PROCESSES USING FISCHER-TROPSCH PRODUCTS

Description

CROSS-REFERENCES TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent Application Ser. No. 63/735,641, filed on Dec. 18, 2024, the entirety of which is incorporated herein by reference.

BACKGROUND

The Fischer-Tropsch process involves converting synthesis gas comprising carbon monoxide (and carbon dioxide) and hydrogen to hydrocarbons using a heterogeneous catalyst.

Fischer-Tropsch synthesis is known to yield a broad mixture of products including primarily paraffins, and some olefins. The individual compounds of such mixture can contain up to about 200 carbons. Typically, the number of carbons is between about 1 and about 150, with an average number of carbons of about 30. Some Fischer-Tropsch processes yield mixtures enriched with C₅-C₃₀ alkanes containing a significant quantity of olefins and oxygenated compounds, such as alcohols or organic acids. Trace amounts of sulfur-containing or nitrogen-containing products or aromatic compounds can be also present. Such mixtures are known as “light Fischer-Tropsch liquids” or “LFTL.” Both typical Fischer-Tropsch product (FT product) and LFTL are frequently used as a raw material for obtaining various petrochemical products, such as lubrication oil, kerosene, petroleum distillates, or diesel fuels, among others.

Fischer-Tropsch complexes are characterized by naphtha production as a main byproduct. Naphtha range material typically constitutes about 15-25 vol % of the complex effluent if the process does not include recycle of this stream. Most jurisdictions do not value the low RON green gasoline.

Therefore, there is a need to convert the naphtha from a Fischer-Tropsch complex to higher value materials.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an illustration of one embodiment of a combined Fischer-Tropsch and light olefins process.

FIG. 2 is one embodiment of a light olefins complex that can be used in the integrated process of FIG. 1.

DESCRIPTION

The present invention meets this need by converting both LFTL naphtha and naphtha produced from hydrocracking FT product (FT-HCU (hydrocracking unit) naphtha) to C₂ and C₃ olefins with a high carbon efficiency using a naphtha to ethylene and propylene process. It is an attractive solution for refiners that want to be involved in renewable fuels and green olefins. The green olefins can be used in petrochemicals.

FIG. 1 illustrates one embodiment of an integrated process 100 combining a Fischer-Tropsch reaction zone with a hydrocracking reaction zone, a dewaxing reaction zone, and an NEP complex including a naphtha to ethane and propane reaction zone and a light olefins reaction zone.

The feed stream 105 comprising synthesis gas is fed to the Fischer-Tropsch reaction zone 110 comprising a Fischer-Tropsch reactor and a Fischer-Tropsch fractionation zone comprising a fractionation column. The synthesis gas stream can be formed from biomass or other sources, municipal solid waste (MSW), biogas, and/or CO or CO₂ and H₂.

The feed stream 105 is converted mainly to normal paraffins with a carbon range of C₁ to about C₁₀₀. The Fischer-Tropsch product is separated into a Fischer-Tropsch liquid stream 115 comprising C₃ to C₂₁ normal paraffins, a Fischer-Tropsch wax stream 120 comprising C₂₂ to C₁₀₀ normal paraffins, an offgas stream 125 comprising C₂—, and a waste water stream 130. The offgas stream 125 can be sent to a recycle reforming unit (not shown) comprising a combination of autothermal reforming and reverse water gas shift to convert it to synthesis gas. The converted synthesis gas can be recycled to the Fischer-Tropsch reaction zone 110.

The Fischer-Tropsch wax stream 120 is sent to a hydrocracking reaction zone 135 comprising a hydrocracking reactor where the C₂₂ to C₁₀₀ normal paraffins are cracked to C₈ to C₁₉ paraffins.

The hydrocracking reaction zone 135 has multiple beds to manage the temperature rise. The hydrocracking reaction zone 135 comprises one or more hydrocracking reactors, and each hydrocracking reactor can have one or more beds. A single hydrocracking reactor would have more than one bed. If there are two or more hydrocracking reactors, each reactor could have a single bed or multiple beds.

