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WO2025224042A1 - Procédé de fabrication de n-butanol ou de 2-éthylhexanol renouvelable - Google Patents

Procédé de fabrication de n-butanol ou de 2-éthylhexanol renouvelable

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Publication number
WO2025224042A1
WO2025224042A1 PCT/EP2025/060833 EP2025060833W WO2025224042A1 WO 2025224042 A1 WO2025224042 A1 WO 2025224042A1 EP 2025060833 W EP2025060833 W EP 2025060833W WO 2025224042 A1 WO2025224042 A1 WO 2025224042A1
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WO
WIPO (PCT)
Prior art keywords
gas stream
stream
propylene
renewably
sourced
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/060833
Other languages
English (en)
Inventor
Stefan WILLERSINN
Alois Kindler
Christian WEINEL
Daniel Keck
Thomas Mackewitz
Dieter RAHN
Johannes Lazaros Friedrich ELLER
Simon Wachter
Samantha Au GEE
Sebastian Pohl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2025224042A1 publication Critical patent/WO2025224042A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
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    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/466—Entrained flow processes
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0255—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a non-catalytic partial oxidation step
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    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
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    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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    • C01—INORGANIC CHEMISTRY
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    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
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    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0495—Composition of the impurity the impurity being water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
    • C—CHEMISTRY; METALLURGY
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    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/12—Heating the gasifier
    • C10J2300/123—Heating the gasifier by electromagnetic waves, e.g. microwaves
    • C10J2300/1238—Heating the gasifier by electromagnetic waves, e.g. microwaves by plasma
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1846—Partial oxidation, i.e. injection of air or oxygen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/463—Gasification of granular or pulverulent flues in suspension in stationary fluidised beds
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/005—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
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    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]

Definitions

  • the different feedstocks for producing ethanol may be sucrose- containing feedstocks, e.g., sugarcane, starchy materials, e.g., corn, starch, wheat, cassava, lignocellulosic biomass, e.g., switchgrass, and/or agricultural waste.
  • sucrose- containing feedstocks e.g., sugarcane, starchy materials, e.g., corn, starch, wheat, cassava, lignocellulosic biomass, e.g., switchgrass, and/or agricultural waste.
  • the purification or isolation of bioethanol is frequently carried out by complicated, multistage distillation.
  • US 2008/0312485 discloses a method for continuously producing propylene by dehydrating ethanol obtained from biomass to obtain ethylene and reacting ethylene with n-butene in a metathesis reaction.
  • the n-butene is made by dimerization of ethylene which is obtained from biomass-derived ethanol.
  • WO 2010/066830 discloses the transformation of bioethanol to ethylene.
  • the bioethanol is produced by fermentation of carbohydrates or from synthesis gas made by gasification of biomass.
  • the ethylene is subsequently dimerized or oligomerized to, e.g., 1 -butene and/or 1-hexene.
  • the dimeric or oligomeric alphaolefins are transformed into internal olefins that are subsequently subjected to metathesis with ethylene.
  • WO 2011/085223 discloses an integrated process to prepare renewable hydrocarbons.
  • the process includes dehydrating renewable isobutanol to form a mixture of linear butenes and isobutene and dehydrating renewable ethanol to ethylene. Subsequently the butene mixture and the ethylene are reacted to form one or more renewable C3-C16 olefins.
  • Downstream conversion of propylene to alcohols generally comprises a hydroformylation step of propylene in the presence of syngas ("synthesis gas"), i.e., a mixture of hydrogen and carbon monoxide, as well as a hydrogenation step in the presence of hydrogen.
  • syngas i.e., a mixture of hydrogen and carbon monoxide
  • gasifier feedstock may be obtained from materials which cannot be efficiently recycled and would otherwise go to waste.
  • the invention seeks to advise a reaction scheme with a low carbon footprint that provide a renewably-sourced alcohol selected from n-butanol and n-hexanol derived from light olefins, such as ethylene and propylene, which at least partially replaces the light olefins output from a steam cracker
  • light olefins such as ethylene and propylene
  • the renewably-sourced light olefins can be blended or used interchangeably with a fossil -derived intermediate of the same chemical structure without necessitating adjustments in downstream processes.
  • the key advantage of the process according to the present invention is that it can be easily integrated into an existing production site in which one or more chemicals of interest are manufactured based on a fossil feedstock, in particular naphtha.
  • a fossil feedstock in particular naphtha.
  • fossil-based propylene can be partially substituted by renewably-sourced propylene.
  • syngas obtained from the gasification of gasifier feedstock is used without the need of adaptions to the existing production.
  • n-butanol or 2-ethylhexanol the carbon atoms of which are partially based on a renewable-sourced carbon (so-called "green” carbon).
  • the expressions "renewable” or “renewably-sourced'' in relation to a chemical compound are used synonymously and mean a chemical compound comprising a quantity of renewable carbon, i.e., having a reduced or no carbon content of fossil origin.
  • Renewable carbon entails all carbon sources that avoid or substitute the use of any additional fossil carbon from the geosphere.
  • Renewable carbon can come from the biosphere, atmosphere or technosphere - but not from the geosphere.
  • the expression “renewable” or “renewably-sourced” includes, in particular, biomass-derived chemical compounds. It also includes compounds derived from waste such as polymer residues, or from waste streams of chemical production processes.
  • the process of the invention envisages producing syngas from gasifier feedstock and allows for obtaining downstream products of propylene having a low product carbon footprint.
  • Reforming processes are often used to make synthesis gas (i.e., a gas mixture having predominant quantities of CO and H2) from natural gas or relatively low-boiling hydrocarbons.
  • the present invention involves gasification-based processes for the conversion of various feedstocks into synthesis gas.
  • the process comprises providing a gasifier feedstock; gasifying the gasifier feedstock by partial oxidation to form a raw product gas stream comprising a plurality of gases comprising methane, hydrogen and carbon monoxide; and recovering syngas from the raw product gas stream.
  • Gasification is a process by which either a solid, gaseous or liquid gasifier feedstock is reacted with an oxidant such as air, oxygen, and/or steam. Sufficient energy is provided to produce a raw product gas stream that may be laced with volatile and condensable organic compounds, e.g., tars.
  • the gasifier feedstock is gasified by partial oxidation. Partial oxidation is intended to produce as much CO as possible, with as little CO2 as possible.
  • a fraction of the feedstock may be burned in the process to provide heat and pressure. Carbon dioxide from the combustion may be co-mingled with the product gas.
  • gasification of the gasifier feedstock by partial oxidation forms a raw product gas stream comprising a plurality of gases comprising methane, hydrogen and carbon monoxide. This raw product gas stream is treated to recover syngas.
  • Synthesis gas or “syngas” refers to a gaseous mixture that is rich in CO and H2.
  • the gasifier feedstock is at least partially renewably-sourced.
  • the gasifier feedstock exhibits a heating value in the range of 15,000 to 45,000 J/g, preferably 20,000 to 40,000 J/g, more preferably 22,000 to 39,000 J/g, even more preferably 25,000 to 39,0000 J/g, most preferably 30,000 to 39,000 J/g, the heating value being measured in accordance with DIN 51900.
  • the sum of the amounts of carbon (C), hydrogen (H), oxygen (O), sulfur (S) and nitrogen (N) in the gasifier feedstock is in the range of from 70 to 100 wt.-%, more preferably of from 80 to 99.9 wt.-%, more preferably of from 90 to 99.5 wt.-%, more preferably of from 95 to 99.5 wt.-%, based on the weight of the gasifier feedstock.
  • the gasifier feedstock may comprise a liquid gasifier feedstock and/or a solid gasifier feedstock.
  • the gasifier feedstock may also comprise a gaseous feedstock, such as bio-natural gas
  • the amount of carbon (C), hydrogen (H), oxygen (O), sulfur (S) and nitrogen (N) is preferably:
  • H 1 to 15 wt.-%, more preferably 2 to 10 wt.-%;
  • S 0 to 5 wt.-%, more preferably 0.005 to 4 wt.-%; N: 0 to 5 wt.-%, more preferably 0.005 to 4 wt.-%, each based on the weight of the liquid gasifier feedstock.
  • the liquid gasifier feedstock may comprise one or more of a pyrolysis oil, which may be derived from end of life tires, solid biomass, municipal solid waste (MSW), and/or industrial waste; and a waste oil, a used oil, a bio-based oil, and/or a bio-based fat
  • the liquid gasifier feedstock comprises one or more of a pyrolysis oil derived from solid biomass, a bio-based oil and a bio-based fat.
  • solid biomass comprises wood, wood pellets, wood chips, straw, lignocellulosic biomass, energy crops, algae, and mixtures thereof.
  • solid biomass is selected from wood, wood pellets, wood chips, straw, and lignocellulosic biomass. More preferably, solid biomass is selected from wood, wood pellets, wood chips and straw.
  • the pyrolysis oil exhibits one or more of the following parameters: a final boiling point in the range of from 190 to 630 °C, as measured in accordance with ASTM D 86; a viscosity in the range of from 1 to 100 mPa s, as measured at 40 °C in accordance with DIN 53019; an ash content in the range of from 30 to 17000 mg/kg, as measured in accordance with ISO 6245.
