Producing renewable hydrocarbons from biomass

Abstract

A process and a system for producing renewable hydrocarbons from biomass are provided.

Description

[0001] Producing Renewable Hydrocarbons from Biomass

[0002] Field of the Invention

[0003] This invention relates to a process for producing renewable hydrocarbons from biomass, the process comprising the steps of

[0004] A) providing biomass;

[0005] B) processing said biomass into a product stream and into at least one by-product stream;

[0006] C) subjecting said at least one by-product stream to anaerobic digestion to obtain biogas;

[0007] D) optionally upgrading said biogas to obtain upgraded biogas;

[0008] E) subjecting said biogas, optionally upgraded according to step D), to hydrogen production to obtain hydrogen; and F) subjecting the product stream to an AtJ process including catalytic hydroprocessing to obtain renewable hydrocarbons, wherein at least a portion of the hydrogen produced in step E) is utilized for said hydroprocessing.

[0009] In addition, the invention relates to a system for carrying out said process for producing renewable hydrocarbons from biomass.

[0010] Background of the Invention

[0011] For decades, fossil carbon resources like coal, oil, and gas have been extensively used as the predominant raw material for energy production and petrochemical processes. This has led to an enormous increase of the carbon dioxide concentration in the atmosphere causing global warming and climate change. In view of the finite availability of fossil resources and the urgency to reduce carbon dioxide emissions, there is a high need to replace fossil carbon resources by renewable carbon resources.

[0012] Thus, the production of hydrocarbons from renewable resources like biomass, in particular for the use as fuels and base materials for chemical processes, has been attracting increasing interest. Such bio-based hydrocarbons exhibit a reduced product carbon footprint and reduce the demand for fossil carbon resources.

[0013] Alcohols like ethanol and butanol (especially n-butanol and iso-butanol) represent important biomass-derived raw materials (“bio-alcohols”) for bio-based hydrocarbon production. Among the major pathways towards bio-based hydrocarbons is the alcohol-to-jet (AtJ) process, a reaction sequence including dehydration, oligomerization, and hydroprocessing, which includes hydrogenation under high temperature and pressure conditions. The AtJ process frequently also includes a catalytic isomerization step, resulting in a hydrocarbon mixture comprising n- and iso-paraffins, among others. These reaction products may be further separated into gaseous and liquid fractions, which constitute valuable transportation fuels and chemical feedstocks, e.g., as renewable diesel (typically hydrocarbons with a final boiling point higher than 180 °C), renewablejetfuel (sustainable aviation fuel: SAF), bio-naphtha (a mixture of hydrocarbons mainly comprising paraffins, e.g., of up to 10 carbon atoms, that can be used - similar to naphtha of fossil origin - as a gasoline blending component or as a chemical feedstock, e.g., for crackers), and other low-boiling hydrocarbons (i.e. mainly C1-4 hydrocarbons, in particular C1-4 alkanes) like bio-based liquefied petroleum gas (LPG; e.g. bio-based butane, propane, and ethane).

[0014] While said product streams are in principle fully bio-based regarding their carbon content, it must be borne in mind that hydrogen is needed for the hydroprocessing step. To date, however, the predominant production routes of hydrogen are based on fossil fuels, mainly on steam reforming of natural gas (above all methane) and other light hydrocarbons. Thus,the production of hydrogen may represent a challenge where there is no well-developed natural gas infrastructure or where the use of natural gas should be avoided for sustainability reasons. In addition, using fossil feedstocks to produce hydrogen increases greenhouse gas emissions of the plant and thus increases the product carbon footprint (carbon intensity) of the products obtained on the basis of said hydrogen.

[0015] According to one approach to address these challenges of the bio-based hydrocarbon production process, low-boiling biobased hydrocarbons (bio-Ci-4-HCs) and bio-naphtha obtained by the AtJ process may be used as a source of hydrogen, e.g., as feedstocks for steam reforming or hydrocarbon pyrolysis. However, steam reforming and pyrolysis of bio-Ci-4-HCs and bio-naphtha is generally less efficient than methane reforming and pyrolysis, respectively. Because of the higher carbon content in such feeds, the product gas obtained in steam reforming contains more carbon oxides compared to a methane feed. Similarly, such feeds provide less hydrogen by pyrolysis than methane. Also, the use of the value products bio-Ci-4-HCs and bio-naphtha as hydrogen production feedstocks may be considered unfavorable from an economic perspective.

[0016] Thus, there is still a need to improve the carbon footprint of renewable diesel, SAF, bio-naphtha, and bio-Ci-4-HCs without compromising the yields and output of the value products.

[0017] Summary of the Invention

[0018] In a first aspect, the present invention relates to a process for producing renewable hydrocarbons from biomass, the process comprising the steps of

[0019] A) providing biomass;

[0020] B) processing said biomass into a product stream comprising at least one bio-alcohol, preferably selected from the group consisting of bio-ethanol, bio-n-butanol, and bio-iso-butanol, and into at least one by-product stream comprising biomass residues and / or biomass waste, wherein said processing comprises a fermentation step;

[0021] C) subjecting said at least one by-product stream to anaerobic digestion to obtain biogas;

[0022] D) optionally upgrading said biogas to obtain upgraded biogas;

[0023] E) subjecting said biogas, optionally upgraded according to step D), to hydrogen production to obtain hydrogen; and F) subjecting the product stream to an alcohol-to-jet process including catalytic hydroprocessing to obtain renewable hydrocarbons, wherein at least a portion of the hydrogen produced in step E) is utilized for said hydroprocessing.

[0024] In a second aspect, the invention relates to a system for producing renewable hydrocarbons from biomass according to the processes described herein, the system comprising

[0025] I) a biomass conversion unit for receiving biomass and processing said biomass into a product stream and into at least one by-product stream;

[0026] II) a biogas plant, connected and arranged downstream to unit I), for receiving at least one by-product stream from unit I), for producing biogas from said at least one by-product stream via anaerobic digestion, and optionally for upgrading said biogas to upgraded biogas;

[0027] III) a hydrogen production unit, connected and arranged downstream to unit II), for receiving said optionally upgraded biogas from unit II) and for producing hydrogen from said optionally upgraded biogas; andIV) an AtJ unit, connected and arranged downstream to units I) and III), for receiving said product stream from unit I) and said hydrogen from unit III) and for producing renewable hydrocarbons from said product stream and said hydrogen.

[0028] Further aspects of the present invention will become apparent to the person skilled in the art directly from the foregoing and following description and the examples.

[0029] Brief Description of the Drawings

[0030] FIG 1 : Flow diagram showing a process for co-producing renewable diesel, SAF, bio-naphtha, and bio-Ci-4-HCs along with upgraded biogas from biomass and hydrogen

[0031] FIG 2: Flow diagram showing a process for co-producing renewable diesel and SAF along with and upgraded biogas from biomass

[0032] FIG 3: Flow diagram showing a process for co-producing renewable diesel, SAF, and bio-naphtha from biomass FIG 4: Flow diagram showing a process for co-producing renewable diesel, SAF, and bio-naphtha from biomass and further biogas feedstock

[0033] FIG 5: Flow diagram showing a process for co-producing renewable diesel, SAF, bio-naphtha, and bio-Ci-4-HCs from biomass

[0034] FIG 6: Flow diagram showing a process for co-producing renewable diesel, SAF, bio-naphtha, and bio-Ci-4-HCs from biomass and further biogas feedstock

[0035] FIG 7: System for performing the processes according to FIGs 1-6

[0036] Legend for FIG 1-7:

[0037] 1 : biomass; 2: biomass residues and biomass waste; 3: biogas; 4: upgraded biogas; 5: hydrogen; 6: bio-alcohol; 6b: olefin; 6c: oligomeric intermediate; 7: renewable diesel; 8: SAF; 9: bio-naphtha; 10: bio-Ci-4-HCs;

[0038] 11: conversion; 11b: dehydration; 11c: oligomerization 12: anaerobic digestion; 13: upgrading; 14: hydrogen production; 15: hydroprocessing; 16: separation; 17: further biogas feedstock

[0039] 101: biomass conversion unit; 102: biogas plant; 103: hydrogen production unit; 104: AtJ unit

[0040] Detailed Description of the Invention

[0041] The present invention provides a process and a system for producing renewable hydrocarbons from biomass.

[0042] The production of renewable hydrocarbons from biomass via the AtJ route starts with the conversion of biomass to bioalcohols, in particular bio-ethanol and bio-butanol (especially iso-butanol), which are then dehydrated, oligomerized, hydroprocessed, and optionally isomerized to hydrocarbon fuels (renewable diesel, SAF), bio-Ci-4-HCs, and bio-naphtha, which can be utilized as a gasoline blending component or as a feedstock for further petrochemical processes, in particular for steam cracking to produce olefins. The conversion of plant biomass into bio-alcohols typically comprises chemical and / or enzymatic as well as fermentative processes. As a side product of these treatments, biomass residues and biomass waste accrue that often are not or cannot be further employed for material use, but are used energetically only, if at all; in the alternative, they are deposited in landfills.It is described herein that such residues and waste may be efficiently used as a feedstock in a biogas plant to produce biogas via anaerobic digestion. For that purpose, said residues and waste may also be complemented with and / or be replaced in full or in part by other biomass residues and biomass waste from other sources than bio-alcohol production. Said biogas, optionally after upgrading, may be utilized for (steam) reforming or hydrocarbon pyrolysis to provide hydrogen which in turn facilitates the hydroprocessing of oligomeric intermediates as a part of the AtJ process to convert bio-alcohols into renewable diesel, SAF, bio-naphtha, and bio-Ci-4-HCs. Thus, by the process of the present invention, (upgraded) biogas produced from biomass residues and biomass waste may fully or at least in part replace other reforming or pyrolysis feedstocks, i.e., hydrogen sources, like natural gas and light hydrocarbons of fossil or renewable origin.

[0043] Therefore, the disclosed process is particularly advantageous where there is no well-established natural gas or light hydrocarbon infrastructure which could secure reliable supply of these raw materials for (steam) reforming or hydrocarbon pyrolysis. In addition, hydrocarbon pyrolysis as a hydrogen production technology delivers not only hydrogen, but also carbon as a value product while carbon dioxide process emissions are avoided; furthermore, it allows for efficient heat integration and changing feed compositions are rather unproblematic. Thus, importantly, the products obtained by hydroprocessing of the oligomeric intermediates with said biomass-derived hydrogen may exhibit an improved carbon footprint. Also, they may be obtained in larger amounts since they do not need to be used partially as raw material for (steam) reforming, which is advantageous especially for renewable hydrocarbons with a limited availability on the market like bionaphtha or bio-Ci-4-HCs. Hence, more of said renewable hydrocarbons may find economically more attractive applications. In turn, also biomass residues and biomass waste may therefore be considered for biogas production that have previously been regarded as hardly suitable for such purposes, e.g., as they may be regarded as poorly biodegradable or yielding low biogas amounts, or due to challenging volume or density characteristics or a vast spatial distribution. Thus, the disclosed process allows for a more complete conversion of biomass into value products. As a further benefit, the use of biomass residues and biomass waste for the biogas production avoids their deposition in landfills and the subsequent often uncontrolled emission of greenhouse gases from these landfills (above all methane and carbon dioxide) due to aerobic and anaerobic decomposition processes; instead, this opportunity to capture and use a relevant raw material resource is not lost but exploited advantageously in the context of the biorefinery processes.

