha is then hydrorefined over an inexpensive sulfurized hydrorefining catalyst to remove oxygenate from Fischer-Tropsch naphtha and sulfur from petroleum-derived naphtha. Again, if any type of sulfur compound is not present in the feedstock, the sulfur in the sulfurized hydrorefining catalyst will eventually be removed and the hydrorefining catalyst will suffer from performance loss. .

  Similarly, in another preferred embodiment, the Fischer-Tropsch distillate is used to increase the sulfur level of the blend distillate above about 1 ppm, preferably above about 10 ppm. Mixed with. This blend distillate is then hydrorefined over an inexpensive sulfurized hydrorefining catalyst to remove oxygenate from the Fischer-Tropsch distillate and sulfur from the petroleum-derived distillate. In the absence of any type of sulfur compound in the feedstock, sulfur in the sulfurized hydrorefining catalyst will eventually be removed and the hydrorefining catalyst will suffer from performance loss.

  Although the need to maintain a sulfurized catalyst in a sulfided state while processing a Fischer-Tropsch feed containing oxygen is known in the art, it is known to use petroleum derived feeds as the sulfur source. Absent. For example, Mobil U.S. Pat. No. 4,080,397 describes the addition of sulfur added to prevent sulfurized hydrorefining catalysts from being oxidized by oxygenates in the Fischer-Tropsch feed. The hydrorefining of 350 ° F. + Fischer-Tropsch distillate in the presence is described. However, the '397 patent does not describe the hydrogen source used during hydrorefining, nor does it describe the use of petroleum derived feedstock as the sulfur compound source.

  It is also within the scope of the present invention that hydrorefining of the blended stream takes place in the same reactor. Accordingly, Fischer-Tropsch naphtha and Fischer-Tropsch distillate, together with petroleum-derived naphtha, condensate, distillate or combinations thereof, have a sulfur content of the blend greater than about 1 ppm, preferably about 10 ppm. It can be hydrorefined in one reactor, provided that it is larger.

In addition, although it may be preferable to perform both naphtha reforming and distillate upgrades in a single process, the method according to the present invention should include both naphtha reforming and distillate upgrades. Absent. That is, it is within the scope of the present invention to have a process in which naphtha reforming or distillate upgrade is performed separately. In such embodiments, hydrogen during start-up and / or hydrogen to be used in upgrade processes, including but not limited to hydrorefining, hydrocracking and hydrodewaxing processes, It will be necessary to provide.

  In a preferred embodiment where naphtha reforming is performed separately, hydrogen may be initially replenished for use in hydrotreating the naphtha prior to reforming. In addition, at least a portion of the hydrogen byproduct produced during reforming can be recycled to hydrotreat the naphtha prior to reforming. Recycling of the hydrogen byproduct produced during reforming will substantially reduce the amount of hydrogen that needs to be added prior to hydrorefining.

  Similarly, in a preferred embodiment where the distillate is upgraded separately, hydrogen will need to be supplied both during hydrorefining and during upgrade.

A preferred embodiment of the present invention in which hydrogen produced during Fischer-Tropsch naphtha reforming is used for distillate upgrade is depicted in FIG. In this embodiment, a methane-containing hydrocarbon gas feed stream 12 is obtained from a methane-containing terrestrial reservoir 11. A separator 13 separates the hydrocarbon gas feed stream 12 into a heavy condensate stream 15, a crude oil fraction stream 14, and a methane-containing hydrocarbon gas effluent stream 16. The hydrocarbon gas effluent stream 16 enters the synthesis gas generator 17. At least a portion of the methane-containing hydrocarbon effluent gas 16 is synthesized gas by a syngas generator 17 through the use of a gaseous oxidant stream 18 (eg, air, O ₂ , enriched air, carbon dioxide, and combinations thereof). Converted to stream 19 (a gas mixture containing at least carbon monoxide and hydrogen). Syngas stream 19 enters Fischer-Tropsch reactor 20. Fischer-Tropsch reactor 20 converts synthesis gas stream 19 to at least Fischer-Tropsch naphtha stream 21 and Fischer-Tropsch distillate stream 22. Fischer-Tropsch naphtha stream 21 enters naphtha hydrorefining reactor 23. Fischer-Tropsch distillate stream 22 enters distillate hydrorefining reactor 24. The naphtha hydrorefining reactor 23 treats the naphtha stream 21 to remove oxygenate to obtain a hydrorefined naphtha stream 25. The distillate hydrorefining reactor 24 processes the distillate stream 22 to remove oxygenate to obtain a hydrorefined distillate stream 26. Hydrorefined naphtha stream 25 enters naphtha reformer 27. Hydrorefined distillate 26 enters distillate upgrader 28, in which the hydrorefined distillate is upgraded, for example, by hydrocracking and / or hydrodewaxing. .