  • the amount of carbon (C), hydrogen (H), oxygen (O), sulfur (S) and nitrogen (N) preferably:
  • H 1 to 15 wt.-%, more preferably 1.2 to 10 wt.-%;
  • O 0 to 25 wt.-% more preferably 1 .2 to 20 wt.-%;
  • the solid gasifier feedstock may comprise one or more of solid biomass, municipal solid waste (MSW), refuse-derived fuel (RDF), shredder residues such as car shredder residues (ASR), textiles, plastic waste and packaging waste.
  • MSW municipal solid waste
  • RDF refuse-derived fuel
  • shredder residues such as car shredder residues (ASR)
  • textiles plastic waste and packaging waste.
  • the solid gasifier feedstock comprises solid biomass.
  • the pre-treatment method for the gasifier feedstock is preferably selected from the group comprising drying, comminution, classification, sorting, agglomeration, thermochemical methods, and biological methods.
  • Suitable gasifiers comprise counter-current fixed bed reactors, co-current-fixed bed reactors, bubbling fluidized bed reactors, circulation fluidized bed reactors, and downdraft or updraft entrained flow reactors.
  • the selection of size and reactor type depends on several parameters, including the composition of the gasifier feedstock, demand of products, moisture content and availability of the gasifier feedstock.
  • the gasifier is an “oxygen blown” gasifier, i.e., oxygen is preferably used as the oxidant.
  • the gasification reaction in a gasifier is typically carried out at a temperature of greater than 400 °C, such as greater than 700 °C, in the presence of a sub-stoichiometric amount of an oxidant such as oxygen, air, steam, supercritical water, CO2, or a mixture of the aforementioned.
  • the gasification is carried out at a temperature in the range of greater than 700 to 1500 °C, more preferably, 850 to 1400 °C, even more preferably 1100 to 1500 °C.
  • the gasification is conducted at an absolute pressure of greater than 1 bar.
  • it is conducted at an absolute pressure in the range from 2 to 80 bar, more preferably 2 to 50 bar.
  • the gasifier feedstock comprises a liquid gasifier feedstock
  • gasifying the liquid gasifier feedstock comprises subjecting the liquid gasifier feedstock to partial oxidation in an entrained flow reactor to obtain the raw product gas stream.
  • the gasifier feedstock may further comprise a gaseous feedstock, such as bio-natural gas.
  • the entrained flow reactor is preferably operated at a temperature above 400 °C, such as 1000 to 2000 °C, more preferably 1250 to 1500 °C, and at a pressure of 1 bar(abs) or more, such as 5 to 200 bar(abs), preferably 10 to 100 bar(abs), more preferably 11 to 50 bar(abs).
  • gasifying the organic matter feedstock comprises introducing the liquid gasifier feedstock, oxygen, and optionally steam, into the entrained flow reactor being operated at a temperature above 400 °C and at a pressure of 1 bar(abs) or more, and bringing the liquid gasifier feedstock into contact with oxygen, and optionally the steam, in said reactor
  • the atomized liquid gasifier feedstock is gasified with oxygen in co-current flow.
  • the gasifier feedstock comprises a solid gasifier feedstock
  • gasifying the solid gasifier feedstock comprises subjecting the solid gasifier feedstock to partial oxidation in a fluidized bed reactor so as to obtain an intermediate gasification product, and directing the intermediate gasification product to gasification in an entrained flow reactor to obtain the raw product gas stream.
  • the gasifier feedstock may further comprise a gaseous feedstock, such as bio-natural gas.
  • the fluidized bed reactor is preferably operated at a temperature in the range of from 350 to 1000 °C, such as 600 to 1000 °C, and at a pressure in the range of from 1 to 200 bar(abs), such as 1 to 10 bar(abs), preferably 1.5 to 8 bar(abs), more preferably 2 to 5 bar(abs);and the entrained flow reactor is operated at a temperature above 400 °C and at a pressure of 1 bar(abs) or more, preferably at a temperature in the range of from 1000 to 1700 °C, such as 1100 to 1450 °C, and at a pressure in the range of from 1 to 200 bar(abs), such as 1 to 50 bar(abs), preferably 3 to 45 bar(abs), more preferably 8 to 40 bar(abs).
  • the process may additionally comprise directing a liquid gasifier feedstock into the entrained flow reactor.
  • gasifying the gasifier feedstock comprises partial oxidation in a plasma reactor.
  • the gasifier feedstock may be contacted in a plasma reactor with a stream comprising one or more of O2, CO2 and steam, and subjected to partial oxidation in the presence of a plasma.
  • the partial oxidation is preferably conducted at a temperature in the range from 1000 to 2000 °C, such as 1100 to 1450 °C, and a pressure of at least 1 bar(abs), such as 1.0 to 6 bar(abs), preferably 1.5 to 6 bar(abs), more preferably 1 .75 to 3 bar(abs).
  • the plasma is obtained by a process comprising generating plasma at at least one plasma torch comprised in the plasma reactor by applying an electric voltage in the range of from 0.5 to 70 MW, more preferably in the range of from 5 to 70 MW, more preferably in the range of from 20 to 60 MW.
  • Oxygen is the most common oxidant used for gasification because of its easy availability and low cost
  • the hydrogen to carbon monoxide molar ratio (“the molar ratio of H2 to CO") depends on the composition of the gasifier feedstock and the amount of steam used in the gasification.
  • the molar ratio of H2 to CO as required for the hydroformylation can for instance be adjusted by choosing an appropriate amount of steam in the gasification.
  • the syngas When steam acts as oxidant, the syngas has a higher molar ratio of H2 to CO than when air is used as oxidant.
  • a typical molar ratio of “air to combined feedstock” ranges from 0.3 to less than 1.
  • Typical impurities in the raw product gas stream obtained from the gasification reaction comprise chlorides, sulfur-containing organic compounds such as sulfur dioxide, trace heavy metals (e.g., as respective salts) and particulate residues.
  • Various chemical and/or physical methods for removal of such impurities from said raw syngas such as filtration, scrubbing, hydrotreatment and ab-/adsorption are known and can be chosen and adapted according to the type and respective concentration of the impurities in said raw syngas and the tolerance to such impurities in the successive process steps.
  • the gasification reaction usually results in further reaction products such as solid and/or highly viscous carbonaceous residues (e.g., char and/or tar) which can be further treated in separate steps not relevant for the systems and methods according to the present invention.
  • further reaction products such as solid and/or highly viscous carbonaceous residues (e.g., char and/or tar) which can be further treated in separate steps not relevant for the systems and methods according to the present invention.
  • Bulk particulate impurities can be removed from the raw syngas by a cyclone and/or filters, fine particles, and chlorides by wet scrubbing, trace heavy metals, catalytic hydrolysis for converting sulfur-containing organic compounds to H2S and acid gas removal for extracting sulfur-containing gases such as H2S.
  • Bulky and fine particles in the syngas may also be removed with a quench in a soot water washing unit.
  • recovering syngas from the raw product gas stream comprises subjecting the raw product gas stream to a washing step to remove particulate solids and to a drying step to remove water.
  • recovering syngas from the raw product gas stream further comprises sweetening the raw product gas stream (removing acid gases such as carbon dioxide and hydrogen sulfide) to form a sweetened product gas stream.
  • the raw product gas stream is subjected to a first purification stage, whereby a purified product gas stream is obtained, the purified product gas stream comprising CO, H2 and CH4 and being depleted in CO2, H2O and solid particles
  • the first purification stage comprises: a') subjecting the raw product gas stream obtained to a washing step in a washing unit, more preferably the washing unit being a column having a spray nozzle or an atomizer located at the top of the column, obtaining a washed product gas stream depleted in particulate solid compared to the raw product gas stream and comprising CO, H2, CO2, H2O, CH4, and optionally H2S; a") subjecting the washed product gas stream obtained according to a') to a drying step in a drying unit, obtaining a dried product gas stream depleted in H2O compared to the raw product gas stream and the washed product gas stream; and a'") optionally, subjecting the washed product gas stream obtained according to
  • a') comprises contacting the raw product gas stream with water in the washing unit.
  • the washing step can be performed as disclosed in WO 2023/161302A1.
  • the washed product gas stream has a temperature in the range of from 80 to 100°C.
  • the drying unit used in a") is a water separation unit.
  • a") comprises cooling the washed product gas stream obtained according to a'), obtaining the dried product gas stream, a gaseous stream, separated from water condensate.
  • the drying step can be performed as disclosed in WO 2023/161302 A1.
  • the acid gas removal step according to a'") is amine scrubbing.
  • o'" comprises using an amine, such as monoethanolamine (MEA). Diethanolamine (DEA), methyl-diethanolamine (MDEA) or diglycolamine (DGA), in the CO 2 /H2S adsorption unit, more preferably the absorption column.
  • the acid gas removal step can be performed as disclosed in WO 2023/161302 A1.