[0044] Along these lines, a system for producing renewable hydrocarbons from biomass that allows to perform the herein-described process and to deliver the above-mentioned advantages may comprise a biomass conversion unit to convert biomass into bio-alcohol, e.g., ethanol or butanol (especially iso-butanol), as a main product and into biomass residues and biomass waste as by-products, a biogas plant to produce (upgraded) biogas via anaerobic digestion of the biomass residues and biomass waste, a hydrogen production unit to produce hydrogen from hydrocarbons, and an AtJ unit to perform dehydration, oligomerization, and hydroprocessing of the bio-alcohol and further upgrading or refinery steps. Said system furthermore allows for a flexibilization of the overall production pathways, both in terms of feedstock and in terms of product spectrum. In principle, the system is run with biomass and hydrogen to produce renewable fuels (renewable diesel, SAF), bio-naphtha, bio-Ci-4-HCs, and (upgraded) biogas as main value products. In case external hydrogen supply is short or no external hydrogen supply is available at all, hydrogen may be produced internally in the hydrogen production unit from (upgraded) biogas obtained from the biogas plant. In this setup, the yields of renewable fuels, bionaphtha, and bio-Ci-4-HCs are maximized. If on the other hand there are not enough biomass residues and biomass waste available, as may be the case for seasonal reasons, the hydrogen production unit may be fed with hydrocarbons, e.g., bio-CI-4-HCS and / or bio-naphtha, from the AtJ unit. Thus, the yields of renewable fuels are maximized. Further, if there is an abundancy of biomass, (upgraded) biogas may be obtained as an additional value product. Also, if there is a high demand for (upgraded) biogas, more of the bio-Ci-4-HCs or bio-naphtha may be used as a hydrogen production feedstock to maximize the (upgraded) biogas output.

[0045] Thus, in a first aspect, the present invention provides a process for producing renewable hydrocarbons from biomass, the process comprising the steps of

[0046] A) providing biomass;

[0047] B) processing said biomass into a product stream comprising at least one bio-alcohol, preferably selected from the group consisting of bio-ethanol, bio-n-butanol, and bio-iso-butanol, and into at least one by-product stream comprising biomass residues and / or biomass waste, wherein said processing comprises a fermentation step;

[0048] C) subjecting said at least one by-product stream to anaerobic digestion to obtain biogas;

[0049] D) optionally upgrading said biogas to obtain upgraded biogas;

[0050] E) subjecting said biogas, optionally upgraded according to step D), to hydrogen production to obtain hydrogen; and F) subjecting the product stream to an alcohol-to-jet process including catalytic hydroprocessing to obtain renewable hydrocarbons, wherein at least a portion of the hydrogen produced in step E) is utilized for said hydroprocessing.

[0051] Step A)

[0052] Biomass is biological material derived from living or recently living organisms. The biomass to be provided in step A) may be any material of vegetable origin that is in principle suitable to be converted at least into ethanol and / or butanol (especially iso-butanol). In particular, the term biomass comprises plants or parts thereof like crops, wood, or residues thereof, and bio waste such as biomass residues and organic food waste. Of note, the biomass provided may be composed of biomass streams from various of the above-mentioned sources.

[0053] According to one embodiment, the biomass provided in step A) is of vegetable origin.

[0054] According to another embodiment, the biomass provided in step A) comprises or is derived from sugar crops (e.g., sucrose-containing crops, sugarcane, sugar beet), starch crops (e.g., corn, wheat, starch, cassava), sugars (especially pentoses and hexoses like glucose, fructose, sucrose, xylose, arabinose), energy crops (e.g. switchgrass, other grasses like napier grass, miscanthus), lignocellulosic biomass, agricultural residues, straw (e.g., wheat straw, oat straw, barley straw, rice straw, corn stover, corn cobbs, rice husks, sugarcane bagasse), forestry residues, wood chips, wood waste, sawdust, degradation products of plants or plant parts, and organic components of municipal solid waste, preferably it comprises or is derived from starch crops, e.g. corn, wheat, sugar crops, e.g. sugarcane, sugar beet, and straw.

[0055] Step B)

[0056] The processing of biomass according to step B) into bio-alcohol is well-known in the art and comprises a biochemical fermentation step, e.g., utilizing (genetically engineered) microorganisms like yeast or bacteria. To make the biomass more amenable to enzymatic hydrolysis and fermentation, pretreatment of the biomass may be necessary, in particular where lignocellulosic biomass is used. Such pretreatment may comprise both mechanical and physical operations, like harvesting and collecting as well as measures of mechanical of physical biomass treatment like crushing, cracking, cutting, shredding,grinding, chipping, milling, extrusion, squeezing, pressing, pelletizing and sieving, thermal treatments such as drying and torrefaction, thermochemical treatments like steam explosion and hydrothermal pretreatment, chemical processes like dilute acid pretreatment (e.g., using sulfuric acid), alkaline pre-treatment (e.g., using sodium hydroxide), extraction, distillation, hydrolysis, neutralization, or ketonization, and biological methods using microorganisms, e.g., to degrade lignin and hemicellulose. Also, the mechanical, physical, and / or chemical separation of the products and by-products of said operations and processes, in particular the separation of gaseous, liquid, and solid fractions, forms part of the processing according to step B). In essence, step B) comprises the removal of all by-products from the product stream that are not suitable or are detrimental for further use as a feedstock for the AtJ process. The right choice of suitable process steps and operating conditions is mainly dependent on the biomass to be processed; but the one skilled in the art will be familiar with such considerations. The product stream obtained by said processing comprises, preferably consists of a bio-alcohol selected from the group consisting of ethanol, n-butanol, and iso-butanol. In particular, the product stream may be a fermentation broth or parts thereof containing bio-alcohol. Step B) may also involve the purification of the product stream, e.g., by distillation or using pressure-swing molecular sieve columns, such that it comprises mainly or consists essentially of bio-alcohol. As used herein, the term “bio-alcohol” refers to an alcohol obtained from a biomass feedstock containing a carbon source that is convertible to alcohol, in particular by microbial metabolism. It includes, but is not limited to bioethanol and bio-butanol as well as its isomers

[0057] In particular, step B) may comprise the production of so-called first-generation bio-alcohol (especially first-generation bioethanol) from starch, comprising the steps of enzymatic saccharification or hydrolysis of starch into sugars, microbial fermentation of said sugars to produce bio-alcohol, purification by distillation, and removal of water to produce anhydrous bio-alcohol.

[0058] Also, step B) may comprise the production of so-called second-generation bio-alcohol (especially second-generation bioethanol) from lignocellulosic materials, e.g., from agricultural crops, comprising the steps of pretreatment (especially milling and exposure to acid and heat to reduce the size of the plant fibers), chemical and / or enzymatic hydrolysis and saccharification, microbial fermentation, distillation, and water removal.

[0059] The at least one by-product stream obtained by said processing comprises biomass residues and / or biomass waste resulting from said processing. The amount and quality of these residues and waste containing streams depend on the biomass feedstocks and the processing steps applied. The by-product streams may comprise in particular solid, semisolid, and liquid components, such as lignin, hemicellulose hydrolysates, vinasse, distillers dried grains with solubles (DDGS), organic acids (like acetic acid, lactic acid, gluconic acid and other organic acids), furfural and glycerol. The above-mentioned by-product components may be comprised in one single by-product stream or in more than one separated byproduct streams.

[0060] It is to be understood that processing the biomass into a product stream and into at least one by-product stream may also comprise purification steps, e.g., to remove contaminants or impurities that may be detrimental for the further process steps or for further use of the end products of the process. Thus, for instance, the by-product stream may comprise biomass residues and biomass waste obtained in the course of the processing.

[0061] Thus, according to one embodiment, the processing of step B) comprises pretreatment comprising mechanical operations and physical operations.According to another embodiment, the processing of step B) comprises pretreatment comprising thermal and / or thermochemical treatments.

[0062] According to another embodiment, the processing of step B) comprises pretreatment comprising chemical processes. According to another embodiment, the processing of step B) comprises pretreatment comprising biological methods. According to another embodiment, the processing of step B) comprises microbial fermentation of the (optionally pretreated) biomass provided in step A).

[0063] According to another embodiment, the processing of step B) comprises the separation of the obtained products and byproducts.

[0064] According to another embodiment, the processing of step B) yields a product stream comprising, preferably consisting of, bio-alcohol, preferably bio-ethanol or bio-iso-butanol.

[0065] According to another embodiment, said bio-alcohol is selected from the group consisting of bio-ethanol, bio-n-butanol, and bio-iso-butanol.

[0066] According to another embodiment, the processing of step B) yields at least one by-product stream comprising biomass residues and / or biomass waste, preferably selected from the group consisting of lignin, hemicellulose hydrolysates, vinasse, and DDGS.

[0067] According to another embodiment, the processing of step B) comprises purification steps applied to the product stream and / or to the at least one by-product stream, in particular distillation of the bio-alcohol and / or water removal from the bio-alcohol.

[0068] Step C)

[0069] Biogas is a mixture of methane (e.g., 45 % to 75 % (v / v)), carbon dioxide, and small quantities of other gases and contaminants like water vapor and nitrogen- or sulfur-containing gases (e.g., ammonia or hydrogen sulfide), its exact composition depending on the type of feedstock and the production route. The production of biogas from organic feedstock, e.g., from the at least one by-product stream in step C), via anaerobic digestion is known in the art and may be conducted as dry or wet digestion. To overcome digestion barriers, to enhance microbial digestion, and to improve dewatering and the quality of the digestate, the actual digestion step is typically preceded by a biomass pretreatment. Biomass pretreatment should be adapted to the biomass structure and characteristics and may include mechanical, physical, thermal, chemical, and biological steps as well as combinations thereof, e.g. biological-physicochemical, electrochemical or thermal-chemical (such as thermal-alkaline) pretreatments. More specifically, pretreatment may comprise process steps like crushing, shredding, slurrifying (i.e. adding liquid, in particular water), adjusting the water content (e.g., to about 5 to 20 weight-%), ultrasonication, microwave irradiation, electrokinetic and high-pressure homogenization.

[0070] Biogas production pathways include biodigesters (airtight systems in which microorganisms degrade organic material diluted in water), landfill gas recovery systems (capturing gas originating from anaerobic decomposition, e.g., of biomass and / or municipal solid waste in landfills, optionally including pipelines for the transport of the biogas from the landfill to the unit producing hydrogen from said biogas), and wastewater treatment plants (recovering organic matter from sewage sludge for use in anaerobic digestion). In addition to biogas, the anaerobic digestion of organic feedstock provides a digestate that may be dried (partly or completely) and further used as a fertilizer or soil conditioner or to feed animals, e.g., ruminants. A wide variety of feedstocks can be used for biogas production like agricultural and crop residues (e.g., fromthe harvest of wheat, maize, rice, other coarse grains, sugarbeets, sugarcane, soybean, or other oilseeds), animal manure (e.g., from livestock including cattle, pigs, poultry, or sheep), organic fractions of industrial and municipal solid waste (e.g., food and green waste like leaves and grass, paper, cardboard, wood, or industrial waste from food-processing industry), and sewage or wastewater sludge.

[0071] Within the scope of this disclosure, it is also contemplated that one or more of the above-mentioned biogas feedstocks may be used for biogas production and that the one or more by-product streams obtained in step B) may be used for biogas production in admixture with one or more of the biogas feedstocks mentioned above (“further biogas feedstocks”, i.e., biogas feedstocks other than the by-product streams obtained in step B)) to increase yield and / or efficiency of the biogas production process. The ratio of the by-product streams to the further biogas feedstocks in said admixture may range from 100 % : 0 % (i.e., by-product streams only) to 0 % : 100 % (i.e., further biogas feedstocks only), e.g., the ratio may be about 10 % : 90 %, about 20 % : 80 %, about 30 % : 70 %, about 40 % : 60 %, about 50 % : 50 %, about 60 % : 40 %, about 70 % : 30 %, about 80 % : 20 %, or about 90 % : 10 %.

[0072] Thus, according to one embodiment, step C) comprises biomass pretreatment, preferably mechanical, physical, thermal, chemical, and biological steps as well as combinations thereof.