The hydrocracking reaction zone 135 includes a hydrocracking catalyst. Any hydrocracking catalyst suitable for hydrocracking the Fischer-Tropsch wax stream 120 can be used. The hydrocracking catalyst may comprise an acidic component, including, but not limited to, an amorphous acidic component such as amorphous silica-alumina (ASA). The hydrocracking catalyst may comprise a noble metal. Noble metals include, but are not limited to, Au, Ag, Pt, Pd, Ru, Rh, Pd, Os, and Ir. One suitable hydrocracking catalyst comprises a noble metal and ASA which provides high middle distillate selectivity. Such suitable hydrocracking catalyst is a good choice if the Fischer-Tropsch product stream does not contain significant concentrations of hetero-atomic components containing sulfur or nitrogen. In another embodiment, a suitable hydrocracking catalyst comprises a noble metal and comprises crystalline acidic components such as a faujasite-based ultra-stable Y-zeolite and a beta zeolite. Typically, a Fischer-Tropsch product stream does not contain sulfur or nitrogen organic components that significantly affect the noble metal functioning. However, when Fischer-Tropsch products comprise higher concentrations of oxygenates utilizing a hydrocracking catalyst comprising base metal may be advantageous. So, yet in another embodiment a suitable hydrocracking catalyst comprises ASA, a crystalline acidic component and the aforementioned base metals.

The hydrocracking reaction conditions typically include a temperature in the range of 315° C. to 415° C., and a pressure in the range of 20.7 to 69.0 bar (300 to 1000 psig), for example.

The hydrocracked Fischer-Tropsch effluent stream 140 is passed to the dewaxing reaction zone 145 comprising a dewaxing reactor where a portion of the C₈ to C₁₉ normal paraffins are converted to isoparaffins.

Suitable dewaxing catalysts may comprise a metal of Group VIII (IUPAC 8-10) of the Periodic Table and a support material. Suitable Group VIII metals include platinum and palladium, each of which may be used alone or in combination. The dewaxing catalyst may include non-noble metals which are not as susceptible to sulfur deactivation in a sour environment. Examples of suitable non-noble metals include Ni, Mo, Co, W, Mn, Cu, Zn or Ru. Mixtures of hydrogenation metals may also be used such as Co/Mo, Ni/Mo and Ni/W. The amount of hydrogenation metal or metals may range from 0.1 to 25 wt. %, based on the catalyst weight. Methods of loading metal onto the support material include, for example, impregnation of the support material with a metal salt of the hydrogenation component and heating. The catalyst support material containing the hydrogenation metal may also be sulfided prior to use.

The support material may be amorphous or crystalline. Suitable support materials include amorphous alumina, amorphous silica-alumina, ferrierite, ALPO-31, SAPO-11, SAPO-31, SAPO-37, SAPO-41, SM-3, MgAPSO-31, FU-9, NU-10, NU-23, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, MeAPO-11, MeAPO-31, MeAPO-41, MgAPSO-11, MgAPSO-31, MgAPSO-41, MgAPSO-46, ELAPO-11, ELAPO-31, ELAPO-41, ELAPSO-11, ELAPSO-31, ELAPSO-41, laumontite, cancrinite, offretite, hydrogen form of stillbite, magnesium or calcium form of mordenite, and magnesium or calcium form of partheite, each of which may be used alone or in combination. ALPO-31 is described in U.S. Pat. No. 4,310,440. SAPO-11, SAPO-31, SAPO-37, and SAPO-41 are described in U.S. Pat. No. 4,440,871. SM-3 is described in U.S. Pat. Nos. 4,943,424; 5,087,347; 5,158,665; and 5,208,005. MgAPSO is a MeAPSO, which is an acronym for a metal aluminumsilicophosphate molecular sieve, where the metal, Me, is magnesium (Mg). Suitable MgAPSO-31 catalysts include MgAPSO-31. MeAPSOs are described in U.S. Pat. No. 4,793,984, and MgAPSOs are described in U.S. Pat. No. 4,758,419. MgAPSO-31 is a preferred MgAPSO, where 31 means a MgAPSO having structure type 31. Many natural zeolites, such as ferrierite, that have an initially reduced pore size can be converted to forms suitable for olefin skeletal isomerization by removing associated alkali metal or alkaline earth metal by ammonium ion exchange and calcination to produce the substantially hydrogen form, as taught in U.S. Pat. Nos. 4,795,623 and 4,924,027. Further catalysts and conditions for skeletal isomerization are disclosed in U.S. Pat. Nos. 5,510,306, 5,082,956, and 5,741,759. The hydroisomerization catalyst may also comprise a modifier selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, and mixtures thereof, as described in U.S. Pat. Nos. 5,716,897 and 5,851,949. Other suitable support materials include ZSM-22, ZSM-23, and ZSM-35, which are described for use in dewaxing in U.S. Pat. No. 5,246,566 and in the article entitled S. J. Miller, “New Molecular Sieve Process for Lube Dewaxing by Wax Isomerization,” 2 Microporous Materials 439-449 (1994), U.S. Pat. Nos. 5,444,032 and 5,608,968 teach a suitable bifunctional catalyst which is constituted by an amorphous silica-alumina gel and one or more metals belonging to Group VHIA and is effective in the hydroisomerization of long-chain normal paraffins containing more than 15 carbon atoms. U.S. Pat. Nos. 5,981,419 and 5,908,134 teach a suitable bifunctional catalyst which comprises: (a) a porous crystalline material isostructural with beta zeolite selected from boro-silicate (BOR-B) and boro-alumino-silicate (Al—BOR—B) in which the molar SiO₂:Al₂O₃ ratio is higher than 300:1; (b) one or more metal(s) belonging to group VIIA, selected from platinum and palladium, in an amount comprised within the range of from 0.05 to 5% by weight. V. Calemma et al., App. Catal. A: Gen., 190 (2000), 207 teaches yet another suitable catalyst. Alumina or silica may be added to the support material.