During the naphtha reforming, a hydrogen byproduct stream 29 is generated. Hydrogen by-product stream 29 enters naphtha hydrorefining reactor 23, distillate hydrorefining reactor 24 and upgrader 28, where additional hydrogen for the hydrorefining process taking place therein. provide. After naphtha reforming, a naphtha reformer 27 exits a marketable gasoline component stream 30 containing at least about 10% aromatic hydrocarbons and having a research octane number of at least 80, preferably at least about 90. Also, a stream 32 of distillate fuel components or lube-based feedstock components that can be sold exits the distillate upgrader 28. Catalysts used to hydrotreat naphtha and distillates and to upgrade hydrofinished distillates are noble metals (but are not limited to Pd, Pt, combinations thereof) , Etc.) or non-noble metals (including but not limited to Ni, Co, W, Mo, combinations thereof, etc.). When used, the non-noble metal catalyst is in a sulfurized form, and preferably sulfur is added to the unit continuously or periodically. Sulfur can be added in the form of chemicals such as dimethyl disulfide. If the hydrorefining catalyst is a precious metal (less preferred), it is preferably not sulfurized.

  Another preferred embodiment of the present invention when the hydrogen produced during Fischer-Tropsch naphtha reforming is used for distillate upgrade is depicted in FIG. In this embodiment, the methane-containing hydrocarbon feed gas 42 is obtained from the methane-containing reservoir 41. Separator 43 separates heavy condensate stream 45 and / or crude oil fraction stream 44 from methane-containing hydrocarbon feed gas 42. A methane-containing hydrocarbon gas effluent 46 exits the separator 43 and enters the synthesis gas generator 48. A gaseous oxidant stream 49 also enters the synthesis gas generator 48. Syngas stream 50 exits generator 48 and enters Fischer-Tropsch reactor 53. Fischer-Tropsch reactor 53 generates at least a Fischer-Tropsch naphtha stream 54 and a Fischer-Tropsch distillate-containing stream 55. Crude oil stream 44 and condensate stream 45 enter distillate reactor 47. At least the petroleum-derived naphtha stream 51 and the petroleum-derived distillate stream 52 exit from the distillate reactor 47. The petroleum-derived naphtha stream 51 is mixed with the Fischer-Tropsch distillate stream 54 to produce a blended naphtha having greater than about 1 ppm sulfur, preferably greater than about 10 ppm sulfur. The blend naphtha then enters the naphtha hydrorefining reactor 56. Petroleum-derived distillate stream 52 is mixed with Fischer-Tropsch distillate stream 55 to produce a blend distillate containing greater than about 1 ppm sulfur, preferably greater than about 10 ppm sulfur. The blend distillate enters distillate hydrorefining reactor 57.

Blend naphtha is hydrorefined to remove oxygenates. Hydrorefined naphtha stream 58 exits naphtha hydrorefining reactor 56. The hydrorefined naphtha stream 58 enters the naphtha reformer 60. The blend distillate is hydrorefined in distillate hydrotreating reactor 57 to remove oxygenate, and the hydrofinished distillate stream 59 exits distillate hydrogenation reactor 57. To go. The hydrorefined distillate stream 59 enters the distillate upgrader 61. During the reforming of the blended naphtha in the naphtha reformer 60, a hydrogen byproduct stream 62 is generated. A portion of the hydrogen byproduct stream 62 is a hydrogen recycle stream 63 to provide the additional hydrogen required for the hydrorefining process taking place in the naphtha and distillate hydrotreating reactors 56, 57. Recirculated into the Also, hydrogen from hydrogen byproduct stream 62 provides additional hydrogen for upgrade processes (eg, hydrorefining and hydrodewaxing processes) performed there to upgrade the blend distillate. In order to enter the distillate upgrader 61. After naphtha reforming, naphtha reformer 60 exits commercially available gasoline component stream 65 containing at least about 10% aromatic hydrocarbons and having a research octane number of at least about 80, preferably at least about 90. . Finally, a distillate fuel component or lube base feed component stream 64 that can be sold exits the distillate upgrader 61.