[0073] According to another embodiment, the anaerobic digestion of step C) is performed as dry and / or wet digestion, preferably as dry digestion.

[0074] According to another embodiment, the anaerobic digestion of step C) is performed in a biodigester, in a landfill, and / or in a wastewater treatment plant, preferably in a biodigester.

[0075] According to another embodiment, step C) comprises, preferably consists of, the substeps C 1 ), C2a), and C3a):

[0076] C 1 ) providing at least one feedstock for biogas production, preferably selected from agricultural and crop residues, animal manure, organic fractions of industrial and municipal solid waste, and sewage or wastewater sludge, more preferably selected from agricultural and crop residues, e.g., from rice, and animal manure;

[0077] C2a) mixing said at least one by-product stream with said at least one feedstock for biogas production; and C3a) subjecting the feedstock mixture of C2a) to anaerobic digestion to obtain biogas.

[0078] According to another embodiment, step C) comprises, preferably consists of, the substeps C 1 ), C2b), and C3b):

[0079] C1) providing at least one feedstock for biogas production, preferably selected from agricultural and crop residues, animal manure, organic fractions of industrial and municipal solid waste, and sewage or wastewater sludge, more preferably selected from agricultural and crop residues, e.g., from rice, and animal manure;

[0080] C2b) optionally mixing at least two of said at least one feedstocks for biogas production; and

[0081] C3b) subjecting the at least one feedstock provided in C1) and / or the feedstock mixture of C2b) to anaerobic digestion to obtain biogas.

[0082] According to another embodiment, step C) comprises (partially or completely) drying the digestate obtained from anaerobic digestion of biogas production feedstock to obtain fertilizer, soil conditioner, and / or animal feed.

[0083] Step D)

[0084] In optional step D), the biogas obtained in step C) is upgraded in that contaminants that might negatively impact subsequent process steps, in particular the hydrogen production step E), are removed completely or their amounts are reduced to levels that are tolerated by the subsequent process steps. Thus, upgraded biogas is obtained. Depending on the biogasand the subsequent process steps used, the skilled person will be well aware of relevant contaminants to be removed, of tolerable levels, and of technical measures to reduce their amounts. In particular, nitrogen- and sulfur-containing contaminants like ammonia or hydrogen sulfide may be subject to said purification. Processes for such biogas upgrading include water scrubbing, amine gas treatment, pressure swing adsorption, and membrane separation techniques, as well as other purification steps.

[0085] In particular, biogas may be upgraded to biomethane, a preferred form of upgraded biogas. Upgrading of biogas to biomethane includes not only removing relevant contaminants, but also lowering the amounts of carbon dioxide in the biogas, which may be achieved by water scrubbing, amine gas treatment, pressure swing adsorption, and membrane separation techniques. Preferably, biomethane meets the specifications commonly used for natural gas grids, e.g., it typically contains not less than 75 % (v / v), preferably not less than 85 % (v / v), more preferably not less than 90 % (v / v) or 95% (v / v) methane. Correspondingly, biomethane typically contains not more than 25 % (v / v), preferably not more than 15 % (v / v), more preferably not more than 10 % (v / v), even more preferably not more than 5 % (v / v) or not more than 3 % (v / v) carbon dioxide. As a further process step of biogas upgrading according to step D), compression of the (upgraded) biogas is contemplated within the scope of this invention. Compression may be necessary or desired to obtain (upgraded) biogas in a form suitable for further applications like storage, shipment, delivery, and / or use in subsequent process steps.

[0086] Thus, according to one embodiment, the optional biogas upgrading of step D) includes reducing the amounts of ammonia, hydrogen sulfide, water, and other impurities in the biogas, preferably reducing the amounts of ammonia and hydrogen sulfide in the biogas, preferably to levels tolerated by subsequent step E).

[0087] According to another embodiment, the optional biogas upgrading of step D) includes reducing the amount of carbon dioxide in the biogas, preferably to amounts of not more than 25 % (v / v), more preferably of not more than 15 % (v / v), even more preferably of not more than 10 % (v / v), most preferably of not more than 5 % (v / v) or of not more than 3 % (v / v) carbon dioxide.

[0088] According to another embodiment, the optional biogas upgrading of step D) includes water scrubbing, amine gas treatment, pressure swing adsorption, and / or membrane separation techniques.

[0089] According to another embodiment, the optional biogas upgrading of step D) includes compression of the (upgraded) biogas.

[0090] Step E)

[0091] Hydrogen production may be carried out by reforming of hydrocarbons or pyrolysis of hydrocarbons.

[0092] Reforming of hydrocarbons is a mature process to produce hydrogen. The most important hydrocarbon reforming technologies are steam (methane) reforming, partial oxidation, and autothermal reforming (the latter being basically a combination of the former two processes), all of which are well-known to the one of skill in the art. For instance, in steam reforming, methane (e.g., provided in the form of natural gas or biogas) is reacted with steam in the presence of a catalyst under high temperature and high-pressure conditions, whereas in partial oxidation, methane is reacted with sub-stoichio-metric amounts of oxygen. In both cases, a mixture consisting primarily of hydrogen, carbon monoxide, and relatively small amounts of carbon dioxide is obtained. A subsequent water-gas shift reaction allows for increasing the hydrogen yield further by converting carbon monoxide and water to hydrogen and carbon dioxide. The resulting gas stream may be finallypurified by a pressure swing adsorption process to remove remaining impurities like carbon dioxide and to yield essentially pure hydrogen.

[0093] In hydrocarbon pyrolysis (also referred to as “hydrocarbon decomposition”), light hydrocarbons, in particular methane (“methane pyrolysis”), e.g., in the form of natural gas or biogas, is decomposed without the involvement of oxygen into hydrogen and solid, high-purity carbon (e.g., as carbon black, carbon powder, or granular carbon). In contrast to reforming, however, no gaseous carbon dioxide is produced, but solid carbon is formed as a by-product, which has a positive effect on economic efficiency and ecologic impact. Further, compared to water electrolysis, methane pyrolysis requires significantly less energy. Therefore, methane pyrolysis is considered a promising sustainable technology for future hydrogen production.

[0094] Hydrocarbon pyrolysis may be carried out in different ways known to the one skilled in the art (Muradov et al., International Journal Hydrogen Energy 2008, 33, 6804-6839; Abbas et al., International Journal Hydrogen Energy 2010, 35, 1160-1190); Dagle et al.: An Overview of Natural Gas Conversion Technologies for Co-Production of Hydrogen and Value-Added Solid Carbon Products, Report by Argonne National Laboratory and Pacific Northwest National Laboratory (ANL-17 / 11, PNNL-26726, November 2017): catalytically or thermally, and with heat input via plasma, microwave, heated carrier gas, resistance heating, induction, liquid metal processes, or autothermally, in particular via plasma pyrolysis (WO 2015 / 116797, WO 2015 / 116800), metal melting / metal salt melting (WO 2020 / 161192, WO 2021 / 183959), moving bed process (US 2982622, WO 2019 / 145279, WO 2020 / 200522, WO 2023 / 057242), (fluidized bed) catalytic process (WO 2011 / 029144, WO 2016 / 154666), or partial / pulsed combustion (WO 2020 / 118417 and US 2022 / 0185664), the moving bed process being particularly advantageous due to its high efficiency, heat integration, flexibility, and favorable product carbon footprint. These processes differ i.a. in the form of the energy used (thermal, electrical, etc.), the process conditions (temperature, pressure, etc.), the catalysts, and / or auxiliary materials used. The pyrolysis process is preferably heated electrically, even more preferably by resistive heating (Joule heating) of the substrate material (US 2982622, WO 2019 / 145279, and WO 2020 / 200522).

[0095] The solid carbon type generated in the methane decomposition depends on the reaction conditions, reactor, and heating technology. Examples are

[0096] carbon black from plasma processes

[0097] carbon powder from liquid metal processes

[0098] granular carbon from thermal decomposition in fixed, moving, or fluidized bed reactors.

[0099] The processing and separation of solid carbon depends on the chosen pyrolysis technology and is known by the person skilled in the art. For example, in a plasma pyrolysis process, the solid carbon in the form of carbon black is discharged from the reactor with the gas and then separated, e.g., by a cyclone. The solid carbon might be post-treated, e.g., agglomerated. Depending on the process and the metals used, in molten metal pyrolysis, the carbon floats on the melt and is skimmed off or leaves the reactor together with the gas stream and is then separated, e.g., by a filter or cyclone. In addition, a purification step to remove residual metal from the carbon could be required e.g., washing or evaporation. In the catalytic pyrolysis technology and in the fixed and moving bed technology, the solid carbon is deposited on the surface of the catalyst and / or support and taken off the reactor via the catalyst and / or support.

[0100] Thus, solid carbon may be separated by a cyclone or a filter and may be post-treated, e.g., to achieve agglomeration; further, the carbon may be purified by washing and / or evaporation techniques to remove, for instance, residual metalcontamination. The resulting gas stream comprising hydrogen may be finally purified by a pressure swing adsorption process to remove remaining impurities like hydrogen sulfide, carbon oxides, hydrocarbons, and inert gases like nitrogen, to yield purified hydrogen.

[0101] Of note, other hydrocarbons than methane, e.g., the hydrocarbons obtained in step F) as described below, may be used as a co-feed for the hydrogen production step; this may be beneficial, for instance, in case the (upgraded) biogas production is insufficient to fully supply the hydrogen production process. In this case, the term “hydrocarbon reforming” and “hydrocarbon pyrolysis” as used herein, shall encompass not only methane reforming and methane pyrolysis, respectively, but also reforming and pyrolysis of such hydrocarbons.

[0102] In addition, while biogas upgraded according to step D) is preferably used as a feedstock, hydrogen production according to step E) may also be carried out with biogas without further upgrading, e.g., with biogas as provided by step C), as a feedstock. For being suitable for hydrogen production, said biogas may comprise up to 50 % (v / v) carbon dioxide, preferably up to 40 %, more preferably up to 30 %, even more preferably up to 25 %, most preferably up to 15 % (v / v) carbon dioxide.

[0103] Thus, the different above-mentioned hydrogen production feedstocks (biogas, upgraded biogas, and hydrocarbons like bio-naphtha and bio-Ci.4-HCs) may be used for hydrogen production according to step E) separately or in admixture, simultaneously or sequentially, with the mass fractions of (upgraded) biogas ranging from 0 % (i.e., bio-naphtha and / or bio-Ci-4-HCs only) to 100 % (i.e., biogas and upgraded biogas only), e.g., the mass fractions of (upgraded) biogas being approximately 20 %, 40 %, 60 %, 80 %, or 100 %, preferably not less than 50 % (m / m).

[0104] Accordingly, the hydrogen obtained in step E) may originate from biogas, upgraded biogas, and hydrocarbons like bionaphtha and bio-Ci-4-HCs, the mass fraction of hydrogen originating from biogas and upgraded biogas accounting for not less than approximately 10 %, 20 %, 30 %, 40 %, 50 %, 60 %, 70 %, 80 %, 90 % (m / m) of the total hydrogen obtained in step E), preferably not less than 25 %, more preferably not less than 50 % (m / m), even more preferably not less than 75 %, most preferably not less than 90 % (m / m). The given hydrogen mass fractions may be determined, calculated, or evaluated on the basis of a certain observation period, production cycle, or batch manufacturing in subsequent process steps.

[0105] Thus, according to one embodiment, hydrogen production in step E) is carried out by hydrocarbon reforming, in particular by steam reforming, partial oxidation, or autothermal reforming, preferably by steam reforming.

[0106] According to another embodiment, hydrogen production is carried out by hydrocarbon pyrolysis.