  • o'" comprises subjecting the dried product gas stream obtained according to a") to an acid gas removal step in a CO2/H2S adsorption unit, more preferably the CO2/H2S adsorption unit is an absorption column, obtaining the sweetened product gas stream and a CO 2 -comprising stream.
  • the CO 2 -comprising stream is recycled in the process of the present invention. Still more preferably, the CO2-comprising stream is recycled in p") as described below as at least a portion of the source of CO2.
  • the molar ratio of H2 to CO in the obtained syngas varies.
  • the molar ratio of H2 to CO may be adjusted by separating CO from the syngas.
  • CO can be separated from the syngas in a syngas separation unit which is downstream of and fluidly connected to a syngas producing unit.
  • CO can be separated from syngas by cryogenic separation methods, commonly referred to as a "cold box” which makes use of the different boiling points of CO and H2.
  • H2 can be separated using Fh-selective membranes thorough which H2 permeates and is thereby separated from a syngas stream. It is also possible to fully separate CO and H2 via cryogenic separation. The resulting CO and H2 can be used to create a syngas having the desired ratio.
  • recovering syngas from the raw product gas stream further comprises adjusting the hydrogen to carbon monoxide molar ratio in the raw product gas stream or the sweetened gas stream, respectively, to obtain an adjusted gas stream comprising CO and H2 at a molar ratio different from the molar ratio in the raw product gas stream or the sweetened gas stream, respectively; and, optionally, separating the adjusted gas stream to provide a CO-comprising gas stream, a F -comprising gas stream and a CHi-comprising gas stream.
  • the molar ratio of H2 to CO in the purified product gas stream may be adjusted, obtaining a modified product gas stream comprising CO and H 2 and having a H2 to CO molar ratio differing from the H2 to CO molar ratio of the purified product gas stream.
  • Adjusting the hydrogen to carbon monoxide molar ratio may involve shift reactions such as a water gas shift reaction according to
  • the H2 to CO molar ratio in the purified product gas stream is adjusted by: p') passing and contacting water with the purified product gas stream obtained in the first purification stage into a reaction unit RU(1) and subjecting to a water gas shift reaction in RU(1), obtaining a CO-depleted product gas stream depleted in CO compared to the purified product gas stream and comprising CO, H2, CH4 and CO2; or p") passing and contacting CO2, optionally the CO2-comprising stream from o'"), with the purified product gas stream into a reaction unit RU(2) for a reverse water gas shift reaction, obtaining a CO-enriched product gas stream enriched in CO compared to the purified product gas stream and comprising CO, H2 and CH4; or
  • the water gas shift reaction is preferably performed according to known processes in the art, such as for example those defined in Wei-Hsin Chen, et al., "Water gas shift reaction for hydrogen production and carbon dioxide capture”, Applied energy 258 (2020) 114078, https://doi.Org/10.1016/j.apenergy.2019.114078.
  • the reverse water gas shift reaction is preferably performed according to known processes in the art such as for example those defined in E. Rezaei, S. Dzuryk “Techno-economic comparison of reverse water gas shift reaction to steam and dry methane reforming reactions for syngas production", Chemical Engineering Research and Design, Vol 144 (2019), S. 354-369, EP2175986, CN103183346 and US8946308.
  • the process further comprises passing CO-depleted product gas stream through an acid gas removal unit, obtaining a sweetened CO-depleted product gas stream depleted in CO2 compared to the CO-depleted product gas stream and comprising CO, H2 and CH4.
  • At least a portion of the added H2 is renewably sourced H2.
  • the process additionally comprises recovering hydrogen from the raw product gas stream or the syngas obtained therefrom, and directing the hydrogen at least partially to p) and/or y).
  • the purified product gas stream or the modified product gas stream i.e., the CO-depleted product gas stream, the CO-enriched product gas stream, the Ftenriched product gas stream or the sweetened CO-depleted product gas stream, are subjected to a second purification stage.
  • the purified product gas stream or the modified product gas stream are subjected to a second purification stage, comprising subjecting the purified product gas stream or the modified product gas stream to cryogenic separation, e.g., in a cold box, obtaining a CO-comprising gas stream, a hb-comprising gas stream and a methane-comprising gas stream.
  • a second purification stage comprising subjecting the purified product gas stream or the modified product gas stream to cryogenic separation, e.g., in a cold box, obtaining a CO-comprising gas stream, a hb-comprising gas stream and a methane-comprising gas stream.
  • cryogenic separation can be performed by method known in the art, such as disclosed in Ullmann's Encyclopedia of Industrial Chemistry, Carbon Monoxide, Chapter 4.3.2, p.685-686.
  • Bioethanol is a preferred form of renewably-sourced ethanol, although the scope of the invention is not limited to the use of bioethanol.
  • Biomass feedstock can originate from several sources.
  • biomass includes wood, wood pellets, wood chips, straw, lignocellulosic biomass, energy crops, algae, biobased-oils, biobased-fats, and mixtures thereof.
  • Bioethanol production may be based on food crop feedstocks such as corn and sugar cane, sugarcane bagasse, cassava (first generation biofeedstock)
  • biomass feedstock is lignocellulosic materials from agricultural crops (second-generation biofeedstock).
  • Potential feedstocks include agricultural residue by-products such as rice, straw (such as wheat, oat and barley straw), rice husk, and corn stover.
  • Biomass feedstock may also be waste material from the forest products industry (wood waste) and saw dust or produced on purpose as an ethanol crop. Switchgrass and napier grass may be used as on-purpose crops for conversion to ethanol.
  • catalysts are activated alumina or silica, phosphoric acid impregnated on coke, heteropoly acids (HPA salts), silica-alumina, molecular sieves such as zeoliths of the ZSM-5 type or SAPO-11 type, other zeolites or modified zeolites of various molecular structures with zeoliths and HPA salts being preferred.
  • HPA salts heteropoly acids
  • silica-alumina molecular sieves
  • zeoliths of the ZSM-5 type or SAPO-11 type other zeolites or modified zeolites of various molecular structures with zeoliths and HPA salts being preferred.
  • 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. 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.
  • 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.
  • 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.
  • the gas 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.
  • Syndol catalysts with the main components of AI2O3- MgO/SIC>2, are employed in this process that was developed by American Halcon Scientific Design, Inc. in the 1980s.
  • the adiabatic reactor feed is diluted with steam to a large extent.
  • 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
  • step b)-(i) comprises: contacting the renewably-sourced ethylene stream with a dimerization catalyst in a dimerization zone; operating said dimerization zone at conditions effective to produce an effluent consisting essentially of n-butenes, a stream consisting essentially of heavier olefins, and optionally an unconverted ethylene stream; and fractionating the effluent to recover a stream consisting essentially of n-butenes, a stream consisting essentially of heavier olefins, and an optional ethylene stream.
  • the dimerization catalyst may be homogeneous or heterogeneous.
  • Typical dimerization catalysts are titanium or nickel compounds activated with alkyl aluminum compounds.
  • the Ti(IV) valency is stabilized by selecting the appropriate ligands, alkyl aluminum compound, the solvent polarity and the Al/Ti ratio.
  • Nickel compounds that can catalyze the selective production of butenes are typically based on cationic nickel salts stabilized with phosphine and activated with alkyl aluminum compounds.
  • the oligomerization of ethylene is implemented in the presence of a catalytic system in the liquid phase comprising a nickel compound and an aluminum compound.
  • a catalytic system in the liquid phase comprising a nickel compound and an aluminum compound.
  • Such catalytic systems are described in the documents FR 2 443 877 and FR 2794 038.
  • the Dimersol ETM process is based on this technology and leads to the industrial production of olefins.
  • the oligomerization of ethylene is implemented in the presence of a catalytic system comprising: i) at least one bivalent nickel compound, ii) at least one hydrocarbyl aluminum dihalide of formula AIRX2, in which R is a hydrocarbyl radical comprising 1 to 12 carbon atoms, such as alkyl, aryl, aralkyl, alkaryl or cycloalkyl, X is a chlorine or bromine atom, and iii) optionally a Bronsted organic acid.
  • a catalytic system comprising: i) at least one bivalent nickel compound, ii) at least one hydrocarbyl aluminum dihalide of formula AIRX2, in which R is a hydrocarbyl radical comprising 1 to 12 carbon atoms, such as alkyl, aryl, aralkyl, alkaryl or cycloalkyl, X is a chlorine or bromine atom, and iii) optionally a Bronsted organic acid.
  • nickel carboxylates of general formula (R 1 COO)2Ni are preferably used, where R 1 is an optionally substituted hydrocarbyl radical, for example alkyl, cycloalkyl, alkenyl, aryl, aralkyl, or alkaryl, containing up to 20 carbon atoms, preferably a hydrocarbyl radical of 5 to 20 carbon atoms, preferably 6 to 18 carbon atoms.
  • Suitable bivalent nickel compounds include: chloride, bromide, carboxylates such as octoate, 2-ethylhexanoate, decanoate, oleate, salicylate, hydroxydecanoate, stearate, phenates, naphthenates, and acetyl acetonates.