In an exemplary embodiment, the dewaxing catalyst is a noble-metal catalyst.

Dewaxing conditions generally include a temperature of 290° C. (550° F.) to about 450° C. (842° F.) and a pressure of about 2.85 MPa (abs) (414 psia) to about 20.8 MPa (abs) (3014 psia). In another embodiment, the dewaxing conditions may include a temperature of about 150° C. (302° F.) to about 432° C. (810° F.) and a pressure of about 1724 kPa (abs) (250 psia) to about 13.8 MPa (abs) (2000 psia). In another embodiment, the dewaxing conditions may include a temperature of 315° C. (600° F.) to 432° C. (810° F.) and a pressure of 2070 kPa (abs) (300 psia) to 6.9 MPa (abs) (1000 psia).

In the dewaxing fractionation zone comprising a fractionation column, the dewaxing reactor effluent comprising C₅ to C₂₀ normal paraffins and C₅ to C₂₀ isoparaffins is separated into an FT-HCU naphtha stream 150 comprising C₅ to C₈ normal paraffins and isoparaffins, and an FT synthetic paraffinic kerosene (FT-SPK) stream 155 comprising C₉ to C₂₀ normal paraffins and isoparaffins. In another embodiment, the FT-HCU naphtha comprises C₅ to C₁₂ normal paraffins and isoparaffins. An offgas stream 160 comprising C₄. can be sent to a recycle reforming unit to be converted to synthesis gas, as discussed above. The converted synthesis gas can be recycled to the Fischer-Tropsch reaction zone 110.

The Fischer-Tropsch liquid stream 115 is sent to a second Fischer-Tropsch fractionation zone 165 comprising a fractionation column where it is separated into a Fischer-Tropsch (FT) naphtha stream 170 comprising C₅ to C₈ normal paraffins and a C₉₊ stream 175 comprising C₉ to C₂₁ normal paraffins. The C₉₊ stream 175 is sent to the hydrocracking reaction zone 135. In another embodiment, the Fischer-Tropsch liquid stream 115 is sent to a second Fischer-Tropsch fractionation zone 165 comprising a fractionation column where it is separated into a Fischer-Tropsch (FT) naphtha stream 170 comprising C₅ to C₁₂ normal paraffins and a C₁₃₊ stream 175 comprising C₁₃ to C₂₁ normal paraffins. The C₁₃₊ stream 175 is sent to the hydrocracking reaction zone 135.

The FT naphtha stream 170 has a higher ratio of normal paraffins to isoparaffins compared to the FT-HCU naphtha stream 150.

The FT naphtha stream 170 from the second Fischer-Tropsch fractionation zone 165 and the FT-HCU naphtha stream 150 from the dewaxing reaction zone 145 are sent to the NEP complex 180 which produces an ethylene stream 185, a propylene stream 190, and an optional aromatics stream 195. A portion of the aromatics stream 195 can be combined with the FT-SPK stream 155 to form a sustainable aviation fuel (SAF) stream 200, if desired.