[0107] According to another embodiment, hydrogen production in step E) is carried out by hydrocarbon reforming and comprises the substeps E1), E2), and E3):

[0108] E1) steam reforming or partial oxidation or autothermal reforming of hydrocarbons, preferably methane, to obtain a first gas stream comprising hydrogen, carbon monoxide, and carbon dioxide;

[0109] E2) water-gas shift reaction of the first gas stream of E1) to obtain a second gas stream comprising, preferably consisting essentially of, hydrogen and carbon dioxide; and

[0110] E3) purification of the second gas stream of E2), preferably by pressure swing adsorption, to obtain a third gas stream consisting essentially of hydrogen.

[0111] According to another embodiment, hydrogen production in step E) is carried out by hydrocarbon pyrolysis and comprises the substeps E4), E5), and E6):E4) hydrocarbon decomposition to obtain a first gas stream comprising hydrogen;

[0112] E5) processing of solid carbon, optionally carbon separation, carbon post-treatment, and / or carbon purification, to obtain a carbon stream comprising solid carbon; and

[0113] E6) purification of the first gas stream of E4), preferably by pressure swing adsorption, to obtain a second gas stream consisting essentially of hydrogen.

[0114] According to another embodiment, hydrogen production is carried out with biogas as provided by step C), wherein the biogas comprises not more than 50 % (v / v) carbon dioxide, preferably not more than 25 % (v / v) carbon dioxide, more preferably not more than 15 % (v / v) carbon dioxide.

[0115] According to another embodiment, hydrogen production is carried out with upgraded biogas as provided by step D). According to another embodiment, step E) additionally comprises subjecting hydrocarbons to hydrogen production to obtain hydrogen, wherein said hydrocarbons, preferably bio-Ci-4-HCs or bio-naphtha, originate preferably from step F) as described below.

[0116] According to another embodiment, the mass fraction of hydrogen originating from biogas and upgraded biogas accounts for not less than approximately 10 %, 20 %, 30 %, 40 %, 50 %, 60 %, 70 %, 80 %, 90 % (m / m) of the total hydrogen obtained in step E), preferably not less than 25 %, more preferably not less than 50 % (m / m), even more preferably not less than 75 %, most preferably not less than 90 % (m / m).

[0117] Step F)

[0118] The alcohol-to-jet (AtJ) step F) comprises the dehydration of bio-alcohols from step B) to produce olefins, their oligomerization to obtain oligomeric intermediates of the AtJ process, the hydroprocessing of said intermediates to produce a mixture of hydrocarbons, and the fractionation of said mixture.

[0119] As a feedstock for the AtJ process, the product stream of step A) containing bio-alcohol, preferably bio-alcohol of step A), is used. Also, said feedstocks may be complemented by bio-alcohol from other sources, e.g., to achieve the necessary amounts for running the AtJ process efficiently.

[0120] The production of olefins by catalytic dehydration of alcohols is a well-known process. E.g., the dehydration of ethanol is commonly carried out at 300 to 400 °C and moderate pressure in the presence of a catalyst. Catalytic effects are reviewed in Ind & Eng Chem Research, 52, 28, 9505-9514 (2013), Materials 6, 101-115 (2013) and ACS Omega, 2, 4287-4296 (2017). Examples for catalysts are activated alumina or silica, phosphoric acid impregnated on coke, heteropoly acids (HPA salts), silica-alumina, molecular sieves such as zeolites of the ZSM-5 type or SAPO-11 type, other zeolites or modified zeolites of various molecular structures with zeolites and HPA salts being preferred.

[0121] Ethanol dehydration is, for example described in WO 2009 / 098268, WO 2010 / 066830, WO 2009 / 070858 and the prior art discussed therein, WO 2011 / 085223 and the prior art discussed therein, US 4,234,752, US 4,396,789, US 4,529,827 and WO 2004 / 078336.

[0122] The ethanol dehydration reaction is in general carried out in the vapor phase in contact with a heterogeneous catalyst bed using either fixed bed or fluidized bed reactors. For fixed bed reactors, the operation can be either isothermal (with external heating system) or adiabatic (in the presence of a heat carrying fluid). The feedstock is vaporized and heated to the desired reaction temperature; the temperature drops as the reaction proceeds in the reactor. Multiple reactor beds are usually used in series to maintain the temperature drop in each bed to a manageable range. The cooled effluent from each bed isfurther heated to bring it to the desired inlet temperature of the subsequent beds. Moreover, a portion of the water is recirculated along with fresh and unreacted ethanol. The presence of water helps in moderating the temperature decrease in each bed.

[0123] Prior to dehydration, the bio-ethanol feedstock may be sent to a pretreatment section to remove mineral contaminants, which would otherwise be detrimental to the downstream catalytic reaction. The pretreatment may involve contacting the bio-ethanol feedstock with cation and / or anion exchange resins. After a certain period of operation, the resins may be regenerated by passing a regenerant solution through the resin bed(s) to restore their ion exchange capacity. Two sets of beds are preferably operated in parallel to maintain continuous operation. One set of resin beds is suitably regenerated while the other set is being used for pretreatment.

[0124] In the isothermal design, the catalyst is placed inside the tubes of multitubular fixed-bed reactors which arranged vertically and surrounded by a shell (tube and shell design). A heat transfer medium, such as molten salts or oil, is circulated inside the shell to provide the required heat. Baffles may be provided on the shell side to facilitate heat transfer. The cooled heating medium is heated externally and is recirculated. The temperature drop on the process side can be reduced as compared to the adiabatic reactor. A better control on the temperature results in increased selectivity for the ethylene formation and reduction in the amounts of undesirable by-products. The temperature is maintained at approximately constant levels within the range of 300° to 350°C. Ethanol conversion is between 98 and 99%, and the selectivity to ethylene is between 94 and 97 mol%. Because of the rate of coke deposition, the catalyst must be regenerated frequently. Depending on the type of catalyst used, the cycle life is between 3 weeks and 4 months, followed by regeneration, for example for 3 days.

[0125] In the adiabatic design, the endothermic heat of reaction is supplied by a preheated inert diluent such as steam. Three fixed-bed reactors may typically be used, with intermediate furnaces to reheat the ethanol / steam mixed feed stream to each reactor. Feeding steam with ethanol results in less coke formation, longer catalyst activity, and higher yields. A further process is a fluidized-bed process. The fluidized-bed system offers excellent temperature control in the reactor, thereby minimizing by-product formation. The heat distribution rate of the fluidized bed operation approaches isothermal conditions. The endothermic heat of reaction is supplied by the hot recycled silica-alumina catalyst returning from the catalyst regenerator. Thus, external heating of the reactor is not necessary.

[0126] After dehydration, the reaction mixture is subjected to a separation step. The general separation scheme consists of quickly cooling the reaction gas, for example in a water quench tower, which separates most of the by-product water and the unreacted ethanol from ethylene and other light components which, for example exit from the top of the quench tower. In one type of separation scheme, the water-washed ethylene stream is immediately caustic-washed, for example in a column, to remove traces of CO2. The gaseous stream may enter a compressor directly or pass to a surge gas holder first and then to a gas compressor. After compression, the gas is cooled with refrigeration and then passed through an adsorber with, for example activated carbon, to remove traces of heavy components, (e.g., C4s), if they are present. The adsorber is followed by a desiccant drying and dust filtering step before the ethylene product leaves the plant. This separation scheme produces 99%+ purity ethylene. If desired, the ethylene is further purified by caustic washing and desiccant-drying and fractionated in a low-temperature column to obtain the final product.

[0127] Several commercial processes are currently in operation, developed by Braskem, Chematur, British Petroleum (BP), and Axens together with Total and IFPEN. The processes differ, e.g., in their process conditions, catalysts and adopted heatintegration scheme. The process by BP (now Technip) is called Hummingbird. In this process, a heteropolyacid is used as catalyst, and the reactor operates at 160 to 270 °C and 1 to 45 bar. The unreacted ethanol in recirculated to the reactor. The process developed by Axens is called Atol. Two fixed bed adiabatic reactors, operating at 400 to 500 °C, are used. Chematur’s process operates with four adiabatic tubular reactors. Syndol catalysts, with the main components of AI2O3-MgO / SiO2, are employed in this process that was developed by American Halcon Scientific Design, Inc. in the 1980s. In the Braskem process, the adiabatic reactor feed is diluted with steam to a large extent. In such a process, the reactor operates at 180 to 600 °C, preferably 300 to 500 °C, and at 1.9 to 19.6 bar. An alumina or silica-alumina catalyst is used. The Braskem process is described in more detail in US 4,232,179. A process control in accordance with the Braskem process is particularly preferred.

[0128] Similar processes may be employed for the dehydration of other bio-alcohols described herein and are in general known to the one of skill in the art. E.g., n-butanol can be dehydrated to 1-butene at 380 °C and 2.1 bar over a y-alumina catalyst and iso-butanol may be dehydrated using acidic catalysts such as ZSM-5 zeolites, Y-type zeolites, and Amberlyst acidic resins.

[0129] The oligomerization of the obtained olefins may be achieved at temperatures between 200 °C and 300 °C in the presence of a catalyst. A variety of catalytic systems, both homogeneous and heterogeneous, e.g., zeolite or other solid acid catalysts, may be employed in single- or multiple-reactor setups. Among others, processes for ethylene oligomerization like the Chevron-Phillips Ziegler one-step process, the Ziegler two-step process, and the Shell higher olefins process are known in the art. The process conditions should be designed with care to achieve appreciable yields of oligomeric intermediates in the desired molecular weight range, e.g., elevated pressures may be used to promote the formation of longer carbon chains. Thus, oligomeric (AtJ) intermediates are formed.

[0130] Also, depending on the catalyst, oligomerization may be accompanied by isomerization and / or cracking processes.

[0131] Catalytic hydroprocessing, i.e., chemical operations using hydrogen in the presence of a catalyst at high temperatures and pressures, is a well-established upgrading technology that includes more specifically the hydrogenation of the oligomeric intermediates to obtain saturated hydrocarbons. Hydroprocessing may also achieve the removal of remaining impurities in the intermediates. Furthermore, hydroisomerization and / or hydrocracking of the obtained renewable hydrocarbons may be encompassed in step F) to shift the relative yields of the different fractions in a desired way and / or to improve their properties and performances (e.g., at low temperatures) during further use, e.g., as fuels, fuel blendstocks, or as chemical feedstocks. Said hydroisomerization and hydrocracking may run simultaneously or sequentially to the other above-mentioned processes encompassed by catalytic hydroprocessing, e.g., to hydrogenation.

[0132] The hydroprocessing may be carried out at about 300 °C to 400 °C in presence of excess hydrogen and at high pressures (e.g., upto 100 bar). Metal-based catalysts such as nickel, cobalt, or platinum on supports like alumina are often employed. Remaining hydrogen is typically separated and recycled to the feed.

[0133] Hydroisomerization may be carried out to increase the degree of branching of the hydrocarbons. Typically, hydroisomerization may be achieved at temperatures between 200 °C and 300 °C in the presence of hydrogen and platinum or palladium catalysts on acidic supports like zeolites or alumina at pressures of 10 to 30 bar.The hydroprocessing typically yields a hydrocarbon mixture mainly comprising paraffins in the diesel-fuel, kerosene, and naphtha range.

[0134] Large amounts of hydrogen are typically needed to accomplish the goal of converting oligomeric AtJ intermediates into renewable hydrocarbons that are suitable for further use, be it as fuels (in particular renewable diesel and renewable jet fuel) or as chemical feedstocks (in particular bio-naphtha). The exact composition of the obtained renewable hydrocarbon mixture will depend, for example, on the feedstock composition, the processing conditions, and the catalyst properties. Most of the available hydrogen being derived from fossil sources, the carbon footprint of such renewable hydrocarbons is often negatively impacted by the hydrogen demand. Therefore, according to the invention a part of the hydrogen needed for hydroprocessing of the oligomeric intermediates in step F) is provided from step E), i.e., from a renewable source. Hence, the carbon intensity of renewable hydrocarbons is further reduced by replacing hydrogen of fossil origin by hydrogen of renewable origin, as obtained in step E).