  • Nickel 2-ethylhexanoate is preferably used.
  • the hydrocarbyl aluminum dihalide compound corresponds to the formula AIRX2, in which R is a hydrocarbyl radical comprising 1 to 12 carbon atoms, such as alkyl, aryl, aralkyl, alkaryl or cycloalkyl, and X is a chlorine or bromine atom.
  • R is a hydrocarbyl radical comprising 1 to 12 carbon atoms, such as alkyl, aryl, aralkyl, alkaryl or cycloalkyl
  • X is a chlorine or bromine atom.
  • ethylaluminum sesquichloride dichloroethyl aluminum, dichloroisobutyl aluminum, chlorodiethyl aluminum or mixtures thereof
  • a Bronsted organic acid is used.
  • the Bronsted acid compound corresponds to the formula HY, where Y is an organic anion, for example carboxylic, sulfonic or phenolic.
  • Halocarboxylic acids of formula R 2 COOH in which R 2 is a halogenated alkyl radical are preferred, in particular those that contain at least one alpha-halogen atom of the group — COOH with 2 to 10 carbon atoms in all.
  • a haloacetic acid of formula CX P H3- P — COOH is used, in which X is fluorine, chlorine, bromine or iodine, with p being an integer from 1 to 3.
  • Trifluoroacetic acid is preferably used.
  • the three components of the catalytic formula can be mixed in any order. However, it is preferable first to mix the nickel compound with the Brpnsted organic acid, and then next to introduce the aluminum compound.
  • the molar ratio of the hydrocarbyl aluminum dihalide to the nickel compound, expressed by the Al/Ni ratio, is 2/1 to 50/1, and preferably 2/1 to 20/1.
  • the molar ratio of the Brpnsted acid to the nickel compound is 0.25/1 to 10/1 , and preferably 0.25/1 to 5/1.
  • the hydrocarbyl aluminum dihalide can be enriched with an aluminum trihalide, the mixture of the two compounds then corresponding to the formula AIR n X3- n , in which R is a hydrocarbyl radical comprising 1 to 12 carbon atoms, such as alkyl, aryl, aralkyl, alkaryl or cycloalkyl, X is a chlorine or bromine atom, and n is a number between 0 and 1.
  • Suitable mixtures include: dichloroethyl aluminum enriched with aluminum chloride, the mixture having a formula AIEto.gCh.i; dichloroisobutyl aluminum enriched with aluminum chloride, the mixture having a formula AliBuo.gClzi; and dibromoethyl aluminum enriched with aluminum bromide, the mixture having a formula AIEto.9Br2.1-
  • the reaction for oligomerization of ethylene can be implemented at a temperature of -20 to 80 °C, preferably 40 to 60 °C, under pressure conditions such that the reagents are kept at least for the most part in the liquid phase or in the condensed phase.
  • the pressure is generally between 0.5 and 5 MPa, preferably between 0.5 MPa and 3.5 MPa.
  • the time of contact is generally between 0.5 and 20 hours, preferably between 1 and 15 hours.
  • the oligomerization stage can be implemented in a reactor with one or more reaction stages in a series, with the ethylene feedstock and/or the catalytic composition that is preferably pre-conditioned in advance being introduced continuously, either in the first stage, or in the first stage and any other one of the stages.
  • the catalyst can be deactivated, for example by injection of ammonia and/or an aqueous solution of soda and/or an aqueous solution of sulfuric acid.
  • the unconverted olefins and alkanes that are optionally present in the feedstock are then separated from the oligomers by a separation stage, for example by distillation or washing cycles by means of caustic soda and/or water.
  • the effluent generally contains less than 0.2% by weight of isobutene, or even less than 0.1 % by weight of isobutene.
  • the separation can be carried out by evaporation, distillation, extractive distillation, extraction by solvent or else by a combination of these techniques. These processes are known by one skilled in the art.
  • a separation of the effluent that is obtained by oligomerization of ethylene is carried out by distillation.
  • the effluent of the oligomerization is sent into a distillation column system comprising one or more columns that makes it possible to separate, on the one hand, n-butenes from ethylene, which can be returned to the oligomerization reactor, and heavier olefins with 5 carbon atoms and more.
  • Such heavier olefins can be used as a gasifier feedstock according to step a) of the process according to the present invention.
  • the heavier olefins can constitute the entire gasifier feedstock or can form a part thereof.
  • the heavier olefins form part of the gasifier feedstock, meaning they are mixed with suitable other materials to form the gasifier feedstock.
  • Step b) inevitably results in the formation of the heavier olefins stream as specified above.
  • This stream is typically considered a waste stream and subjected to incineration, resulting in a loss of renewable carbon atoms for synthesis.
  • the renewable carbon can be recycled to the synthesis of n-butanol and 2-ethy I hexanol.
  • the heavier olefins may be subjected to hydrogenation so as to obtain renewably-sourced naphtha.
  • "Renewably-sourced naphtha” shall mean naphtha produced from renewable sources. It is a hydrocarbon composition, consisting of mainly paraffins. The molecular weight of this renewably-sourced naphtha may range from hydrocarbons having 5 to 8 carbon atoms. Renewably-sourced naphtha can be used as a feedstock in steam-cracking to produce renewably-sourced light olefins, dienes and aromatics.
  • step b)-(i) comprises:
  • step a) optionally directing the stream consisting essentially of heavier olefins to step a) as a gasifier feedstock or subjecting the stream consisting essentially of heavier olefins to hydrogenation so as to obtain renewably-sourced naphtha.
  • Step b)-(ii) comprises a metathesis reaction between n-butenes obtained according to step (i) and ethylene to obtain propylene.
  • the n-butenes obtained according during ethylene dimerization (i) are a mixed stream including 1 -butene and 2-butenes. Essentially only the 2-butenes react in a metathesis reaction, while 1 -butene is essentially inert.
  • step b)-(ii) comprises removal of 1-butene from the mixed stream to obtain a stream rich in 2-butenes, and subjecting the stream rich in 2-butenes to the metathesis reaction.
  • a stream rich in 2-butenes may comprise at least 90 wt.-% of 2-butenes, based on the total amount of n-butenes.
  • 1-butene may be converted to 2-butene by double bond isomerization.
  • Double bond isomerization is an equilibrium-limited reaction It is thus advantageous to subject the mixed stream of n-butenes to metathesis so as to react 2-butene with ethylene prior to double bond isomerization of 1-butene.
  • the n-butenes are a mixed stream including 1 -butene and 2-butenes
  • b)-(ii) comprises b)-(iia) subjecting the mixed stream to the metathesis reaction to obtain propylene and unreacted 1-butene; b)-(iib) subjecting the unreacted 1 -butene to double bond isomerization to obtain 2-butenes; and b)-(iic) recycling the 2-butenes obtained in step b)-(iib) to step b)-(iia).
  • step b)-(ii) is carried out by passing the mixed stream through a metathesis/isomerization zone comprising both a metathesis catalyst and an isomerization catalyst.
  • 2-butene is consumed due to the metathesis reaction over the metathesis catalyst, it is thus replenished by isomerization of 1 -butene to 2-butene over the isomerization catalyst.
  • the reaction is carried out in the presence of a metathesis catalyst on the basis of a metal which is selected from tungsten, molybdenum, rhenium, niobium, tantalum, vanadium, ruthenium, rhodium, iridium, osmium and nickel and the like.
  • a metal which is selected from tungsten, molybdenum, rhenium, niobium, tantalum, vanadium, ruthenium, rhodium, iridium, osmium and nickel and the like.
  • Tungsten, molybdenum and rhenium are preferred and tungsten is particularly preferred.
  • tungsten catalysts are supported on silica
  • molybdenum and rhenium are supported on alumina based carriers.
  • Especially preferred metathesis catalysts are WOs-based catalysts, for example silica-supported WOg in the form of granules.
  • Suitable isomerization catalysts include magnesium-based catalysts such as MgO-based catalysts, for example tableted MgO.
  • Metathesis is carried out under conditions effective to produce an effluent comprising propylene, unconverted ethylene, and optionally 1-butene
  • Unconverted ethylene and/or unconverted n-butenes may be recycled and combined with fresh ethylene and n-butenes to provided the metathesis feedstock.
  • the reaction may be conducted at 340 - 375°C, 25-40 bar, a weight hourly space velocity (WHSV) of 7.5-30 hr 1 , and an ethylene to 2-butene molar ratio of 3:1 to 10:1.
  • WHSV weight hourly space velocity
  • the reactor effluent may be sent to a deethenizer to remove C2 and lighter material.
  • the bottoms from the deethenizer are sent to the depropenizer.
  • High-purity, polymer-grade propylene (> 99.9% molar purity) is recovered from the depropenizer overhead.
  • the lighter material from the deethenizer and heavier C4+ material from the depropenizer are partly recycled to the reactors. Purge streams are provided for the lighter and heavier material to prevent buildup of inerts.
  • propane is not produced during the metathesis reaction. Consequently, polymer- grade propylene can be produced from the process, without the need for an expensive propylene-propane superfractionator.