FIG. 2 illustrates one embodiment of the NEP complex 180 which includes an ethane steam cracking reaction zone, a propane dehydrogenation reaction zone, and associated separation zones.

The FT naphtha stream 170 from the second Fischer-Tropsch fractionation zone 165 and the FT-HCU naphtha stream 150 from the dewaxing reaction zone 145 are sent to the NEP reaction zone 205 comprising an NEP reactor where the C₁₂-isoparaffins and normal paraffins are cracked, with some hydrogenation and dehydrogenation taking place.

The NEP reactors can be fixed bed downflow reactors.

The NEP catalyst for converting naphtha to ethane and propane may contain a molecular sieve comprising large or medium pore mouths, that is, comprising 10 or 12 member rings, respectively. Examples of suitable molecular sieves include MFI, MEL, MFI/MEL intergrowth, MTW, TUN, UZM-39, IMF, UZM-44, UZM-54, MWW, UZM-37, UZM-8, UZM-8HS. Examples of suitable molecular sieves further include FER, AHT, AEL (SAPO-11), AFO (SAPO-41), MRE, MFS, EUO-1, TON (ZSM-22), MTT (ZSM-23) and UZM-53. Additional molecular sieves with larger pores include FAU, EMT, FAU/EMT intergrowth, UZM-14, MOR, BEA, UZM-50, MTW, ZSM-12. Additional examples include MSE and UZM-35.

MFI is a suitable molecular sieve for the NEP catalyst. It will be appreciated that ZSM-5 is an MFI-type aluminosilicate zeolite belonging to the pentasil family of zeolites and having a chemical formula of Na_nA1_nSi₉₆-nO₁₉₂·16H₂O (0<n<10). In various embodiments, the ZSM-5 zeolite may comprise a silica-to-alumina molar ratio of 20 to 1000, 20 to 800, 20 to 600, 20 to 400, 20 to 200 or 20 to 80. In various embodiments, the ZSM-5 zeolite may comprise a crystal size in the range of 10 to 600 nm, 20 to 500 nm, 30 to 450, 40 to 400 nm, or 50 to 300 nm.

The NEP catalyst may comprise a bound zeolite. The binder may comprise an oxide of aluminum, silicon, zinc, titanium, zirconium and mixtures of thereof. The binder may comprise a phosphate in the binder or a phosphate of the forenamed oxide binder materials. Preferably, the binder is a silicon oxide. The MFI zeolite may be supported in a silicon oxide containing binder or an alumina containing binder such as aluminum phosphate.

MFI zeolite slurry may be first mixed with a binder in the form of colloidal suspension (sol) and gelling reagent and then dropped into hot oil to make spheres controlled to produce 1/888-inch to about 1/32-inch diameter calcined supports. Alternatively, the zeolite may be mixed with a silicon oxide containing binder and extruded to 1/32 to ¼ inch diameter extrudates. Extrudates may be washed with ammonia to remove sodium ions from the zeolite, dried and calcined to remove the organic structural directing agent (OSDA) from the synthesized zeolite. Optionally, the calcined support may be ammonium-ion exchanged using an ammonium nitrate solution to remove residual sodium ions and dried at about 110° C.

The NEP catalyst comprises a metal on the catalyst. The metal may comprise a transition metal. In a further example, the metal may comprise platinum, palladium, iridium, rhenium, ruthenium and mixtures thereof. The metal may be a noble metal. A modifier metal may also be included on the catalyst. The modifier metal may include tin, germanium, gallium, indium, thallium, zinc, silver and mixtures thereof. The modifier metal should be more concentrated on the binder than on the zeolite. About 0.01 to about 5 wt % of each of the transition metal and the modifier metal may be on the catalyst.

Metal may be incorporated into the binder by evaporative impregnation. A solution of platinum such as tetraamine platinate nitrate or chloroplatinic acid may be contacted with the bound spherical or extrudate supports which have been calcined and ion-exchanged in a rotary evaporator, followed by drying and oxidation.

The NEP catalyst comprises a metal on the bound spherical or extrudate supports of the catalyst. Preferably, more of the metal is on the binder than on the zeolite. At least 60 wt %, suitably at least 70 wt %, preferably at least 80 wt % and most preferably at least 90 wt % of the metal is on the binder. The zeolite and/or the entire NEP catalyst is steam oxidized to drive the metal off the zeolite. Steaming is preferably effected after the metal is added to the catalyst. The dried, impregnated spherical or extrudate supports may be steam oxidized in air for sufficient time to provide NEP catalysts. Steam oxidation in air at a temperature of about 500° C. to about 650° C. and about 5 mol % to about 30 mol % steam for about 1 to 3 hours may be suitable.