[0135] Finally, the hydrocarbon mixture obtained by the above-mentioned process steps is separated to obtain different hydrocarbon fractions with different properties. Typically, said fractionation is achieved using distillation processes at atmospheric pressure or slightly elevated pressure. Typical fractions to be obtained include renewable diesel, SAF, bio-naphtha, and bio-Ci-4-HCs.

[0136] Thus, according to one embodiment, for the catalytic hydroprocessing in step F), at least a portion of the hydrogen produced in step E), preferably essentially all of the hydrogen produced in step E), is utilized.

[0137] According to another embodiment, for the catalytic hydroprocessing in step F), at least a portion of the hydrogen needed, preferably all of the hydrogen needed, is provided by the hydrogen produced in step E).

[0138] According to another embodiment, the AtJ process of step F) comprises the substeps

[0139] F1) subjecting the bio-alcohol in the product stream, preferably selected from the group consisting of bio-ethanol, bio-n-butanol, and bio-iso-butanol, to a dehydration to obtain an olefin, preferably selected from the group consisting of ethylene, 1 -butene, 2-butene, and iso-butene;

[0140] F2) subjecting said olefin to an oligomerization to obtain oligomerized intermediates;

[0141] F3) subjecting said oligomerized intermediates to catalytic hydroprocessing to obtain renewable hydrocarbons; and optionally

[0142] F4) subjecting said renewable hydrocarbons to fractionation to obtain at least one fraction comprising renewable diesel, renewable jet fuel, bio-naphtha, and / or bio-Ci-4-HC (like propane).

[0143] According to another embodiment, the renewable hydrocarbons obtained in step F) comprise one or more of renewable diesel, renewable jet fuel, bio-naphtha, and / or bio-Ci-4-HC (like propane) fractions, preferably they comprise a bio-naphtha fraction.

[0144] According to another embodiment, step F) comprises hydroisomerization to obtain renewable hydrocarbons.

[0145] According to another embodiment, step F) comprises hydrocracking to obtain renewable hydrocarbons.Further process steps

[0146] The process according to the invention may comprise further optional steps where needed or advisable to improve the overall performance of the process. In particular, purification and separation steps may be applied to the product and / or by-product streams, e.g., in step B), and / or to any downstream process intermediates or products thereof, to improve their properties or to meet certain specifications.

[0147] Also, the products of step F) may be separated into different value products according to established fractionation techniques, especially to obtain separated renewable diesel, renewable jet fuel, bio-naphtha, and / or bio-Ci-4-HC (like propane) fractions.

[0148] Furthermore, an isomerization and / or cracking step of the obtained renewable hydrocarbons may be included in step F) to shift the relative yields of the different fractions in a desired way and / or to improve their properties and performances (e.g., at low temperatures) during further use, e.g., as fuels, fuel blendstocks, or as chemical feedstocks. Isomerization may, for example, be carried out as hydroisomerization and / or catalytic isomerization of the bio-naphtha fraction, with or without prior separation, to convert n-paraffins to iso-paraffins. Cracking may, for example, be carried out as hydrocracking and / or catalytic cracking of renewable diesel and / or renewable jet fuel fractions, with or without prior separation, e.g., to increase the yield of bio-naphtha and / or bio-Ci.4-HC (like propane) fractions and to decrease the yields of renewable diesel and SAF fractions.

[0149] In addition, the products of said separation, e.g., the bio-naphtha fraction, and of said optional isomerization step may be further utilized in refinery or petrochemical processes, for instance as a blend stock for fuel blending or as a feedstock for steam cracking. Fuel blending is common to improve the characteristics of fuels, e.g., to optimize vapor pressure, octane number, boiling point, viscosity, sulfur content, color, stability, aromatics or olefin content. Steam cracking is the most important industrial process for producing lighter olefins, e.g., from naphtha.

[0150] Thus, according to one embodiment, the process according to the invention optionally comprises one or more of the following steps:

[0151] G) separating the renewable hydrocarbons into different fractions, preferably to obtain at least a separate bio-naph- tha fraction, at least a separate renewable diesel fraction, or at least a separate renewable jet fuel fraction; H) subjecting the renewable hydrocarbons, preferably the bio-naphtha fraction, to isomerization, preferably to form iso-paraffins or

[0152] subjecting the renewable hydrocarbons, preferably the renewable diesel fraction and / or the renewable jet fuel fraction to cracking, preferably to increase the yield of bio-naphtha; and / or

[0153] J) blending the bio-naphtha fraction of the renewable hydrocarbons with at least one fuel, e.g., with gasoline, to obtain a fuel blend with improved characteristics,

[0154] or

[0155] subjecting the bio-naphtha fraction of the renewable hydrocarbons to steam cracking to obtain olefins.

[0156] Step K)

[0157] The process according to the invention may also comprise a step of controlling hydrogen production, in terms of both sufficient amounts and desired attributes:The controlling of the hydrogen production includes the determination of the hydrogen amount needed, i.e. , the hydrogen demand, for the catalytic hydroprocessing of step F). This demand of course depends on the amount, type, composition, and properties (e.g., the degree of saturation, level of impurities) of the product stream used as well as on the type and goals of the hydroprocessing reaction, i.e., to which degree hydrogenation, hydrocracking, and hydroisomerization of the product stream are to be achieved. Determining the hydrogen demand includes establishing a reasonable amount of excess hydrogen for the catalytic hydroprocessing and taking into account hydrogen amounts that may be recovered after the hydroprocessing step. The term “determination” and the like as used herein refers to the process of reaching a conclusion or result and may encompass means and steps suitable for that purpose, in particular to gather information, including by way of measurements, analysis, research, or investigation, and to use technical considerations and logical reasoning, including process knowledge, mathematical calculations, and computer-aided approaches like simulations and predictions. The one of skill in the art will be aware of such methods and considerations to successfully perform the determination steps described herein. The determination of hydrogen demands and obtainable hydrogen amounts may refer to different time periods, e.g., to an hourly, daily, weekly, or monthly basis.

[0158] The controlling of the hydrogen production further includes the determination of the amount of hydrogen obtainable from step E), which depends on the amount, type, composition, and properties of the by-product stream used as well as on the process conditions applied in step E).

[0159] Thus, the controlling of the hydrogen production includes the determination of the amounts and compositions of the feedstocks available for the hydrogen production of step E), especially the amounts and compositions of the biogas feedstocks for step C), i.e., of the by-product stream as well as of the further biogas feedstocks, of the biogas obtained from steps C) and D), and of other hydrocarbons for hydrogen production, e.g., as obtained from step F). Again, these amounts and compositions will depend on the amounts, types, compositions, and properties of the used product and by-product streams, respectively, as well as on the process conditions applied in steps C), D), and F). Also, these amounts and compositions will depend on the desired output of the different hydrocarbon fractions to be delivered from step F). On the basis of this information and the process knowledge of the hydrogen production techniques, the one of skill in the art will be able to predict and thus to determine with reasonable accuracy the amounts of hydrogen that are obtainable and are to be expected from the hydrogen production according to step E).

[0160] Controlling the hydrogen production is intended to meet the hydrogen demand of step F) and to ensure a continuous and sufficient hydrogen supply to step F). Thus, said controlling includes the controlling of the supply means to provide biogas feedstock to step C) and (upgraded) biogas and / or hydrocarbons to hydrogen production of step E). Controlling supply means may include controlling volumes, flow rates, and the like. Also said controlling includes controlling the hydrogen production of step E) and the hydroprocessing process of step F), e.g., by controlling their process parameters and conditions.

[0161] Controlling the hydrogen production may also be intended to adjust or modify attributes of the products of steps F) or J) and any downstream products obtained therefrom. In particular, these attributes may be sustainability attributes like product carbon footprint, carbon intensity, greenhouse gas emissions, sustainability certifications, renewable content, biobased or biogenic content, recycling content, fossil-based content, energy sources used, energy efficiency, and the like. Controlling the hydrogen production allows for such attribute adjustment or modification due to the potentially different origins of the hydrogen employed, e.g., the feedstock from which it is obtained, the pathway according to which it isproduced, or the energy which is used for its production. For instance, said controlling may accordingly be used to minimize the product-carbon footprint or the fossil-based content of products of steps F) or J) or downstream products obtained therefrom or to optimize their renewable content or energy efficiency. Thus, said controlling may include the assignment of qualitative and / or quantitative attributes, in particular sustainability attributes, to the hydrogen production input streams. On this basis, the volumes of the different hydrogen production input streams may be varied and adjusted to obtain a hydrogen stream with desired qualitative and / or quantitative attributes that is then provided to step F). Thus, products of steps F) or J) and downstream products with pre-defined desired attributes may be produced.

[0162] Of note, computer-aided methods and applications may be used to achieve the above-mentioned objectives by allowing for a straightforward, precise, and rapid controlling of the hydrogen production as described hereinbefore.

[0163] Thus, according to one embodiment, the process according to the invention further comprises step K)

[0164] K) controlling the hydrogen production.

[0165] According to another embodiment, step K) comprises the substeps

[0166] K1) determining the hydrogen demand of step F) (H-dem);

[0167] K2) determining the amount of hydrogen obtainable from step E) carried out with biogas derived from said by-product stream via step C) and optional step D) (H-obt1) and

[0168] determining the amount of hydrogen obtainable from step E) carried out with biogas obtained from further biogas feedstocks via step C) and optional step D) H-obt2) and

[0169] determining the amount of hydrogen obtainable from step E) carried out with said hydrocarbons obtained from step F) (H-obt3)', and

[0170] K3) controlling supply means for providing said biogas from steps C) and optional step D) to step E) and controlling supply means for providing said hydrocarbons from step F) to step E),

[0171] such that a total amount of hydrogen is provided by step E) that is sufficient to meet the hydrogen demand of step F) as determined in substep K1) and preferably such that the amount of said hydrocarbons from step F) used in step E) is minimized.

[0172] According to another embodiment, step K) comprises the substeps

[0173] K1 a) determining the hydrogen demand of step F) H-dem) and defining at least one qualitative and / or quantitative attribute that said hydrogen should fulfill;

[0174] K2a) determining the amount of hydrogen obtainable from step E) carried out with biogas derived from said byproduct stream via step C) and optional step D) (H-obt1) and

[0175] determining the amount of hydrogen obtainable from step E) carried out with biogas obtained from further biogas feedstocks via step C) and optional step D) H-obt2) and

[0176] determining the amount of hydrogen obtainable from step E) carried out with said hydrocarbons obtained from step F) H-obt3 );

[0177] and assigning at least one qualitative and / or quantitative attribute to said amounts of hydrogen from each of said sources; and

[0178] K3a) controlling supply means for providing said biogas from steps C) and optional step D) to step E) and controlling supply means for providing said hydrocarbons from step F) to step E),such that a total amount of hydrogen is provided by step E) that is sufficient to meet the hydrogen demand of step F) as determined in substep K1a) and that fulfills the at least one qualitative and / or quantitative attribute as defined in substep K1a)

[0179] and preferably such that the amount of said hydrocarbons from step F) used in step E) is minimized.

[0180] According to another embodiment, step K3) and step K3a), respectively, comprise the substeps of

[0181] determining the difference H-diff = (H-obt1 + H-obt2) - (H-dem) and

[0182] if H-diff 0, controlling the supply means for providing said hydrocarbons from step F) to step E) such that no hydrocarbons from step F) are passed to step E), and

[0183] if H-diff < 0, controlling the supply means such that hydrocarbons from step F) are passed to step E) such that H-obt3 > -(H-diff).

[0184] Of note, whenever used hereinbefore or hereinafter, the terms “comprise(s)”, “comprising” etc. are inclusive of and may, in a preferred embodiment, be replaced by the terms “consist(s) of”, “consisting of’ etc.