  • the process comprises: blending the renewably-sourced ethylene with complementary ethylene prior to step b), the complementary ethylene not being obtained from renewably-sourced ethanol in accordance with step a); and/or blending the renewably-sourced n-butenes with complementary n-butenes prior to step b)-(ii), the complementary n-butenes not being obtained from renewably-sourced ethanol in accordance with steps a) and b)-(i).
  • Examples for complementary ethylenes are ethylenes obtained by steam cracking of fossil based feeds, like naphtha, natural gas or crude oil.
  • Examples for complementary propylenes are propylenes obtained by steam cracking of fossil based feeds, like naphtha, natural gas or crude oil.
  • Examples for complementary n-butenes are n-butenes obtained by steam cracking of fossil based feeds, like naphtha, natural gas or crude oil.
  • step c) the propylene obtained from renewably-sourced ethanol is mixed with propylene not obtained from renewably-sourced ethanol to form mixed propylene.
  • the mixed propylene comprises 5 to 95 wt.-% of propylene obtained from renewably-sourced ethanol, more preferably 10 to 90 wt.-% of propylene obtained from renewably-sourced ethanol, based on the total weight of the mixed propylene.
  • the process comprises mixing the propylene obtained from renewably-sourced ethanol with propylene not obtained from renewably-sourced ethanol to form mixed propylene as step c).
  • This can ensure the efficient utilization of downstream processes, e.g. , for transitional periods when supply of propylene obtained from renewably-sourced ethanol is limited.
  • the complementary may be fossil-based, partially renewably-sourced or renewably-sourced by another production route.
  • Hydroformylation of the mixed propylene produces n-butyraldehyde, isobutyraldehyde or a mixture thereof.
  • the produced aldehydes can be separated by fractionation.
  • Hydroformylation or the oxo process is an important large-scale industrial process for preparing aldehydes from olefins, carbon monoxide and hydrogen. These aldehydes can be hydrogenated with hydrogen in the same operation or subsequently in a separate hydrogenation step, to produce the corresponding alcohols.
  • hydroformylation is carried out in the presence of catalysts which are homogeneously dissolved in the reaction medium.
  • Catalysts used are generally the carbonyl complexes of metals of transition group VIII, in particular Co, Rh, Ir, Pd, Pt or Ru, which may be unmodified or modified with, for example, amine- containing or phosphine-containing ligands.
  • Propylene is preferably hydroformylated using ligand-modified rhodium carbonyls as the catalyst. Hydroformylation of propylene can be carried out at temperatures in the range of 50 °C to 200 °C, preferably 60 °C to 150 °C, and more preferably 70 °C to 120 °C.
  • the hydroformylation reaction is conducted at a low pressure, e.g., a pressure in the range of 0.05 to 50 MPa (absolute), and preferably in the range of about 0.1 MPa to 30 MPa, most preferably at a pressure below 5 MPa.
  • a pressure in the range of 0.05 to 50 MPa (absolute) e.g., 0.05 to 50 MPa (absolute)
  • preferably in the range of about 0.1 MPa to 30 MPa most preferably at a pressure below 5 MPa.
  • the partial pressure of carbon monoxide is not greater than 50% of the total pressure.
  • the proportions of carbon monoxide, hydrogen, and propylene in the hydroformylation reaction medium can be selected within a wide range.
  • CO is from about 1 to 50 mol-%, preferably about 1 to 35 mol-%
  • H2 is from about 1 to 98 mol-%, preferably about 10 to 90 mol-%
  • propylene is from about 0.1 to 35 mol-%, preferably about 1 to 35 mol-%.
  • the hydroformylation reaction preferably takes place in the presence of both liquid and gas phases.
  • the reactants generally are in the gas phase.
  • the catalyst typically is in the liquid phase. Because the reactants are gaseous compounds, a high contact surface area between the gas and liquid phases is desirable to enhance good mass transfer.
  • a high contact surface area between the catalyst solution and the gas phase may be provided in any suitable manner.
  • the reactor feed gas can be contacted with the catalyst solution in, for example, a continuous-flow stirred autoclave where the gas is introduced and dispersed at the bottom of the vessel, preferably through a perforated inlet (e.g., a sparger).
  • High contact between the catalyst and the gas feed may also be provided by dispersing the solution of the Rh catalyst on a high surface area support, a technique well known in the art as supported liquid phase catalysis, or providing the Rh as part of a permeable gel.
  • the reaction may be conducted either in a batch mode or, preferably, on a continuous basis.
  • One or more reactors may be used in continuous modes to carry out the reaction in one or more stages.
  • the ratio of H2to CO in the syngas used for hydroformylation is desirably in the range from 1.1 : 1 to 1.01: 1 , preferably 1.06:1 to 1.02: 1.
  • syngas may be made or otherwise initially provided in a manner such that the ratio of hydrogen to CO is much higher than this
  • the excess hydrogen can be separated and used in other reaction stages as desired.
  • the excess hydrogen may be used to reduce n-butyraldehyde to n-butanol.
  • syngas in the practice of the present invention is anhydrous.
  • the obtained n-butyraldehyde is hydrogenated in the presence of hydrogen.
  • the hydrogenation of n-butyraldehyde to n-butanol is a well-known reaction and can be conducted by any suitable known process.
  • the hydrogenation is carried out with hydrogen in the liquid or gas phase in the presence of a hydrogenation catalyst.
  • Homogeneous or heterogeneous catalysts can be used. Copper catalysts have proved to be the most suitable.
  • the reaction is carried out in the liquid phase on fixed-bed catalysts at 20 to 200 °C and pressures of up to 30 MPa. Hydrogenation in the gas phase is preferably carried out continuously. Further details can be taken from Ullmann’s Encyclopedia of Industrial Chemistry, 5 th edition, vol. A1 , 1984.
  • the obtained n-butyraldehyde is condensed to produce 2-ethyl-3-hydroxyhexanal, and the 2-ethyl-3-hydroxyhexanal is subjected to a hydrogenation reaction produces 2-ethylhexanol.
  • An aldol condensation is a well-known condensation reaction in which an enol or an enolate ion reacts with a carbonyl compound to form a
  • n-butyraldehyde is reacted in a self-aldol condensation to obtain 2-ethy l-3-hydroxyhexanal .
  • Aldol condensations can occur under a variety of conditions under weak acidic or strong basic conditions and in the presence of various catalysts.
  • the reaction can typically be carried out in liquid phase using an aqueous caustic catalyst at a temperature of about 80 to 140 °C.
  • the reaction can be carried out in gaseous phase by contacting the aldehyde in the vapor phase with a particulate catalyst comprising at least one basic alkali metal compound on an inert substrate at a temperature above 175 °C. Further details are provided in WO 2000/031011 .
  • the hydrogenation of the obtained 2-ethyl-3-hydroxyhexanal to 2-ethylhexanol can be carried out analogously to the above-described hydrogenation of n-butyraldehyde.
  • sequence of chemical conversion according to step d) additionally comprises 5) and E):
  • Acrylic acid is an important basic chemical. Owing to its very reactive double bond and the acid function, it is suitable in particular for use as monomer for preparing polymers. Of the amount of acrylic acid monomer produced, the major part is esterified before polymerization, for example to form acrylate adhesives, dispersions or coatings. Only the smaller part of the acrylic acid monomer produced is polymerized directly, for example to form water-absorbent resins. Whereas, in general, the direct polymerization of acrylic acid requires high purity monomer, the acrylic acid for conversion into acrylate before polymerization does not have to be so pure.
  • acrylic acid can be produced by heterogeneously catalyzed gas phase oxidation of propylene with molecular oxygen over solid catalysts at temperatures between 200° to 400° C. in two stages via acrolein (cf. for example DE-A 19 62 431 , DE-A 29 43 707, DE-C 1 205 502, EP-A 257 565, EP-A 253 409, DE-B 22 51 364, EPA 117 146, GB-C 1 450 986 and EP-A 293 224).
  • acrolein cf. for example DE-A 19 62 431 , DE-A 29 43 707, DE-C 1 205 502, EP-A 257 565, EP-A 253 409, DE-B 22 51 364, EPA 117 146, GB-C 1 450 986 and EP-A 293 224.
  • catalyst additives iron, cobalt, nickel, tungsten, potassium and phosphorous.
  • Typical catalyst supports are inert porous solids, such as SiO2, AI2O3, MgO, TiC>2, ZrO2, aluminosilicates, zeolites, activated carbon, and ceramics
  • the oxidation of propylene to acrylic acid can be carried out in one stage or two stages.
  • Catalysts used for the heterogeneously catalyzed reaction are as a rule multimetal oxide materials which generally contain heavy metal molybdates as main component and compounds of various elements as promoters.
  • the oxidation of propylene takes place in a first step to give acrolein and in a second step to give acrylic acid. Since the two oxidation steps may differ in their kinetics, uniform process conditions and a single catalyst do not as a rule lead to optimum selectivity. Recently, two-stage processes with optimum adaptation of catalyst and process variables have therefore preferably been developed.