The naphtha stream may be heated to a reaction temperature of about 300° C. to about 600° C., suitably between about 325° C. and about 550° C., and preferably between about 350° C. and about 525° C. in the NEP reactor. A total pressure in the NEP reactor should be about 0.1 to about 3 MPa (abs), preferably greater than 1 MPa (abs).

The ethane to propane product ratio can be designed from 0.25 to ethane only.

The ethane and propane yield from the NEP reaction can be over 80%.

The NEP effluent stream 210 comprises ethane, propane, hydrogen, and heavy naphtha primarily comprising aromatics. It may also include other components such as methane and butanes. The NEP effluent stream 210 is sent to an NEP separation zone 215 where it is separated into a hydrogen stream 220, ethane stream 225, propane stream 230, and the optional aromatics stream 195 comprising about 98% aromatics. A portion of the aromatics stream 195 can be combined with the FT-SPK stream 155 to form the SAF stream 200, as discussed above. There can also be an optional light paraffin recycle stream 235 which can be recycled to the NEP reaction zone 205.

Ethane stream 225 is passed to an ethane steam cracking reaction zone 240 comprising an ethane cracking reactor where the ethane is converted to ethylene. Ethylene effluent stream 245 is sent to a light olefins fractionation zone 250. The by-product hydrogen from the ethane steam cracking reaction zone 240 can be used in hydrogen consuming process units in the complex, such as NEP, reverse water gas shift, hydrocracking, and hydroisomerization, for example.

Propane stream 230 is sent to a propane dehydrogenation reaction zone 255 comprising a propane dehydrogenation reactor where the propane is dehydrogenated to propylene. Propylene effluent stream 260 is sent to the light olefins fractionation zone 250.

The ethylene effluent stream 245 from the ethane steam cracking reaction zone 240 and the propylene effluent stream 260 from the propane dehydrogenation reaction zone 255 are sent to the light olefins fractionation zone 250 comprising a light olefins fractionation column where they are separated into a hydrogen stream 265, an ethylene stream 270, and a propylene stream 275.

EXAMPLES

Below are two exemplary applications of this novel configuration. These examples represent a pathway to process a complicated and difficult to process feed and convert these feeds to high value light olefins. These feeds would not directly provide high yields of olefins in either a mixed feed steam cracker or a propane dehydrogenation unit. Therefore, these feeds are processed in an NEP process unit to form the ethane and propane intermediates, which will become the feed components to the ethane steam cracker and the propane dehydrogenation unit, respectively. The ethane and propane products from the NEP unit will have very high yields of ethylene and propylene. Otherwise, these feeds would typically require multiple additional processing steps or reliance on low-yielding, low-efficiency processes.

Maximum SPK—This embodiment directs higher molecular weight components comprising C₉ to C₁₂ normal paraffins and isoparaffins to the SAF product stream. This impacts the amount and composition of NEP feed, though the NEP unit will remain at operating conditions as previously described. Of the two examples, this NEP feed is a lower average molecular weight. In terms of fresh feed to the overall complex, this NEP configuration delivers higher production rates of final products such as light olefins and SAF with increased proportion towards the SAF product stream.

Maximum Light Olefins—This embodiment directs higher molecular weight components comprising C₉ to C₁₂ normal paraffins and isoparaffins to the NEP and light olefins production. The maximum light olefins embodiment significantly increases the feed availability in comparison to the maximum SPK configuration example. In this configuration the NEP feed is a higher molecular weight. The NEP unit will remain within the operating conditions ranges as previously described. In terms of fresh feed to the overall complex, this NEP configuration delivers higher production rates final products such as light olefins and SAF with increased proportion towards the light olefin stream.

Both cases as shown in the table below demonstrate high yields to high value light olefins (as high as 65% conversion of the NEP feed to light olefins) in comparison use of existing or traditional process units that would typically yield 20% to 25% of NEP feed to light olefins. These high yielding cases deliver higher operator value and reduce operator expenses by eliminating the production of low value by products.

SPECIFIC EMBODIMENTS

While the following is described in conjunction with specific embodiments, it will be understood that this description is intended to illustrate and not limit the scope of the preceding description and the appended claims.