[0185] Further embodiments of the first aspect of the invention are described by the combination of any and each of the above definitions and embodiments with one another, in particular by way of FIGs 1-6.

[0186] FIG 1 depicts a process for the co-production of renewable diesel (7), SAF (8), bio-naphtha (9), and bio-Ci-4-HCs (10) along with (upgraded) biogas (3, 4) from biomass (1) and hydrogen (5). The initial step is the conversion (11) of biomass (1) into a bio-alcohol (6) and biomass residues and biomass waste (2). Said biomass residues and biomass waste (2) undergo anaerobic digestion (12) to form biogas (3) which is optionally further upgraded to upgraded biogas (4). The bio-alcohol (6) is dehydrated (11b) to an olefin (6b) and oligomerized (11c) to oligomeric intermediates (6c), subjected to hydroprocessing (15) in the presence of hydrogen (5) and the obtained products are separated (16) to yield fractions like renewable diesel (7), SAF (8), bio-naphtha (9), and bio-Ci-4-HCs (10).

[0187] FIG 2 depicts a process for the co-production of renewable diesel (7), SAF (8) along with (upgraded) biogas (3, 4) from biomass (1). The process of FIG 2 differs from the one depicted in FIG 1 by the fact that bio-naphtha (9) and / or bio-Ci-4-HCs (10) are used as feedstocks for hydrogen production (14) to produce hydrogen (5) needed for hydroprocessing (15). Of note, FIG 2 is intended to include the case that not all of the bio-naphtha (9) and / or not all of the bio-Ci-4-HCs (10), but only portions thereof are used for hydrogen production (14). Likewise, FIG 2 is intended to include the case that not all the hydrogen (5) needed for hydroprocessing (15) originates from bio-naphtha (9) and / or bio-Ci-4-HCs (10), but a portion thereof may originate from other sources.

[0188] FIG 3 depicts a process for the co-production of renewable diesel (7), SAF (8), and bio-naphtha (9) from biomass (1). The process of FIG 3 differs from the one depicted in FIG 1 by the fact that bio-Ci-4-HCs (10) and upgraded biogas (4) are used as feedstocks for hydrogen production (14) to produce hydrogen (5) needed for hydroprocessing (15). Of note, FIG 3 is intended to include the cases that not all of the bio-Ci-4-HCs (10) and / or not all the upgraded biogas (4), but only portions thereof are used for hydrogen production (14). Likewise, FIG 3 is intended to include the case that not all the hydrogen (5) needed for hydroprocessing (15) originates from bio-Ci-4-HCs (10) and / or upgraded biogas (4), but a portion thereof may originate from other sources. It is also contemplated that the biogas upgrading step (13) is optional such that biogas (3) may be used as a hydrogen production (14) feedstock in addition to or instead of upgraded biogas (4).FIG 4 depicts a process for the co-production of renewable diesel (7), SAF (8), and bio-naphtha (9) from biomass (1) and further biogas feedstock (17). The process of FIG 4 differs from the one depicted in FIG 3 by the fact that, along with biomass residues and biomass waste (2), further biogas feedstock (17) is used for anaerobic digestion (12) to produce biogas (3).

[0189] FIG 5 depicts a process for the co-production of renewable diesel (7), SAF (8), bio-naphtha (9), and bio-Ci-4-HCs (10) from biomass (1). The process of FIG 5 differs from the one depicted in FIG 1 by the fact that upgraded biogas (4) is used as a feedstock for hydrogen production (14) to produce hydrogen (5) needed for hydroprocessing (15). Of note, FIG 5 is intended to include the case that not all the upgraded biogas (4), but only portions thereof are used for hydrogen production (14). Likewise, FIG 5 is intended to include the case that not all the hydrogen (5) needed for hydroprocessing (15) originates from upgraded biogas (4), but a portion thereof may originate from other sources. It is also contemplated that the biogas upgrading step (13) is optional such that biogas (3) may be used as a hydrogen production (14) feedstock in addition to or instead of upgraded biogas (4).

[0190] FIG 6 depicts a process for the co-production of renewable diesel (7), SAF (8), bio-naphtha (9), and bio-Ci-4-HCs (10) from biomass (1). The process of FIG 6 differs from the one depicted in FIG 5 by the fact that, along with biomass residues and biomass waste (2), further biogas feedstock (17) is used for anaerobic digestion (12) to produce biogas (3).

[0191] Thus, in a second aspect, the present invention provides a system for producing renewable hydrocarbons from biomass according to the processes described herein, the system comprising

[0192] I) a biomass conversion unit for receiving biomass and processing said biomass into a product stream and into at least one by-product stream;

[0193] II) a biogas plant, connected and arranged downstream to unit I), for receiving at least one by-product stream from unit I), for producing biogas from said at least one by-product stream via anaerobic digestion, and optionally for upgrading said biogas to upgraded biogas;

[0194] III) a hydrogen production unit, connected and arranged downstream to unit II), for receiving said optionally upgraded biogas from unit II) and for producing hydrogen from said optionally upgraded biogas; and

[0195] IV) an alcohol-to-jet unit, connected and arranged downstream to units I) and III), for receiving said product stream from unit I) and said hydrogen from unit III) and for producing renewable hydrocarbons from said product stream and said hydrogen.

[0196] Unit I)

[0197] The biomass conversion unit is fed with biomass as described hereinbefore. It is equipped to process said biomass as described for step B) above, including its different embodiments.

[0198] Thus, according to one embodiment, the biomass conversion unit is equipped to carry out pretreatment, preferably comprising one or more of mechanical operations, physical operations, thermal treatments, thermochemical treatments, chemical processes, and biological methods, optionally also the separation of the obtained products and by-products.

[0199] According to another embodiment, the biomass conversion unit is equipped to yield a product stream comprising, preferably consisting of bio-alcohol.According to another embodiment, the biomass conversion unit is equipped to yield at least one by-product stream comprising biomass residues and / or biomass waste, preferably selected from the group consisting of lignin, hemicellulose hydrolysates, vinasse, and DDGS.

[0200] According to another embodiment, the biomass conversion unit is equipped to apply purification steps to the product stream and / or to the at least one by-product stream.

[0201] Unit II)

[0202] The biogas plant may be fed with at least one by-product stream from unit I); also, it may be fed with other feedstocks for biogas production, as described hereinbefore, as well as with admixtures of said by-product streams and other feedstocks. The biogas plant is equipped to produce biogas from said at least one by-product stream as described for step C) above, including its different embodiments, and is optionally equipped to upgrade said biogas to upgraded biogas, as described for step D) above, including its different embodiments.

[0203] Thus, according to one embodiment, the biogas plant comprises a biomass pretreatment unit.

[0204] According to another embodiment, the biogas plant is equipped to perform anaerobic digestion of said at least one byproduct stream as dry and / or wet digestion, preferably as dry digestion.

[0205] According to another embodiment, the biogas plant comprises a biodigester, a landfill, and / or a wastewater treatment plant, preferably a biodigester, to perform the anaerobic digestion of said at least one by-product stream.

[0206] According to another embodiment, the biogas plant comprises the subunits IIA) and IIB):

[0207] IIA) mixing unit, connected and arranged downstream to unit I), for receiving at least one by-product stream from unit I) and for mixing it with at least one feedstock for biogas production, preferably selected from agricultural and crop residues, animal manure, organic fractions of industrial and municipal solid waste, and wastewater sludge, more preferably selected from agricultural and crop residues and animal manure; and

[0208] IIB) anaerobic digestion unit, connected and arranged downstream to unit IIA), for receiving the feedstock mixture from unit IIA) and for subjecting said feedstock mixture to anaerobic digestion to obtain biogas.

[0209] According to another embodiment, the biogas plant is equipped to upgrade said biogas via water scrubbing and / or membrane separation techniques, especially to remove carbon dioxide from the biogas.

[0210] According to another embodiment, the biogas plant comprises a compression unit for compressing biogas and / or upgraded biogas.

[0211] Unit III)

[0212] The hydrogen production unit comprises, preferably consists of, a reforming unit and / or a pyrolysis unit. It may be fed with (optionally upgraded) biogas from unit II). It is equipped to perform hydrogen production, e.g., hydrocarbon reforming and / or hydrocarbon pyrolysis, as described for step E) above, including its different embodiments.

[0213] Also, the hydrogen production unit may be connected to unit IV), as described hereinbefore and hereinafter, such that it may be fed with hydrocarbons from unit IV) for reforming and / or pyrolysis. In this case, the terms “hydrocarbon reforming” and “hydrocarbon pyrolysis” as used herein, shall encompass not only methane reforming and methane pyrolysis, respectively, but also reforming and pyrolysis of hydrocarbons, e.g., from unit IV). Thus, in this case, unit III) is connected downstream to unit IV) in respect of the product stream (i.e. in respect of the hydrocarbon stream), while it is connected upstreamto unit IV) in respect of the by-product stream (i.e. in respect of the hydrogen stream); i.e., unit III) may provide hydrogen to unit IV) and may receive hydrocarbons from unit IV).

[0214] In this situation, where both (upgraded) biogas from unit II) and hydrocarbons from unit IV) may serve as feedstocks for the hydrogen production unit, unit III) may also comprise means like a control unit to adjust the flow rates of the (upgraded) biogas and hydrocarbon streams such that a continuous and sufficient feedstock supply of unit III) is ensured.

[0215] Thus, according to one embodiment, the hydrogen production unit comprises, preferably consists of, a reforming unit and / or a pyrolysis unit.

[0216] According to another embodiment, the hydrogen production unit comprises, preferably consists of, a reforming unit that is equipped to perform hydrocarbon reforming by steam reforming, partial oxidation, or autothermal reforming.

[0217] According to another embodiment, the hydrogen production unit comprises, preferably consists of, a pyrolysis unit that is equipped to perform hydrocarbon pyrolysis.

[0218] According to another embodiment, the hydrogen production unit comprises, preferably consists of, a reforming unit that comprises the subunits IIIA), IIIB), and IIIC):

[0219] IIIA) steam reforming unit or partial oxidation unit or autothermal reforming unit, connected and arranged downstream to unit II), for reforming hydrocarbons, preferably methane, to obtain a first gas stream comprising hydrogen, carbon monoxide, and carbon dioxide;

[0220] IIIB) water-gas shift unit, connected and arranged downstream to unit IIIA), for performing the water-gas shift reaction for the first gas stream from unit IIIA) to obtain a second gas stream comprising, preferably consisting essentially of, hydrogen and carbon dioxide; and

[0221] IIIC) purification unit, connected and arranged downstream to unit IIIB), for purifying the second gas stream from unit IIIB), preferably by pressure swing adsorption, to obtain a third gas stream consisting essentially of hydrogen. According to another embodiment, the hydrogen production unit comprises, preferably consists of, a pyrolysis unit that comprises the subunits HID), HIE), and IIIF):

[0222] HID) hydrocarbon decomposition unit, connected and arranged downstream to unit II), for decomposing methane to obtain a first gas stream comprising hydrogen;

[0223] HIE) solid processing unit, connected and arranged downstream to unit HID), for processing solid carbon, optionally comprising a carbon separation unit, a carbon post-treatment unit, and / or a carbon purification unit, to obtain a carbon stream comprising, preferably consisting essentially of, solid carbon; and

[0224] IIIF) purification unit, connected and arranged downstream to unit HID), for purifying the first gas stream from unit HID), preferably by pressure swing adsorption, to obtain a second gas stream consisting essentially of hydrogen. According to another embodiment, the unit III) is connected downstream to unit IV) in respect of the product stream and it is connected upstream to unit IV) in respect of the by-product stream.