  • Particularly preferred multimetal oxide materials have the formula I or II
  • X 1 is bismuth, tellurium, antimony, tin and/or copper, preferably bismuth, X 2 is molybdenum and/or tungsten, X 3 is an alkali metal, thallium and/or samarium, preferably potassium,
  • X 4 is an alkaline earth metal, nickel, cobalt, copper, manganese, zinc, tin, cadmium and/or mercury, preferably nickel and/or cobalt,
  • X 5 is iron, chromium, cerium and/or vanadium, preferably iron,
  • X 6 is phosphorus, arsenic, boron and/or antimony
  • X 7 is a rare earth metal, titanium, zirconium, niobium, tantalum, rhenium, ruthenium, rhodium, silver, gold, aluminum, gallium, indium, silicon, germanium, lead, thorium and/or uranium, preferably silicon, aluminum, titanium and/or zirconium, a is from 0.01 to 8, b is from 0.1 to 30, c is from 0 to 4, d is from 0 to 20, e is from 0 to 20, f is from 0 to 6, g is from 0 to 15, h is from 8 to 16, x and y are numbers which are determined by the valency and frequency of the elements other than oxygen in I, p and q are numbers whose ratio p/q is from 0.1 to 10,
  • X 8 is cobalt and/or nickel, preferably cobalt
  • X 9 is silicon and/or aluminum, preferably silicon
  • X 10 is an alkali metal, preferably potassium, sodium, cesium and/or rubidium, in particular potassium, i is from 0.1 to 2, k is from 2 to 10, I is from 0.5 to 10, m is from 0 to 10, n is from 0 to 0 5, z is a number which is determined by the valency and frequency of the elements other than oxygen in II.
  • Multimetal oxide materials of the formula I are known per se from EP 0 000 835 and EP 0 575 897, and multimetal oxide materials of the formula II are known per se from DE 198 55 913.
  • a process for preparing acrylic acid typically comprises the steps of:
  • Step (a) affords not pure acrylic acid, but a gaseous mixture which in addition to acrylic acid can substantially include unconverted acrolein and/or propylene, water vapor, carbon monoxide, carbon dioxide, nitrogen, oxygen, acetic acid, propionic acid, formaldehyde, further aldehydes and maleic anhydride.
  • the remaining, unabsorbed reaction gas of step (a) is further cooled down so that the condensable part of the low-boiling co-components thereof, especially water, formaldehyde and acetic acid, may be separated off by condensation.
  • This condensate is known as acid water.
  • the remaining gas stream hereinafter called recycle gas, consists predominantly of nitrogen, carbon oxides and unconverted starting materials.
  • the recycle gas is partly recirculated into the reaction stages as diluting gas.
  • the propylene oxidation reaction progresses under formation of CO X as a side product, and the process further comprises subjecting said CO X to hydrogenation to produce at least one of synthesis gas, methanol, formaldehyde and formic acid.
  • the carbon monoxide and/or carbon dioxide may be sequestered by, e.g., underground storage, it may be beneficial to subject said CO X to hydrogenation to produce at least one of synthesis gas, methanol, formaldehyde and formic acid.
  • the synthesis gas, methanol, formaldehyde and/or formic acid thus produced may then be certified as carbon negative, and can at least partly displace their fossil-based counterparts and reduce the carbon footprint of chemical conversion processes making use of synthesis gas, methanol, formaldehyde and/or formic acid.
  • the sequence of chemical conversion according to step d) further comprises esterification of the n-butanol, the isobutanol and/or the 2-ethylhexanol with carboxylic acids.
  • carboxylic acids include saturated and non-saturated Ci-Ci6-carboxylic acid, in particular (meth)acrylic acid.
  • a polymerization inhibitor is not required.
  • esters of C4-C10 carboxylic acids such as phthalic acid and adipic acid, and n-butanol and/or 2-ethylhexanol are widely used as plasticizers in plastics, such as cellulose acetates, polyurethanes, PVC, polyacrylates, etc. They may be prepared by reacting the acid component or an anhydride thereof with the alcohol component in the presence of an esterification catalyst. The reaction is an equilibrium reaction. The equilibrium may be shifted to the product side, i.e. the ester side, by continuous removal of the water produced as by-product from the reaction.
  • 2-Ethylhexanol has a region in which it is not miscible with water; hence it is possible to distill off continuously from the reaction mixture a mixture of the water of the reaction and 2-ethylhexanol, and, after phase separation, to return the organic phase to the esterification, while the aqueous phase is removed from the system.
  • Esterification of the acrylic acid with an alcohol yields an acrylic ester.
  • esterification of acrylic acid with n-butanol obtained in p) yields n-butyl acrylate
  • esterification of acrylic acid with 2-ethylhexanol obtained in y) yield 2-ethylhexyl acrylate.
  • Acrylic esters are generally known and are important, for example, as reactive monoethylenically unsaturated monomers for the preparation of aqueous polymer dispersions by the free radical aqueous emulsion polymerization method, which dispersions are used, for example, as adhesives.
  • the acrylic acid can be esterified in a conventional manner to produce the desired acrylic acid ester using the corresponding alkanol, i.e., n-butanol or 2-ethylhexanol.
  • alkanol i.e., n-butanol or 2-ethylhexanol.
  • Processes for the preparation of alkyl acrylates by reacting acrylic acid with alkanols in the homogeneous liquid phase at elevated temperatures and in the presence of catalysts are equilibrium reactions in which the conversion of the acrylic acid and of the alkanol to the corresponding ester is limited by the equilibrium constant. Consequently, for an economical procedure, the unconverted starting materials have to be separated from the resulting ester and recycled to the reaction zone.
  • the reaction zone may consist of a cascade of reaction regions, connected in series, and the discharge stream of one reaction region forms a feed stream of a subsequent reaction region and the concentration of the esterification catalyst increases along the reaction cascade.
  • Acrylic acid, the alkanol and the catalyst are fed continuously to the reaction zone.
  • An azeotropic mixture comprising the alkyl acrylate, water and optionally starting alkanol is separated off by rectification via the top of a rectification zone mounted on the reaction zone.
  • the azeotropic mixture is separated into an organic phase containing the alkyl acrylate and an aqueous phase, with a part of the organic phase being recycled to the reaction zone.
  • the alkyl acrylate is isolated from the excess organic phase. The latter is usually carried out by separation steps involving rectification (cf. for example DE 19536178).
  • the temperature in the reaction zone depends on the type of alcohol used and is suitably in the range of 70 to 160 °C, preferably 100 to 140 °C.
  • the total residence time of the reactants in the reaction zone is as a rule from 0.25 to 15 h, frequently from 1 to 7 h, or from 2 to 5 h.
  • Suitable acidic esterification catalysts include acidic ion exchange resins and strong mineral acids, e.g. sulfuric acid, or organic sulfonic acids, such as methanesulfonic acid, benzenesulfonic acid, dodecanesulfonic acid or para-toluenesulfonic acid, or a mixture of some or all of the abovementioned acids.
  • Sulfuric acid is particularly suitable for carrying out the novel process. This applies in particular to the preparation of n-butyl acrylate.
  • the content of acidic esterification catalyst in the reaction zone is expediently from 0.1 to 20wt.-%, frequently from 0.5 to 5 wt.-%, based on the reaction mixture contained therein.
  • a polymerization inhibitor is typically used during esterification.
  • suitable polymerization inhibitors are hydroquinone, 4-methoxyphenol, and phenothiazine, which may be used singly or in admixture with each other. It is usual to add from about 0.01 to 0.1 wt.-% of polymerization inhibitor to the esterification mixture and mixtures containing the methacrylic ester.
  • the examples are based on simulations performed via the flow sheet simulation platform Aspen Plus V14.0.
  • This example is a plasma gasification process comprising a plasma fixed bed gasifier, converting a first feed stream of refuse derived fuel into a clean synthesis gas.
  • the plasma reactor is fed with the feed stream at a mass flow ratio of 1.00 t/(t clean syngas) at 1 bar(abs) and 25 °C.
  • the feed stream comprises 40 wt.-% carbon, 8 wt.-% hydrogen, 40 wt.-% oxygen, 1 wt.-% sulfur and 1 wt.-% nitrogen, rest percentage is ash
  • gasification agents are injected into the plasma reactor, enabling a gasification reaction at a temperature of 1350°C.
  • the gasification agent is steam with a mass flow ratio of 0.10 t/(t clean syngas) at 5.4 bar(abs) and 180°C, forming a plasma in the reactor with 3.26 MWh/(t clean syngas) of electricity.
  • the resulting raw synthesis gas stream is sent to the gasifier outlet.
  • the resulting high-temperature synthesis gas stream comprising CO, H2O, CO2, H2, CH4, H2S, N2, NH3, is washed with water and dried in order to reduce the amount of ash and tars.
  • the raw synthesis gas exits the wash a d drying step at a temperature of 25 °C.
  • the acid gas removal is used to separate acids like H2S and CO2 with a mass flow ratio of 0.002 t/(t clean syngas) from the raw synthesis gas.