  Another preferred embodiment of the present invention in which hydrogen produced during Fischer-Tropsch naphtha reforming is used for distillate upgrade is depicted in FIG. In this embodiment, a methane-containing hydrocarbon feed gas 72 is obtained from the methane-containing reservoir 71. Separator 73 separates heavy condensate stream 75 and / or crude oil fraction stream 76 from methane-containing hydrocarbon feed gas 72. Methane-containing hydrocarbon effluent gas 74 exits separator 73 and enters synthesis gas generator 77. A gaseous oxidant stream 78 also enters the synthesis gas generator 77. A synthesis gas stream 79 exits the synthesis gas generator 77 and enters a Fischer-Tropsch reactor 80. A Fischer-Tropsch product stream 81 exits from the Fischer-Tropsch reactor 80. Crude oil stream 76 and condensate stream 75 exit from separator 73 and enter distillate reactor 89. A blend comprising at least a petroleum-derived naphtha stream 90 and a petroleum-derived distillate stream 91 exiting the distillate reactor 89 and a Fischer-Tropsch product stream 81 comprising at least about 1 ppm sulfur, preferably at least about 10 ppm sulfur. Mix to obtain product stream.

The blend product stream enters the hydrorefining reactor 82 where oxygenate is removed from the Fischer-Tropsch distillate and naphtha and sulfur is removed from the petroleum-derived distillate and naphtha. Hydrorefined product stream 82 A exits hydrorefining reactor 82 and enters distillate reactor 83. At least the blend naphtha stream 84 and the blend distillate stream 85 exit from the distillate reactor 83. Blend naphtha stream 84 enters naphtha reformer 86 where the naphtha is reformed to produce hydrogen by-product stream 88 and marketable gasoline product stream 93. The gasoline product stream 93 contains at least about 10% aromatic hydrocarbons and has a research octane number of at least about 80, preferably at least about 90. Blend distillate stream 85 exits distillate reactor 83 and enters distillate upgrader 87. Hydrogen by-product stream 88 exiting the naphtha reformer enters distillate upgrader 87 and upgrades performed there to upgrade the distillate (eg, hydrorefining and hydrodewaxing processes). For additional hydrogen. Also, a portion of the hydrogen byproduct stream 88 is hydrogen recycled to the hydrorefining reactor 82 to provide the additional hydrogen necessary for the hydrorefining process performed there to remove oxidate and sulfur. Recirculated into stream 92. Finally, a distillate fuel component or lube base feed component stream 94 that can be sold exits the distillate upgrader 87.

(Example)
The invention is further illustrated by the following examples in which particularly useful method embodiments are described. The examples are provided to illustrate the invention and are not intended to limit the invention.

  The Fischer-Tropsch naphtha and distillate products are blended to provide a mixture containing about 1% by weight oxygen and less than about 10 ppm sulfur. This mixture is hydrocracked over a nickel tungsten sulfide catalyst at 663 ° F., 1.0 LHSV, 77% conversion, 1100 psig, and 10,000 SCFB hydrogen recycle gas rate. After 1500 hours of operation, at this point the product is rectified and the 300-650 ° F. diesel portion is isolated. The sulfur content of the diesel fraction is about 3.2 ppm by weight as measured by the Antek method. This same sample was run in duplicate on a Dohrmann analyzer and the resulting sulfur level is about 2.4 and about 2.6 nanograms / microliter or about 3 ppm sulfur by weight. Both the Dollman analyzer and the Antec analyzer use oxidative techniques for sulfur measurement and are reliable methods. The presence of sulfur in this product has been confirmed in later experiments, which is believed to be due to sulfur from the catalyst replaced with oxygenate in the feed. This problem can be avoided by adding sulfur-containing compounds to the Fischer-Tropsch feed so that the blend has greater than about 1 ppm sulfur, preferably greater than about 10 ppm sulfur.

  While this invention has been described with reference to specific embodiments, this application is intended to cover various modifications and substitutions that may be made by those skilled in the art without departing from the spirit and scope of the following claims. is doing.

1 is a schematic diagram of a preferred embodiment of the present invention. FIG. 3 is a schematic diagram of another preferred embodiment of the present invention. FIG. 3 is a schematic diagram of another preferred embodiment of the present invention.

