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Processes for making hydrogen and optionally carbon monoxide and their integrations in a Carbon-to-Liquids plant are disclosed. A first syngas produced by a first syngas generator is converted in a hydrocarbon synthesis process to hydrocarbon products, oxygenates and product water comprising dissolv

Processes for making hydrogen and optionally carbon monoxide and their integrations in a Carbon-to-Liquids plant are disclosed. A first syngas produced by a first syngas generator is converted in a hydrocarbon synthesis process to hydrocarbon products, oxygenates and product water comprising dissolved oxygenates. The first syngas generator may use partial oxidation, reforming, gasifying, or pyrolysis of any solid, liquid or gaseous carbonaceous feedstock. The product water may be treated, for example by distillation and/or by stripping, to form an oxygenates-rich stream which comprises a reforming reactant and oxygenates originating from the product water. Oxygenates from the oxygenates-rich stream fed to a second syngas generator are converted under reforming conditions to form at least hydrogen. The hydrogen formed by reforming may be supplied to one or more units using hydrogen within a Carbon-to-Liquids plant.

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1. A process for producing synthetic hydrocarbons and further producing hydrogen and optionally CO in a carbon-to-liquids system comprising two syngas generators operated in parallel, the process comprising: (a) converting a carbonaceous feedstream in a first syngas generator to form a first synthes