  • This example is a plasma gasification process comprising a plasma fixed bed gasifier, converting a first feed stream of refuse derived fuel into a clean synthesis gas.
  • the plasma reactor is fed with the feed stream at a mass flow ratio of 1.07 t/(t clean syngas) at 1 bar(abs) and 25 °C.
  • the feed stream comprises 40 wt.-% carbon, 8 wt.-% hydrogen, 40 wt.-% oxygen, 1 wt.-% sulfur and 1 wt.-% nitrogen, rest percentage is ash.
  • gasification agents are injected into the plasma reactor, enabling a gasification reaction at a temperature of 1350°C.
  • the gasification agent is steam with a mass flow ratio of 1.07 t/(t clean syngas) at 5.4 bar(abs) and 180°C, forming a plasma in the reactor with 5.06 MWh/(t clean syngas) of electricity.
  • the resulting raw synthesis gas stream is sent to the gasifier outlet.
  • the resulting high-temperature synthesis gas stream comprising CO, H2O, CO2, H2, CH4, H2S, N2, NH3, is washed with water and dried in order to reduce the amount of ash and tars.
  • the raw synthesis gas exits the wash and drying step at a temperature of 25 °C
  • the acid gas removal enabled by an amine scrubbing, is used to separate acids like H2S and CO2 with a mass flow ratio of 0.31 t/(t clean syngas) from the raw synthesis gas.
  • This example is a plasma gasification process comprising a plasma fixed bed gasifier, converting a first feed stream of refuse derived fuel into a clean synthesis gas.
  • the plasma reactor is fed with the feed stream at a mass flow ratio of 0.95 t/(t clean syngas) at 1 bar(abs) and 25 °C.
  • the feed stream comprises 65 wt.-% carbon, 9 wt.-% hydrogen, 21 wt.-% oxygen, 0 wt.-% sulfur and 0 wt.-% nitrogen, rest percentage is ash.
  • gasification agents are injected into the plasma reactor, enabling a gasification reaction at a temperature of 1350°C.
  • the gasification agent is steam with a mass flow ratio of 0.10 t/(t clean syngas) at 5.4 bar(abs) and 180°C, forming a plasma in the reactor with 2.95 MWh/(t clean syngas) of electricity.
  • the resulting raw synthesis gas stream is sent to the gasifier outlet.
  • the resulting high-temperature synthesis gas stream comprising CO, H2O, CO2, H2, CH4, H2S, N2, NH3, is washed with water and dried in order to reduce the amount of ash and tars.
  • the raw synthesis gas exits the wash a d drying step at a temperature of 25 °C
  • the acid gas removal enabled by an amine scrubbing, is used to separate acids like H2S and CO2 with a mass flow ratio of 0.001 t/(t clean syngas) from the raw synthesis gas.
  • This example is a plasma gasification process comprising a plasma fixed bed gasifier, converting a first feed stream of refuse derived fuel into a clean synthesis gas.
  • the plasma reactor is fed with the feed stream at a mass flow ratio of 1.43 t/(t clean syngas) at 1 bar(abs) and 25 °C.
  • the feed stream comprises 30 wt.-% carbon, 6 wt.-% hydrogen, 20 wt.-% oxygen, 2 wt.-% sulfur and 2 wt.-% nitrogen, rest percentage is ash.
  • gasification agents are injected into the plasma reactor, enabling a gasification reaction at a temperature of 1350°C.
  • the gasification agent is steam with a mass flow ratio of 0.14 t/(t clean syngas) at 5.4 bar(abs) and 180°C, forming a plasma in the reactor with 3.09 MWh/(t clean syngas) of electricity.
  • the resulting raw synthesis gas stream is sent to the gasifier outlet.
  • the resulting high-temperature synthesis gas stream comprising CO, H2O, CO2, H2, CH4, H2S, N2, NH3, is washed with water and dried in order to reduce the amount of ash and tars.
  • the raw synthesis gas exits the wash and drying step at a temperature of 25 °C
  • the acid gas removal enabled by an amine scrubbing, is used to separate acids like H2S and CO2 with a mass flow ratio of 0.001 t/(t clean syngas) from the raw synthesis gas.
  • This example is a two-step gasification process comprising a fluidized bed reactor, followed by an entrained flow gasifier, converting a first feed stream of refuse derived fuel into a clean synthesis gas.
  • the fluidized bed reactor is fed with the feed stream at a mass flow ratio of 1.40 t/(t clean syngas) at 4 bar(abs) and 35 °C.
  • the feed stream comprises 40 wt.-% carbon, 8 wt.-% hydrogen, 40 wt.-% oxygen, 1 wt -% sulfur and 1 wt.-% nitrogen, rest percentage is ash.
  • gasification agents are injected into the fluidized bed reactor, enabling a gasification reaction at a temperature of 800°C.
  • the gasification agents are steam with a mass flow ratio of 0.7 t/(t clean syngas) at 5.4 bar(abs) and 180°C, as well as oxygen with a mass flow ratio of 0.46 t/(t clean syngas) at 25 °C and 6 bar(abs).
  • the resulting raw synthesis gas stream is sent to the top of the entrained flow gasifier whereby being kept at a temperature of 800 °C as a second stage and injected via the burner. No second fuel is added.
  • additional oxygen at a mass flow ratio of 0.22 t/(t clean syngas) at 15 bar(abs) and 100°C is used to increase the temperature up to 1350 °C at the gasifier outlet and convert remaining hydrocarbons, tars, and soot into synthesis gas.
  • This example is a two-step gasification process comprising a fluidized bed reactor, followed by an entrained flow gasifier, converting a first feed stream of refuse derived fuel into a clean synthesis gas.
  • the fluidized bed reactor is fed with the feed stream at a mass flow ratio of 1.13 t/(t clean syngas) at 4 bar(abs) and 35 °C.
  • the feed stream comprises 40 wt.-% carbon, 8 wt.-% hydrogen, 40 wt.-% oxygen, 1 wt.-% sulfur and 1 wt.-% nitrogen, rest percentage is ash.
  • gasification agents are injected into the fluidized bed reactor, enabling a gasification reaction at a temperature of 800°C.
  • the gasification agents are steam with a mass flow ratio of 0.56 t/(t clean syngas) at 5.4 bar(abs) and 180°C, as well as oxygen with a mass flow ratio of 0.37 t/(t clean syngas) at 25 °C and 6 bar(abs).
  • the resulting raw synthesis gas stream is sent to the top of the entrained flow gasifier whereby being kept at a temperature of 800 °C as a second stage and injected via the burner.
  • a bio oil is added as a second fuel to the entrained flow gasifier with a mass ratio of 0.11 t/(t clean syngas) at 100 °C and 20 bar comprising 75 wt.-% carbon, 7 wt.-% hydrogen and 18 wt.-% oxygen.
  • additional oxygen at a mass flow ratio of 0.27 t/(t clean syngas) at 15 bar(abs) and 100°C is used to increase the temperature up to 1350 °C at the gasifier outlet and convert remaining hydrocarbons, tars, and soot into synthesis gas.
  • the resulting high-temperature synthesis gas stream comprising CO, H2O, CO2, H2, CH4, H2S, N2, N H3, is washed with water and dried in order to reduce the amount of ash and tars.
  • the raw synthesis gas exits the wash and drying step at a temperature of 25 °C.
  • the acid gas removal is used to separate acids like H2S and CO2 with a mass flow ratio of 0.55 t/(t clean syngas) from the raw synthesis gas.
  • This example is a two-step gasification process comprising a fluidized bed reactor, followed by an entrained flow gasifier, converting a first feed stream of refuse derived fuel into a clean synthesis gas.
  • the fluidized bed reactor is fed with the feed stream at a mass flow ratio of 1.09 t/(t clean syngas) at 4 bar(abs) and 35 °C.
  • the feed stream comprises 40 wt.-% carbon, 8 wt.-% hydrogen, 40 wt.-% oxygen, 1 wt.-% sulfur and 1 wt.-% nitrogen, rest percentage is ash.
  • gasification agents are injected into the fluidized bed reactor, enabling a gasification reaction at a temperature of 800°C.
  • the gasification agents are steam with a mass flow ratio of 0.55 t/(t clean syngas) at 5.4 bar(abs) and 180°C, as well as oxygen with a mass flow ratio of 0.36 t/(t clean syngas) at 25 °C and 6 bar(abs).
  • the resulting raw synthesis gas stream is sent to the top of the entrained flow gasifier whereby being kept at a temperature of 800 °C as a second stage and injected via the burner.
  • a bio oil is added as a second fuel to the entrained flow gasifier with a mass ratio of 0.11 t/(t clean syngas) at 100 °C and 20 bar comprising 85 wt.-% carbon, 8 wt.-% hydrogen and 7 wt.-% oxygen.
  • additional oxygen at a mass flow ratio of 0.27 t/(t clean syngas) at 15 bar(abs) and 100°C is used to increase the temperature up to 1350 °C at the gasifier outlet and convert remaining hydrocarbons, tars, and soot into synthesis gas.