Claims (37)

A full Issha-Tropsch naphtha and how to upgrade the Fischer-Tropsch distillate product,
(A) generating a gasoline component having an 8 0 research octane number also a Fischer-Toropushunafu support the least reforming hydrogen byproduct, and,
(B) hydrogen byproduct distillate fuel components to upgrade the Fischer-Tropsch distillate product using lubricating oil base stock blending components, or combinations thereof, to generate,
Including said method. The method of claim 1, further comprising hydrotreating Fischer-Tropsch naphtha to remove oxygenate prior to reforming to produce hydro-purified Fischer-Tropsch naphtha. The method of claim 2, wherein the hydrorefined Fischer-Tropsch naphtha is reformed to produce hydrogen by-products and gasoline components having a research octane number of at least 80. The method of claim 1, further comprising hydrotreating the Fischer-Tropsch distillate to remove oxygenate prior to upgrading to produce a hydrofinished Fischer-Tropsch distillate. 5. The method of claim 4, wherein the hydrogen by-product is used to upgrade the hydrorefined Fischer-Tropsch distillate to produce a distillate fuel component, a lubricant-based feed blend component, or a combination thereof. Obtaining a blend naphtha Fischer-Tropsch naphtha is mixed with petroleum-derived naphtha; and full Issha-Tropsch distillate obtained blend distillate is mixed with petroleum derived distillate method of claim 1, wherein . So as to obtain a blend naphtha having a sulfur level of 1 ppm to as low rather, be mixed with petroleum-derived naphtha Fischer-Tropsch naphtha,
Hydrorefining the blend naphtha to remove oxygenate from Fischer-Tropsch naphtha and oxygenate from petroleum-derived naphtha to produce a hydrorefined blend naphtha; and
Generating a gasoline component containing 1 0% aromatic hydrocarbons with less hydrogenated purified blend naphtha reforming hydrogen byproduct,
The method of claim 1, further comprising a. Mixing a Fischer-Tropsch distillate with a petroleum-derived distillate to obtain a blended naphtha having a sulfur level of at least 1 ppm;
Hydrotreating the blend distillate to generate a hydrorefined blend distillate; and
Using hydrogen by-products to upgrade the hydrorefined blend distillate to produce a distillate fuel component, a lubricant based feed blend component, or a combination thereof;
The method according to claim 1 or 7, further comprising: The process according to any one of claims 2 to 5, 7 and 8 , wherein the hydrorefining is carried out with an initial supply of hydrogen. Fischer-Tropsch distillate or hydrorefined Fischer-Tropsch distillate or hydrorefined blend distillate is upgraded using at least one of hydrocracking and hydrodewaxing 9. The method according to any one of claims 1, 4-6 and 8 . At least a portion of the hydrogen by-product prior to Fischer-Tropsch naphtha , Fischer-Tropsch distillate , or both, or blend naphtha , blend distillate , or both, before naphtha reforming or distillate upgrade 9. The process according to any one of claims 2-5, 7 , and 8 , wherein the process is recycled for hydrorefining . The method according to any one of claims 2 to 5, 7 and 8, wherein the hydrorefining is carried out using a catalyst comprising at least one of a noble metal and a non-noble metal. 13. The method of claim 12 , wherein the noble metal is selected from Pd, Pt and combinations thereof and the non-noble metal is selected from Ni, Co, W, Mo and combinations thereof. Or a noble metal is not sulfurized or non-noble metal is sulfided, or precious metals and non-precious metals not be sulfurized is sulfided, the method according to claim 12 or 13. 15. The method of claim 14 , wherein the non-noble metal is sulfided using sulfur or sulfur containing chemicals. Sulfur is added in the process, and sulfur-containing chemicals are di methyl disulfide, The method of claim 15. Just prior to hydrotreating, including whether naphtha containing sulfur least 1ppm, or sulfur-containing 1 ppm to as little distillate, or sulfur of at least 1ppm both naphtha and distillate, respectively, 9. A method according to any one of claims 2-5, 7 , and 8 . The naphtha contains at least 10 ppm sulfur, the distillate contains at least 10 ppm sulfur, or both the naphtha and distillate each contain at least 10 ppm sulfur immediately prior to hydrorefining. A method according to any one of -5, 7, and 8. The naphtha contains at least 30 ppm sulfur, the distillate contains at least 30 ppm sulfur, or both the naphtha and distillate each contain at least 30 ppm sulfur immediately prior to hydrorefining. A method according to any one of -5, 7, and 8. Resulting gasoline component has a 80 re search method octane number also less method according to any one of claims 1 to 19. 