[0225] According to another embodiment, when connected downstream to unit IV) in respect of the product stream, unit III) additionally comprises a control unit to adjust the flow rates of (upgraded) biogas from unit II) and hydrocarbons from unit IV), in particular to ensure continuous and sufficient feedstock supply.Unit IV)

[0226] TheAtJ unit is fed with the product stream from unit I) (or the purified bio-alcohol) and hydrogen from unit III). It is equipped to perform bio-alcohol dehydration, olefin oligomerization, and hydroprocessing of bio-alcohol-derived oligomeric intermediates, and further upgrading or refinery steps, as described for step F) above, including its different embodiments. In particular, it is equipped to perform substeps F1), F2), F3), and optionally F4) as described above.

[0227] Thus, according to one embodiment, the AtJ unit is equipped to perform an AtJ process, wherein at least a portion of the hydrogen produced from unit III), preferably essentially all of the hydrogen from unit III), is utilized for the hydroprocessing. According to another embodiment, the AtJ unit is equipped to perform an AtJ process, wherein at least a portion of the hydrogen needed, preferably all of the hydrogen needed for the hydroprocessing, is provided by the hydrogen from unit

[0228] According to another embodiment, the AtJ unit is equipped to perform bio-alcohol dehydration, olefin oligomerization, hydroprocessing of oligomeric intermediates, and optionally fractionation of the obtained renewable hydrocarbons. According to another embodiment, the AtJ unit is equipped to produce renewable hydrocarbons comprising renewable diesel, renewable jet fuel, bio-naphtha, and / or bio-Ci-4-HC (like propane) fractions, preferably comprising a bio-naphtha fraction.

[0229] According to another embodiment, the AtJ unit is equipped to further perform isomerization of the renewable hydrocarbons, preferably to form iso-paraffins.

[0230] Further units

[0231] The system according to the invention may comprise further units and sub-units, e.g., for performing the further process steps described above, like purification and separation of product and / or by-product streams and / or to any downstream process intermediates or products thereof, for instance, it may also comprise one or more fractionation and isomerization units.

[0232] Thus, according to one embodiment, the system according to the invention optionally comprises unit V):

[0233] V) fractionation unit, connected and arranged downstream to unit IV) for separating the renewable hydrocarbons into different fractions, preferably to obtain at least a separate bio-naphtha fraction.

[0234] Unit VI)

[0235] The system according to the invention may also comprise a hydrogen production control unit VI) that is equipped to interact with other units of the system and to carry out the controlling of the hydrogen production as described above for step K) and its different embodiments. In particular, the hydrogen production control unit VI) may adjust flow volumes and flow rates between the units of the system such that a continuous and sufficient hydrogen supply for the AtJ unit IV) is ensured and / or the hydrogen provided to unit IV) furthermore fulfills certain desired attributes. To this end, it may comprise computer systems to aid in a straightforward, precise, and rapid controlling of the hydrogen production as described for step K).

[0236] Thus, according to one embodiment, the system according to the invention further comprises the unit VI)

[0237] VI) a hydrogen production control unit for controlling the hydrogen production.

[0238] According to another embodiment, unit VI) is equipped to interact with units II), III), IV), and V).According to another embodiment, unit VI) is equipped

[0239] to determine the hydrogen demand of unit IV) (H-dem),

[0240] to determine the amounts of hydrogen obtainable from unit III) on the basis of biogas from unit II) obtained from said by-product stream H-obt1) and / or from further biogas feedstocks H-obt2) and on the basis of said hydrocarbons from unit IV) (H-obt3), and

[0241] to control supply means for providing said biogas from unit II) and said hydrocarbons from unit IV) to unit III), so that a total amount of hydrogen is provided that is sufficient to meet the hydrogen demand of unit IV) and preferably such that the amount of said hydrocarbons from unit IV) used in unit III) is minimized.

[0242] The term “being equipped to” as used herein means that a device, unit, or system has the necessary components, tools, mechanisms, features, or capabilities that enable it to carry out the specified operations, tasks, or functions and that it may be configured to do so.

[0243] Further embodiments of the second aspect of the invention are described by the combination of any and each of the above definitions and embodiments with one another, in particular by way of FIG 7.

[0244] FIG 7 depicts a system for performing the processes according to FIG 1-6. A biomass conversion unit (101) receives biomass (1) to produce bio-alcohol (6) and biomass residues and biomass waste (2). The latter (2) is fed into a biogas plant (102), which may receive further biogas feedstock (17), to produce (optionally upgraded) biogas (3, 4). The hydrogen production unit (103) may receive said (optionally upgraded) biogas (3, 4) or a part thereof to produce hydrogen (5); also, the hydrogen production unit (103) may receive bio-naphtha (9) or a part thereof and / or bio-Ci-4-HCs (10) or a part thereof as feedstocks. The AtJ unit (104) receives bio-alcohol (6) as well as hydrogen (5), either from an external source or from the hydrogen production unit (103), to produce and separate renewable diesel (7), SAF (8), bio-naphtha (9), and / or bio-CI-4-HCS (10).

[0245] Preferred Embodiments

[0246] 1. A process for producing renewable hydrocarbons from biomass, the process comprising the steps of

[0247] A) providing biomass;

[0248] B) processing said biomass into a product stream comprising at least one bio-alcohol and into at least one byproduct stream comprising biomass residues and / or biomass waste,

[0249] wherein said processing comprises a fermentation step;

[0250] C) subjecting said at least one by-product stream to anaerobic digestion to obtain biogas;

[0251] D) optionally upgrading said biogas to obtain upgraded biogas;

[0252] E) subjecting said biogas, optionally upgraded according to step D), to hydrogen production to obtain hydrogen;

[0253] and

[0254] F) subjecting the product stream to an alcohol-to-jet process including catalytic hydroprocessing to obtain renewable hydrocarbons,

[0255] wherein at least a portion of the hydrogen produced in step E) is utilized for said hydroprocessing.2. The process of claim 1, wherein in step A)

[0256] the biomass comprises or is derived from one or more of sugar crops, starch crops, energy crops, lignocellulosic biomass, agricultural residues, straw, forestry residues, and organic components of municipal solid waste.

[0257] 3. The process of one or more of claims 1-2,

[0258] wherein step C) is replaced by step Ca) comprising the substeps C1), C2a), and C3a):

[0259] C 1 ) providing at least one feedstock for biogas production, preferably selected from agricultural and crop residues, animal manure, organic fractions of industrial and municipal solid waste, and sewage or wastewater sludge, more preferably selected from agricultural and crop residues, e.g., from rice, and animal manure;

[0260] C2a) mixing said at least one by-product stream with said at least one feedstock for biogas production; and C3a) subjecting the feedstock mixture of C2a) to anaerobic digestion to obtain biogas

[0261] or

[0262] wherein step C) is replaced by step Cb) comprising the substeps C1), C2b), and C3b):

[0263] C1) providing at least one feedstock for biogas production, preferably selected from agricultural and crop residues, animal manure, organic fractions of industrial and municipal solid waste, and sewage or wastewater sludge, more preferably selected from agricultural and crop residues, e.g., from rice, and animal manure;

[0264] C2b) optionally mixing at least two of said at least one feedstocks for biogas production; and

[0265] C3b) subjecting the at least one feedstock provided in C1) and / or the feedstock mixture of C2b) to anaerobic digestion to obtain biogas.

[0266] 4. The process of one or more of claims 1-3, wherein in step C)

[0267] the anaerobic digestion is performed in a biodigester.

[0268] 5. The process of one or more of claims 1-4, wherein in step D)

[0269] the upgrading includes water scrubbing, amine gas treatment, pressure swing adsorption, and / or membrane separation techniques.

[0270] 6. The process of one or more of claims 1-5, wherein in step E)

[0271] hydrogen production is carried out by hydrocarbon reforming and comprises the substeps E1), E2), and E3)

[0272] E1) steam reforming to obtain a first gas stream comprising hydrogen, carbon monoxide, and carbon dioxide; E2) water-gas shift reaction of the first gas stream of E1) to obtain a second gas stream comprising hydrogen and carbon dioxide; and

[0273] E3) purification of the second gas stream of E2), preferably by pressure swing adsorption, to obtain a third gas stream consisting essentially of hydrogen; or

[0274] hydrogen production is carried out by hydrocarbon pyrolysis and comprises the substeps E4), E5), and E6):

[0275] E4) hydrocarbon decomposition to obtain a first gas stream comprising hydrogen;

[0276] E5) processing of solid carbon, optionally carbon separation, post-treatment, and / or carbon purification, to obtain a carbon stream comprising solid carbon; andE6) purification of the first gas stream of E4), preferably by pressure swing adsorption, to obtain a second gas stream consisting essentially of hydrogen.

[0277] 7. The process of one or more of claims 1-6, wherein in step F)

[0278] the alcohol-to-jet process comprises the substeps

[0279] F1) subjecting the bio-alcohol in the product stream, preferably selected from the group consisting of bio-ethanol, bio-n-butanol, and bio-iso-butanol, to a dehydration to obtain an olefin, preferably selected from the group consisting of ethylene, 1 -butene, 2-butene, and iso-butene;

[0280] F2) subjecting said olefin to an oligomerization to obtain oligomerized intermediates;

[0281] F3) subjecting said oligomerized intermediates to catalytic hydroprocessing to obtain renewable hydrocarbons; and optionally

[0282] F4) subjecting said renewable hydrocarbons to fractionation to obtain at least one fraction comprising renewable diesel, renewable jet fuel, bio-naphtha, and / or bio-Ci-4-HC (like propane).

[0283] 8. The process of one or more of claims 1-7, additionally comprising step G)

[0284] G) separating the renewable hydrocarbons into different fractions, preferably to obtain at least a separate naphtha fraction.

[0285] 9. The process of one or more of claims 1-8, additionally comprising step H)

[0286] H) subjecting the renewable hydrocarbons, preferably the naphtha fraction, to isomerization, preferably to form isoparaffins.

[0287] 10. The process of one or more of claims 1-9, additionally comprising step J)

[0288] J) blending the naphtha fraction of the renewable hydrocarbons with at least one fuel, e.g., with gasoline, to obtain a fuel blend with improved characteristics,

[0289] or

[0290] subjecting the naphtha fraction of the renewable hydrocarbons to steam cracking to obtain olefins.

[0291] 11. The process of one or more of claims 1-10, the process further comprising step K)

[0292] K) controlling the hydrogen production.

[0293] and wherein preferably step K) comprises the substeps

[0294] K1) determining the hydrogen demand of step F) (H-dem);

[0295] K2) determining the amount of hydrogen obtainable from step E) carried out with biogas derived from said by-product stream via step C) and optional step D) (H-obt1) and

[0296] determining the amount of hydrogen obtainable from step E) carried out with biogas obtained from said further biogas feedstocks via step C) and optional step D) H-obt2) and

[0297] determining the amount of hydrogen obtainable from step E) carried out with said hydrocarbons obtained from step F) (H-obt3)', andK3) controlling supply means for providing said biogas from steps C) and optional step D) to step E) and controlling supply means for providing said hydrocarbons from step F) to step E),

[0298] such that a total amount of hydrogen is provided by step E) that is sufficient to meet the hydrogen demand of step F) as determined in substep K1) and preferably such that the amount of said hydrocarbons from step F) used in step E) is minimized,

[0299] wherein preferably step K3) further comprises the substeps of

[0300] determining the difference H-diff = (H-obt1 + H-obt2) - (H-dem) and

[0301] if H-diff 0, controlling the supply means for providing said hydrocarbons from step F) to step E) such that no hydrocarbons from step F) are passed to step E), and

[0302] if H-diff < 0, controlling the supply means such that hydrocarbons from step F) are passed to step E) such that H-obt3 > -(H-diff).