  • the resulting high-temperature synthesis gas stream comprising CO, H2O, CO2, H2, CH4, H2S, N2, NH3, is washed with water and dried in order to reduce the amount of ash and tars.
  • the raw synthesis gas exits the wash and drying step at a temperature of 25 °C.
  • the acid gas removal is used to separate acids like H2S and CO2 with a mass flow ratio of 0.52 t/(t clean syngas) from the raw synthesis gas.
  • This example is a two-step gasification process comprising a fluidized bed reactor, followed by an entrained flow gasifier, converting a first feed stream of refuse derived fuel into a clean synthesis gas.
  • the fluidized bed reactor is fed with the feed stream at a mass flow ratio of 1.23 t/(t clean syngas) at 4 bar(abs) and 35 °C.
  • the feed stream comprises 40 wt.-% carbon, 8 wt.-% hydrogen, 40 wt.-% oxygen, 1 wt.-% sulfur and 1 wt.-% nitrogen, rest percentage is ash.
  • gasification agents are injected into the fluidized bed reactor, enabling a gasification reaction at a temperature of 800°C.
  • the gasification agents are steam with a mass flow ratio of 0.62 t/(t clean syngas) at 5.4 bar(abs) and 180°C, as well as oxygen with a mass flow ratio of 0.41 t/(t clean syngas) at 25 °C and 6 bar(abs).
  • the resulting raw synthesis gas stream is sent to the top of the entrained flow gasifier whereby being kept at a temperature of 800 °C as a second stage and injected via the burner.
  • a bio oil is added as a second fuel to the entrained flow gasifier with a mass ratio of 0.12 t/(t clean syngas) at 100 °C and 20 bar comprising 50 wt.-% carbon, 5 wt.-% hydrogen and 45 wt.-% oxygen.
  • additional oxygen at a mass flow ratio of 0.26 t/(t clean syngas) at 15 bar(abs) and 100°C is used to increase the temperature up to 1350 °C at the gasifier outlet and convert remaining hydrocarbons, tars, and soot into synthesis gas.
  • the resulting high-temperature synthesis gas stream comprising CO, H2O, CO2, H2, CH4, H2S, N2, NHg, is washed with water and dried in order to reduce the amount of ash and tars.
  • the raw synthesis gas exits the wash and drying step at a temperature of 25 °C.
  • This example is a one-step gasification process comprising an entrained flow gasifier, converting a first feed stream of bio oil into a clean synthesis gas.
  • the entrained flow reactor is fed with the feed stream at a mass flow ratio of 0.57 t/(t clean syngas) at 50 bar(abs) and 100 °C.
  • the feed stream comprises 75 wt.-% carbon, 7 wt.-% hydrogen and 18 wt.-% oxygen.
  • gasification agents are injected into the reactor, enabling a gasification reaction at a temperature of 1350°C.
  • the gasification agents are steam with a mass flow ratio of 0.11 t/(t clean syngas) at 70 bar(abs) and 400°C, as well as oxygen with a mass flow ratio of 0.45 t/(t clean syngas) at 25 °C and 50 bar(abs).
  • the resulting raw synthesis gas stream is sent to the gasifier outlet.
  • the resulting high-temperature synthesis gas stream comprising CO, H2O, CO2, H2, CH4, H2S, N2, NH3, is washed with water and dried in order to reduce the amount of ash and tars.
  • the raw synthesis gas exits the wash and drying step at a temperature of 25 °C.
  • the acid gas removal is used to separate acids like H2S and CO2 with a mass flow ratio of 0.08 t/(t clean syngas) from the raw synthesis gas.
  • This example is a one-step gasification process comprising an entrained flow gasifier, converting a first feed stream of pyrolysis oil into a clean synthesis gas.
  • the entrained flow reactor is fed with the feed stream at a mass flow ratio of 0.51 t/(t clean syngas) at 50 bar(abs) and 100 °C.
  • the feed stream comprises 86 wt.-% carbon, 6 wt.-% hydrogen, 6 wt.-% oxygen and 2 wt.-% sulfur.
  • gasification agents are injected into the reactor, enabling a gasification reaction at a temperature of 1350°C.
  • the gasification agents are steam with a mass flow ratio of 0.10 t/(t clean syngas) at 70 bar(abs) and 400°C, as well as oxygen with a mass flow ratio of 0.41 t/(t clean syngas) at 25 °C and 50 bar(abs).
  • the resulting raw synthesis gas stream is sent to the gasifier outlet.
  • the resulting high-temperature synthesis gas stream comprising CO, H2O, CO2, H2, CH4, H2S, N2, NH3, is washed with water and dried in order to reduce the amount of ash and tars.
  • the raw synthesis gas exits the wash and drying step at a temperature of 25 °C.
  • the acid gas removal enabled by an amine scrubbing, is used to separate acids like H2S and CO2 with a mass flow ratio of 0.01 t/(t clean syngas) from the raw synthesis gas.
  • This example is a one-step gasification process comprising an entrained flow gasifier, converting a first feed stream of pyrolysis oil into a clean synthesis gas.
  • the entrained flow reactor is fed with the feed stream at a mass flow ratio of 0.51 t/(t clean syngas) at 50 bar(abs) and 100 °C.
  • the feed stream comprises 92 wt.-% carbon, 7 wt.-% hydrogen, 1 wt.-% oxygen and 0 wt.-% sulfur.
  • gasification agents are injected into the reactor, enabling a gasification reaction at a temperature of 1350°C.
  • the gasification agents are steam with a mass flow ratio of 0.10 t/(t clean syngas) at 70 bar(abs) and 400°C, as well as oxygen with a mass flow ratio of 0.41 t/(t clean syngas) at 25 °C and 50 bar(abs).
  • the resulting raw synthesis gas stream is sent to the gasifier outlet.
  • the resulting high-temperature synthesis gas stream comprising CO, H2O, CO2, H2, CH4, H2S, N2, NH3, is washed with water and dried in order to reduce the amount of ash and tars.
  • the raw synthesis gas exits the wash and drying step at a temperature of 25 °C
  • the acid gas removal enabled by an amine scrubbing, is used to separate acids like H2S and CO2 with a mass flow ratio of 0.01 t/(t clean syngas) from the raw synthesis gas.
  • This example is a one-step gasification process comprising an entrained flow gasifier, converting a first feed stream of pyrolysis oil into a clean synthesis gas.
  • the entrained flow reactor is fed with the feed stream at a mass flow ratio of 0.63 t/(t clean syngas) at 50 bar(abs) and 100 °C.
  • the feed stream comprises 70 wt.-% carbon, 3 wt.-% hydrogen, 23 wt.-% oxygen and 4 wt.-% sulfur.
  • gasification agents are injected into the reactor, enabling a gasification reaction at a temperature of 1350°C.
  • the gasification agents are steam with a mass flow ratio of 0.13 t/(t clean syngas) at 70 bar(abs) and 400°C, as well as oxygen with a mass flow ratio of 0.44 t/(t clean syngas) at 25 °C and 50 bar(abs).
  • the resulting raw synthesis gas stream is sent to the gasifier outlet.
  • the resulting high-temperature synthesis gas stream comprising CO, H2O, CO2, H2, CH4, H2S, N2, N H3, is washed with water and dried in order to reduce the amount of ash and tars.
  • the raw synthesis gas exits the wash and drying step at a temperature of 25 °C.
  • the acid gas removal is used to separate acids like H2S and CO2 with a mass flow ratio of 0.14 t/(t clean syngas) from the raw synthesis gas.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'un alcool choisi parmi le n-butanol et le 2-éthylhexanol, qui comprend la fourniture d'une charge d'alimentation de gazéifieur ; la gazéification de la charge d'alimentation de gazéifieur par oxydation partielle pour former un flux de gaz de produit brut comprenant une pluralité de gaz comprenant du méthane, de l'hydrogène et du monoxyde de carbone ; et la récupération de gaz de synthèse à partir du flux de gaz de produit brut. En outre, le procédé comprend l'obtention de propylène à partir d'éthanol d'origine renouvelable par soumission de l'éthanol d'origine renouvelable à une déshydratation pour produire un flux d'éthylène d'origine renouvelable ; et la soumission du flux d'éthylène d'origine renouvelable à une interconversion d'oléfine. Le propylène obtenu à partir d'éthanol d'origine renouvelable est mélangé avec du propylène non obtenu à partir d'éthanol d'origine renouvelable pour former du propylène mélangé ; et le propylène mélangé est soumis à une séquence de conversions chimiques pour obtenir du n-butanol ou du 2-éthylhexanol. Le procédé peut être facilement intégré dans un site de production existant, un ou plusieurs produits chimiques d'intérêt étant fabriqués sur la base d'une charge d'alimentation fossile, permettant au propylène à base de fossile d'être partiellement substitué par du propylène d'origine renouvelable.
PCT/EP2025/060833 2024-04-23 2025-04-22 Procédé de fabrication de n-butanol ou de 2-éthylhexanol renouvelable Pending WO2025224042A1 (fr)

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