20. A method according to any one of the preceding claims, wherein the gasoline component obtained has a research octane number of at least 90. Resulting gasoline component containing 1 0% aromatic hydrocarbons with less process according to any one of claims 1 to 21. The process according to claim 7 or 8 , wherein the hydrorefining of the blend naphtha and the blend distillate is carried out in a single hydrorefining reactor. 9. The method of any one of claims 2-5, 7 , and 8, further comprising initially adding sulfur during the process so that the catalyst used during hydrorefining is fully sulfided. the method of. Gasoline components having 8 0 research octane number also the least produced by the method of any one of claims 1-24. A distillate fuel component produced by the method according to any one of claims 1 to 24 . A lubricating oil-based raw material component produced by the method according to any one of claims 1 to 24 . A plant for upgrading the full Issha-Tropsch naphtha and Fischer-Tropsch distillate product,
(A) a hydrocarbon source to provide hydrocarbons;
(B) a separator for separating hydrocarbon gas, hydrocarbon condensate and crude oil from hydrocarbon;
(C) a synthesis gas generator located downstream of the separator for producing synthesis gas from hydrocarbon gas;
(D) a Fischer-Tropsch reactor located downstream of the syngas generator to obtain a Fischer-Tropsch naphtha and Fischer-Tropsch distillate on the synthesis gas;
(E) a naphtha hydrotreating reactor located downstream of the Fischer-Tropsch reactor for hydrotreating Fischer-Tropsch naphtha produced from the Fischer-Tropsch reactor;
(F) to obtain a gasoline component containing 1 0% aromatic hydrocarbons hydrogenation purified naphtha produced from naphtha hydrotreating reactor reforms a least hydrogen byproduct, naphtha A naphtha reformer located downstream of the hydrotreating reactor;
(G) a distillate hydrotreating reactor located downstream of the Fischer-Tropsch reactor for hydrotreating a Fischer-Tropsch distillate produced from the Fischer-Tropsch reactor; and
(H) the hydrogenation purified distillate produced from distillate hydrotreating reactor upgrading of distillate fuels, lubricating oil base feedstock components, or combinations thereof, to generate a A distillate up located downstream of the distillate hydrotreating reactor, and so that, for naphtha reformers, hydrogen by-products from the naphtha reformer are recycled to the distillate upgrader. Graders ,
Including said plant. A distillation reactor located downstream of the separator for distilling hydrocarbon condensate and crude oil to obtain petroleum-derived naphtha and petroleum-derived distillate;
30. The plant of claim 28, further comprising: Distillation reactor, for a Fischer-Tropsch reactor and the naphtha hydrotreating reactor, 1 ppm even with less mixed before the Fischer-Tropsch naphtha and petroleum naphtha enters the naphtha hydrotreating reactor to form a blend naphtha having a sulfur level, that is situated, and, the distillation reactor, for a Fischer-Tropsch reactor and distillates hydrotreating reactor, and Fischer-Tropsch distillate to form a blend distillate having a sulfur level of 1 ppm even with less mixed before petroleum distillate enters distillate hydrotreating reactor, are located, according to claim 29 The plant described. Hydrorefining reactor contains at least one catalyst comprising at least one noble metal and non-noble metals, the plant according to any one of claims 28 to 30. 32. The plant of claim 31 , wherein the noble metal is selected from Pd, Pt and combinations thereof and the non-noble metal is selected from Ni, Co, W, Mo and combinations thereof . The plant according to claim 31 or 32, wherein the noble metal is not sulfided, the non-noble metal is sulfided, or the noble metal is not sulfided and the non-noble metal is sulfided. 34. The plant of claim 33, wherein the non-noble metal is sulfided using sulfur or sulfur containing chemicals. 35. The plant of claim 34, wherein the sulfur containing chemical is dimethyl disulfide. Furthermore, it is possible to sulfur is supplied initially to ensure that the catalyst present in the BiTome distillate hydrotreating reactor Oyo reactor naphtha hydrotreating is sufficiently sulfide 36. A plant according to any one of claims 28 to 35 , comprising a sulfur source located in such a way. The plant according to any one of claims 28 to 36 , wherein the naphtha hydrotreating reactor and the distillate hydrotreating reactor constitute a single hydrotreating reactor.

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