1. A process for producing synthetic hydrocarbons and further producing hydrogen and optionally CO in a carbon-to-liquids system comprising two syngas generators operated in parallel, the process comprising: (a) converting a carbonaceous feedstream in a first syngas generator to form a first synthesis gas stream comprising carbon monoxide and hydrogen;(b) feeding said first synthesis gas stream or a portion thereof to a hydrocarbon synthesis reactor comprising a hydrocarbon synthesis catalyst, under conversion promoting conditions sufficient to produce synthetic hydrocarbons, product water, and oxygenates, thereby generating a hydrocarbon product stream and a process water stream, said hydrocarbon product stream comprising at least a portion of said synthetic hydrocarbons, said process water stream comprising at least a portion of the produced oxygenates dissolved in at least a portion of product water, and said hydrocarbon synthesis catalyst is selected from a group 9 or 10 element;(c) treating said process water stream to form an oxygenates-rich stream, said oxygenates-rich stream comprising a reforming reactant and oxygenates originating from said hydrocarbon synthesis product water, wherein said treating to form said oxygenates-rich stream comprises passing said process water stream through a distillation unit to form an oxygenates overhead stream and stripping said oxygenates overhead stream with a stripping fluid comprising said reforming reactant; and(d) passing said oxygenates-rich stream in a reforming zone in a second syngas generator under steam reforming promoting conditions with a steam reforming catalyst sufficient for the conversion of said oxygenates and said reforming reactant to form at least hydrogen and optionally carbon monoxide, wherein the steam reforming catalyst comprises rhodium, iridium, osmium, cerium, lanthanum, or mixtures thereof, and to generate a second synthesis gas stream comprising said formed hydrogen and optionally said formed carbon monoxide. 2. The process according to claim 1, wherein step (c) comprises passing said oxygenates overhead stream through a steam generator to generate a steam product which provides said oxygenates-rich stream, said oxygenates-rich stream comprising steam as the reforming reactant. 3. The process according to claim 1, wherein said reforming zone comprises steam reforming promoting conditions, wherein the treating in step (c) further comprises stripping said oxygenates overhead stream with a stripping fluid comprising steam to provide said oxygenates-rich stream, said oxygenates-rich stream comprising steam as said reforming reactant. 4. The process according to claim 1, wherein said reforming zone comprises steam reforming promoting conditions, wherein the treating in step (c) further comprises stripping said oxygenates overhead stream with a stripping fluid comprising an organic reforming reactant to provide said oxygenates-rich stream, said oxygenates-rich stream comprising said organic reforming reactant, said organic reforming reactant being selected from the group consisting of a C1-C5 hydrocarbon, a mixture of C1-C5 hydrocarbons, an alcohol, a mixture of alcohols, and combinations thereof; and further wherein step (d) further comprises feeding steam to said reforming zone. 5. The process according to claim 1, wherein said oxygenates-rich stream comprises an organic reforming reactant selected from the group consisting of a C1-C5 hydrocarbon, a mixture of C1-C5 hydrocarbons, an alcohol, a mixture of alcohols, and combinations thereof; and further wherein step (d) further comprises feeding CO2 to said reforming zone. 6. The process according to claim 1, wherein the treating in step (c) is effective in removing acidic oxygenates from said process water stream to form said oxygenates-rich stream to be substantially free of acidic oxygenates. 7. The process according to claim 1, wherein said reforming reactant in said oxygenates-rich stream comprises an organic reforming reactant selected from the group consisting of a C1-C5 hydrocarbon, a mixture of C1-C5 hydrocarbons, an alcohol, a mixture of alcohols, and combinations thereof; and further wherein step (d) further comprises feeding an inorganic reforming reactant to said reforming zone, said inorganic reforming reactant being selected from the group consisting of steam, carbon dioxide, and combinations thereof. 8. The process according to claim 1, wherein said reforming reactant in said oxygenates-rich stream is water in liquid phase, water in vapor phase, carbon dioxide, or combinations thereof. 9. The process according to claim 1, wherein said reforming zone comprises steam reforming promoting conditions, and wherein the process further comprises after step (c) and prior to step (d) the following step: passing said oxygenates-rich stream through a steam generator to generate a steam product, whereby said generated steam product comprising steam as said reforming reactant and at least a portion of said oxygenates originating from said hydrocarbon synthesis process water stream; and further wherein said generated steam product is fed to said reforming zone in step (d). 10. The process according to claim 1, further comprising pretreating said process water stream prior to performing step (c), said pretreating comprising at least one of the following steps selected from the group consisting of: adjusting the pH of said process water stream to a desired value; adjusting the temperature of said process water stream; removing solids from said process water stream; removing metals from said process water stream; removing insoluble or suspended organics from said process water stream; removing acidic oxygenates from said process water stream; concentrating oxygenates in said process water stream; diluting said process water stream with freshwater or purified water; and any combinations of two or more of these steps. 11. The process according to claim 1, wherein said oxygenates-rich stream comprises at least one oxygenate selected from the group consisting of alcohols, aldehydes, ketones, esters, aldols, ethers, organic acids, organic anions, and any combinations of two or more thereof. 12. The process according to claim 1, further comprising the following step: (e) supplying at least a portion of the hydrogen formed in step (d) in at least one of the units selected from the group consisting of a water-gas shift reactor; a hydrogen separation unit; a hydrocarbon synthesis reactor; a catalyst activation unit; a catalyst regeneration unit, a product upgrading unit, and combinations thereof, in order to enhance at least one factor selected from the group consisting of market value of synthetic hydrocarbons; productivity of a hydrocarbon synthesis reactor; activity of a hydrocarbon synthesis catalyst; longevity of a hydrocarbon synthesis catalyst; and any combinations of two or more factors thereof. 13. The process according to claim 1, wherein said carbonaceous feedstream in step (b) comprises a material selected from the group consisting of coal, coke, biomass, tar sand, shale oil, natural gas, any light hydrocarbon having 1 to 5 carbon atoms, and any combinations of two or more materials thereof. 14. The process according to claim 1, wherein said second synthesis gas stream generated by second syngas generator has a H2:CO molar greater than said first synthesis gas stream generated to aid first syngas generator. 15. A process for producing synthetic hydrocarbons and further producing hydrogen and optionally CO in a carbon-to-liquids system comprising two syngas generators operated in parallel, the process comprising: (a) converting a carbonaceous feedstream in an oxidative first syngas generator to form a first synthesis gas stream comprising carbon monoxide and hydrogen;(b) feeding said first synthesis gas stream or a portion thereof to a hydrocarbon synthesis reactor comprising a hydrocarbon synthesis catalyst under conversion promoting conditions sufficient to produce synthetic hydrocarbons, product water, and oxygenates, thereby generating a hydrocarbon product stream and a process water stream, said hydrocarbon product stream comprising at least a portion of said synthetic hydrocarbons, said process water stream comprising at least a portion of the produced oxygenates dissolved in at least a portion of product water, and said hydrocarbon synthesis catalyst is selected from a group 9 or 10 element;(c) treating said process water stream to form an oxygenates-rich stream comprising a reforming reactant and oxygenates originating from said product water, said reforming reactant comprising C1-C5 light hydrocarbon or natural gas, said treating comprising the following steps: (c1) passing said process water stream through a distillation unit to form an oxygenates overhead stream; and then(c2) stripping said oxygenates overhead stream with a stripping fluid comprising said reforming reactant; and(d) passing said oxygenates-rich stream and steam in a non-oxidative second syngas generator under steam reforming promoting conditions with a steam reforming catalyst sufficient for the conversion of said oxygenates and said reforming reactant to form at least hydrogen and optionally carbon monoxide, wherein the steam reforming catalyst comprises rhodium, iridium, osmium, cerium, lanthanum, or mixtures thereof, and to generate a second synthesis gas stream comprising said formed hydrogen and optionally said formed carbon monoxide. 16. The process according to claim 15, wherein said carbonaceous feedstream is a methane-containing stream, and further wherein said reforming reactant in said stripping fluid comprises natural gas or at least one C1-C5 hydrocarbon component of natural gas.