A first embodiment of the invention is an integrated process for making synthetic paraffinic kerosene and olefins comprising converting a synthesis gas stream comprising H₂ and CO, or CO₂, or CO and CO₂ in a Fischer-Tropsch reaction zone comprising a Fischer-Tropsch reactor in the presence of a Fischer-Tropsch catalyst under Fischer-Tropsch reaction conditions into a Fischer-Tropsch reaction mixture comprising C₁ to about C₁₀₀ normal paraffins; separating the Fischer-Tropsch mixture into a Fischer-Tropsch liquid stream comprising C₃ to C₂₁ normal paraffins and a Fischer-Tropsch wax stream comprising C₂₂ to C₁₀₀ normal paraffins in an FT fractionation zone; hydrocracking the Fischer-Tropsch wax stream in a hydrocracking reaction zone comprising a hydrocracking reactor in the presence of a hydrocracking catalyst under hydrocracking conditions forming a hydrocracking effluent stream comprising C₈ to C₁₉ normal paraffins; dewaxing the hydrocracking effluent stream in a dewaxing reaction zone comprising a dewaxing reactor in the presence of a dewaxing catalyst under dewaxing conditions forming a dewaxing reaction mixture comprising C₈ to C₁₉ normal paraffins and isoparaffins; separating the dewaxing reaction mixture into a FT-HCU naphtha stream comprising C₅ to C₁₂ normal paraffins and isoparaffins, and a FT synthetic paraffinic kerosene (FT-SPK) stream comprising C₉ to C₂₀ normal paraffins and isoparaffins in a dewaxing separation zone; separating the Fischer-Tropsch liquid stream into a FT naphtha stream comprising C₅ to C₁₂ normal paraffins and a C₁₃₊ stream comprising C₁₃ to C₂₁ normal paraffins in a second FT fractionation zone; cracking the FT naphtha stream from the second Fischer-Tropsch fractionation zone and the FT-HCU naphtha stream from the dewaxing reaction zone in an NEP reaction zone comprising an NEP reactor in the presence of an NEP catalyst under NEP reaction conditions to form an NEP effluent stream comprising C_1-3 paraffins and C_6-9 aromatics; separating the NEP effluent stream into an ethane stream and a propane stream in an NEP fractionation zone; steam cracking the ethane stream in a cracking reaction zone comprising a cracking reactor to form an ethylene effluent stream comprising ethylene; dehydrogenating the propane in a dehydrogenation reaction zone comprising a dehydrogenation reactor in the presence of a dehydrogenation catalyst to form a propylene effluent stream comprising propylene. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the C₁₃₊ stream to the hydrocracking reaction zone. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein separating the NEP effluent stream into the ethane stream and the propane stream comprises separating the NEP effluent stream into the ethane stream, the propane stream, a hydrogen stream, and an aromatics stream, and further comprising combining the FT-SPK stream and a portion of the aromatics stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising recycling the hydrogen stream to the NEP reaction zone, or recovering the hydrogen stream, or passing the hydrogen stream to a H₂ consuming process unit, or combinations thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein separating the NEP effluent stream into the ethane stream and the propane stream comprises separating the NEP effluent stream into the ethane stream, the propane stream, and a light paraffin stream, and further comprising recycling the light paraffin stream to the NEP reaction zone. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising separating the ethylene effluent stream and the propylene effluent stream into an ethylene stream comprising ethylene, a propylene stream comprising propylene, and a second hydrogen stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising recycling the second hydrogen stream to the NEP reaction zone, or recovering the second hydrogen stream, or passing the second hydrogen stream to a H₂ consuming process unit, or combinations thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising conditioning the synthesis gas to a H₂:CO mole ratio of 2:1 and removing contaminants from the synthesis gas to form clean conditioned synthesis gas before converting the synthesis gas in the Fischer-Tropsch reaction zone; and wherein converting the synthesis gas in the Fischer-Tropsch reaction zone comprises converting the cleaned conditioned synthesis gas in the Fischer-Tropsch reaction zone. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the hydrocracking catalyst comprises acidic components, base metals, and noble metals; or wherein the hydrocracking reaction conditions comprise a temperature in a range of 315 to 415° C., or a pressure in a range of 20.7 to 69.0 bar, or both; or both. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the dewaxing catalyst comprises a metal of Group VIII and a support material; or wherein the dewaxing reaction conditions comprise a temperature in a range of 150 to 450° C., or a pressure in a range of 2.8 MPa to 20.8 MPa, or both; or both. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the NEP catalyst comprises medium or large pore zeolites, oxide binders, MFI catalysts with transition, or noble, or modifier metals, or combinations thereof; or wherein the NEP reaction conditions comprise a temperature about 300° C. to about 600° C., suitably between about 325° C. and about 550° C., or a pressure of 0.1 to about 3 MPa (abs). both.