[0303] 12. A system for producing renewable hydrocarbons from biomass according to the processes described herein, the system comprising

[0304] I) a biomass conversion unit for receiving biomass and processing said biomass into a product stream and into at least one by-product stream;

[0305] II) a biogas plant, connected and arranged downstream to unit I), for receiving at least one by-product stream from unit I), for producing biogas from said at least one by-product stream via anaerobic digestion, and optionally for upgrading said biogas to upgraded biogas;

[0306] III) a hydrogen production unit, connected and arranged downstream to unit II), for receiving said optionally upgraded biogas, from unit II) and for producing hydrogen from said optionally upgraded biogas; and

[0307] IV) an alcohol-to-jet unit, connected and arranged downstream to units I) and III), for receiving said product stream from unit I) and said hydrogen from unit III) and for producing renewable hydrocarbons from said product stream and said hydrogen.

[0308] 13. The system according to claim 12, wherein the biogas plant comprises the subunits IIA) and I IB)

[0309] IIA) mixing unit, connected and arranged downstream to unit I), for receiving at least one by-product stream from unit I) and for mixing it with at least one feedstock for biogas production, preferably selected from agricultural and crop residues and animal manure; and

[0310] IIB) anaerobic digestion unit, connected and arranged downstream to unit IIA), for receiving the feedstock mixture from unit IIA) and for subjecting said feedstock mixture to anaerobic digestion to obtain biogas.

[0311] 14. The system according to one or more of claims 12-13, wherein the hydrogen production unit comprises, preferably consists of, a reforming unit that comprises the subunits II I A), 111 B), and II IC):

[0312] IIIA) steam reforming unit or partial oxidation unit or autothermal reforming unit, connected and arranged downstream to unit II), for reforming hydrocarbons, preferably methane, to obtain a first gas stream comprising hydrogen, carbon monoxide, and carbon dioxide;IIIB) water-gas shift unit, connected and arranged downstream to unit IIIA), for performing the water-gas shift reaction for the first gas stream from unit IIIA) to obtain a second gas stream comprising hydrogen and carbon dioxide; and

[0313] IIIC) purification unit, connected and arranged downstream to unit IIIB), for purifying the second gas stream from unit IIIB), preferably by pressure swing adsorption, to obtain a third gas stream consisting essentially of hydrogen; or

[0314] wherein the hydrogen production unit comprises, preferably consists of, a pyrolysis unit that comprises the subunits HID), HIE), and IIIF):

[0315] HID) hydrocarbon decomposition unit, connected and arranged downstream to unit II), for decomposing methane to obtain a first gas stream comprising hydrogen;

[0316] HIE) solid processing unit, connected and arranged downstream to unit HID), for processing solid carbon, optionally comprising a carbon separation unit, carbon post-treatment unit, and / or a carbon purification unit, to obtain a carbon stream comprising, preferably consisting essentially of, solid carbon; and

[0317] IIIF) purification unit, connected and arranged downstream to unit HID), for purifying the first gas stream from unit HID), preferably by pressure swing adsorption, to obtain a second gas stream consisting essentially of hydrogen.

[0318] 15. The system according to one or more of claims 12-14, additionally comprising unitV):

[0319] V) fractionation unit, connected and arranged downstream to unit IV) for separating the renewable hydrocarbons into different fractions, preferably to obtain at least a separate naphtha fraction.

Claims

29Claims1. A process for producing renewable hydrocarbons from biomass, the process comprising the steps ofA) providing biomass;B) processing said biomass into a product stream comprising at least one bio-alcohol selected from the group consisting of bio-ethanol, bio-n-butanol, and bio-iso-butanol and into at least one by-product stream comprising biomass residues and / or biomass waste,wherein said processing comprises a fermentation step;C) subjecting said at least one by-product stream to anaerobic digestion to obtain biogas;D) optionally upgrading said biogas to obtain upgraded biogas;E) subjecting said biogas, optionally upgraded according to step D), to hydrogen production to obtain hydrogen;andF) subjecting the product stream to an alcohol-to-jet process including catalytic hydroprocessing to obtain renewable hydrocarbons,wherein at least a portion of the hydrogen produced in step E) is utilized for said hydroprocessing.

2. The process of claim 1, wherein in step A)the biomass comprises or is derived from one or more of sugar crops, starch crops, energy crops, lignocellulosic biomass, agricultural residues, straw, forestry residues, and organic components of municipal solid waste.

3. The process of one or more of claims 1-2,wherein step C) comprises the substeps C1), C2a), and C3a):C 1 ) providing at least one feedstock for biogas production, preferably selected from agricultural and crop residues, animal manure, organic fractions of industrial and municipal solid waste, and sewage or wastewater sludge, more preferably selected from agricultural and crop residues, e.g., from rice, and animal manure;C2a) mixing said at least one by-product stream with said at least one feedstock for biogas production; and C3a) subjecting the feedstock mixture of C2a) to anaerobic digestion to obtain biogas.

4. The process of one or more of claims 1-3, wherein in step D)the upgrading includes water scrubbing, amine gas treatment, pressure swing adsorption, and / or membrane separation techniques.

5. The process of one or more of claims 1-4, wherein in step E)said hydrogen production is carried out by hydrocarbon reforming and comprises the substeps E1), E2), and E3) E1) steam reforming to obtain a first gas stream comprising hydrogen, carbon monoxide, and carbon dioxide; E2) water-gas shift reaction of the first gas stream of E1) to obtain a second gas stream comprising hydrogen and carbon dioxide; and30E3) purification of the second gas stream of E2), preferably by pressure swing adsorption, to obtain a third gas stream consisting essentially of hydrogen.

6. The process of one or more of claims 1-4, wherein in step E)said hydrogen production is carried out by hydrocarbon pyrolysis and comprises the substeps E4), E5), and E6):E4) hydrocarbon decomposition to obtain a first gas stream comprising hydrogen;E5) processing of solid carbon, optionally carbon separation, post-treatment, and / or carbon purification, to obtain a carbon stream comprising solid carbon; andE6) purification of the first gas stream of E4), preferably by pressure swing adsorption, to obtain a second gas stream consisting essentially of hydrogen.

7. The process of one or more of claims 1-6, wherein in step F)the alcohol-to-jet process comprises the substepsF1) subjecting the bio-alcohol in the product stream, preferably selected from the group consisting of bio-ethanol, bio-n-butanol, and bio-iso-butanol, to a dehydration to obtain an olefin, preferably selected from the group consisting of ethylene, 1 -butene, 2-butene, and iso-butene;F2) subjecting said olefin to an oligomerization to obtain oligomerized intermediates;F3) subjecting said oligomerized intermediates to catalytic hydroprocessing to obtain renewable hydrocarbons; and optionallyF4) subjecting said renewable hydrocarbons to fractionation to obtain at least one fraction comprising renewable diesel, renewable jet fuel, bio-naphtha, and / or bio-Ci-4-HC.

8. The process of one or more of claims 1-7, additionally comprising step G)G) separating the renewable hydrocarbons into different fractions, preferably to obtain at least a separate bionaphtha fraction.

9. The process of one or more of claims 1-8, additionally comprising step H)H) subjecting the renewable hydrocarbons, preferably a bio-naphtha fraction thereof, to isomerization, preferably to form iso-paraffins.

10. The process of one or more of claims 7-9, additionally comprising step J)J) blending the bio-naphtha fraction of the renewable hydrocarbons with at least one fuel, e.g., with gasoline, to obtain a fuel blend with improved characteristics,orsubjecting the bio-naphtha fraction of the renewable hydrocarbons to steam cracking to obtain olefins.

11. The process of one or more of claims 1-10, the process further comprising step K)K) controlling the hydrogen production.and wherein step K) comprises the substepsK1) determining the hydrogen demand of step F) (H-dem);K2) determining the amount of hydrogen obtainable from step E) carried out with biogas derived from said by-product stream via step C) and optional step D) (H-obt1) anddetermining the amount of hydrogen obtainable from step E) carried out with biogas obtained from further biogas feedstocks via step C) and optional step D) H-obt2) anddetermining the amount of hydrogen obtainable from step E) carried out with said hydrocarbons obtained from step F) (H-obt3)', andK3) controlling supply means for providing said biogas from steps C) and optional step D) to step E) and controlling supply means for providing said hydrocarbons from step F) to step E),such that a total amount of hydrogen is provided by step E) that is sufficient to meet the hydrogen demand of step F) as determined in substep K1) and preferably such that the amount of said hydrocarbons from step F) used in step E) is minimized,wherein preferably step K3) further comprises the substeps ofdetermining the difference H-diff = (H-obt1 + H-obt2) - (H-dem) andif H-diff 0, controlling the supply means for providing said hydrocarbons from step F) to step E) such that no hydrocarbons from step F) are passed to step E), andif H-diff < 0, controlling the supply means such that hydrocarbons from step F) are passed to step E) such that H-obt3 > -(H-diff).

12. A system for producing renewable hydrocarbons from biomass according to the processes described herein, the system comprisingI) a biomass conversion unit for receiving biomass and processing said biomass into a product stream and into at least one by-product stream;II) a biogas plant, connected and arranged downstream to unit I), for receiving at least one by-product stream from unit I), for producing biogas from said at least one by-product stream via anaerobic digestion, and optionally for upgrading said biogas to upgraded biogas;III) a hydrogen production unit, connected and arranged downstream to unit II), for receiving said optionally upgraded biogas, from unit II) and for producing hydrogen from said optionally upgraded biogas; andIV) an alcohol-to-jet unit, connected and arranged downstream to units I) and III), for receiving said product stream from unit I) and said hydrogen from unit III) and for producing renewable hydrocarbons from said product stream and said hydrogen.

13. The system according to claim 12, wherein the biogas plant comprises the subunits IIA) and I IB)IIA) mixing unit, connected and arranged downstream to unit I), for receiving at least one by-product stream from unit I) and for mixing it with at least one feedstock for biogas production, preferably selected from agricultural and crop residues and animal manure; andIIB) anaerobic digestion unit, connected and arranged downstream to unit IIA), for receiving the feedstock mixture from unit IIA) and for subjecting said feedstock mixture to anaerobic digestion to obtain biogas.

14. The system according to one or more of claims 12-13, wherein the hydrogen production unit comprises, preferably consists of, a reforming unit that comprises the subunits 111 A), 111 B), and IIIC):IIIA) steam reforming unit or partial oxidation unit or autothermal reforming unit, connected and arranged downstream to unit II), for reforming hydrocarbons, preferably methane, to obtain a first gas stream comprising hydrogen, carbon monoxide, and carbon dioxide;IIIB) water-gas shift unit, connected and arranged downstream to unit IIIA), for performing the water-gas shift reaction for the first gas stream from unit IIIA) to obtain a second gas stream comprising hydrogen and carbon dioxide; andIIIC) purification unit, connected and arranged downstream to unit IIIB), for purifying the second gas stream from unit IIIB), preferably by pressure swing adsorption, to obtain a third gas stream consisting essentially of hydrogen; orwherein the hydrogen production unit comprises, preferably consists of, a pyrolysis unit that comprises the subunits HID), HIE), and IIIF):HID) hydrocarbon decomposition unit, connected and arranged downstream to unit II), for decomposing methane to obtain a first gas stream comprising hydrogen;HIE) solid processing unit, connected and arranged downstream to unit HID), for processing solid carbon, optionally comprising a carbon separation unit, carbon post-treatment unit, and / or a carbon purification unit, to obtain a carbon stream comprising, preferably consisting essentially of, solid carbon; andIIIF) purification unit, connected and arranged downstream to unit HID), for purifying the first gas stream from unit HID), preferably by pressure swing adsorption, to obtain a second gas stream consisting essentially of hydrogen.

15. The system according to one or more of claims 12-14, additionally comprising unitV):V) fractionation unit, connected and arranged downstream to unit IV) for separating the renewable hydrocarbons into different fractions, preferably to obtain at least a separate bio-naphtha fraction.

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