A second embodiment of the invention is a process for making synthetic paraffinic kerosene and olefins comprising conditioning a synthesis gas comprising H₂ and CO, or CO₂, or CO and CO₂ to a H₂:CO mole ratio of 2:1 and removing contaminants from the synthesis gas to form clean conditioned synthesis gas; converting the clean conditioned synthesis gas in a Fischer-Tropsch reaction zone comprising a Fischer-Tropsch reactor in the presence of a Fischer-Tropsch catalyst under Fischer-Tropsch reaction conditions into a Fischer-Tropsch reaction mixture comprising C₁ to about C₁₀₀ normal paraffins; separating the Fischer-Tropsch mixture into a Fischer-Tropsch liquid stream comprising C₃ to C₂₁ normal paraffins and a Fischer-Tropsch wax stream comprising C₂₂ to C₁₀₀ normal paraffins in a FT separation zone; hydrocracking the Fischer-Tropsch wax stream in a hydrocracking reaction zone comprising a hydrocracking reactor in the presence of a hydrocracking catalyst under hydrocracking conditions forming a hydrocracking effluent stream comprising C₈ to C₁₉ normal paraffins; dewaxing the hydrocracking effluent stream in a dewaxing reaction zone comprising a dewaxing reactor in the presence of a dewaxing catalyst under dewaxing conditions forming a dewaxing reaction mixture comprising C₈ to C₁₉ normal paraffins and isoparaffins; separating the dewaxing reaction mixture into a FT-HCU naphtha stream comprising C₅ to C₁₂ normal paraffins and isoparaffins, and a FT synthetic paraffinic kerosene (FT-SPK) stream comprising C₉ to C₂₀ normal paraffins and isoparaffins in a dewaxing separation zone; separating the Fischer-Tropsch liquid stream into a FT naphtha stream comprising C₅ to C₁₂ normal paraffins and a C₁₃₊ stream comprising C₁₃₊ normal paraffins a second FT separation zone; cracking the FT naphtha stream from the second Fischer-Tropsch fractionation zone and the FT-HCU naphtha stream from the dewaxing reaction zone in an NEP reaction zone comprising an NEP reactor in the presence of an NEP catalyst under NEP reaction conditions to form an NEP effluent stream comprising C_1-3 paraffins and C_6-9 aromatics; separating the NEP effluent stream into an ethane stream, a propane stream, a hydrogen stream, and an aromatics stream in an NEP separation zone; steam cracking the ethane stream in a cracking reaction zone comprising a cracking reactor to form an ethylene effluent stream comprising ethylene; dehydrogenating the propane in a dehydrogenation reaction zone comprising a dehydrogenation reactor in the presence of a dehydrogenation catalyst to form a propylene effluent stream comprising propylene; combining the FT-SPK stream and the aromatics stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising passing the C₁₃₊ stream to the hydrocracking reaction zone. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein separating the NEP effluent stream into the ethane stream and the propane stream comprises separating the NEP effluent stream into the ethane stream, the propane stream, and a light paraffin stream, and further comprising recycling the light paraffin stream to the NEP reaction zone. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising separating the ethylene effluent stream and the propylene effluent stream into an ethylene stream comprising ethylene, a propylene stream comprising propylene, and a second hydrogen stream; recycling the second hydrogen stream to the NEP reaction zone, or recovering the second hydrogen stream, or passing the second hydrogen stream to a H₂ consuming process unit, or combinations thereof.

Without further elaboration, it is believed that using the preceding description that one skilled in the art can utilize the present invention to its fullest extent and easily ascertain the essential characteristics of this invention, without departing from the spirit and scope thereof, to make various changes and modifications of the invention and to adapt it to various usages and conditions. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limiting the remainder of the disclosure in any way whatsoever, and that it is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.

In the foregoing, all temperatures are set forth in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated.