WO2015027043A1 - Procédés, systèmes, et appareils pour l'hydrogénation à basse température d'une cire fischer-tropsch - Google Patents

Procédés, systèmes, et appareils pour l'hydrogénation à basse température d'une cire fischer-tropsch Download PDF

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Publication number
WO2015027043A1
WO2015027043A1 PCT/US2014/052052 US2014052052W WO2015027043A1 WO 2015027043 A1 WO2015027043 A1 WO 2015027043A1 US 2014052052 W US2014052052 W US 2014052052W WO 2015027043 A1 WO2015027043 A1 WO 2015027043A1
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Prior art keywords
wax
low
temperature
pressure
hydrogenation
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PCT/US2014/052052
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English (en)
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WO2015027043A4 (fr
Inventor
John Hemmings
Juan R. INGA
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Gi-Gasification International (Luxembourg), S.A.
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Priority to EP14837199.0A priority Critical patent/EP3036210A4/fr
Priority to US14/904,122 priority patent/US20160168486A1/en
Priority to CA2918834A priority patent/CA2918834C/fr
Publication of WO2015027043A1 publication Critical patent/WO2015027043A1/fr
Publication of WO2015027043A4 publication Critical patent/WO2015027043A4/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
    • B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
    • B01J8/224—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement
    • B01J8/226—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement internally, i.e. the particles rotate within the vessel
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/005—Separating solid material from the gas/liquid stream
    • B01J8/006—Separating solid material from the gas/liquid stream by filtration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
    • B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
    • B01J8/224—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement
    • B01J8/228—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement externally, i.e. the particles leaving the vessel and subsequently re-entering it
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/14—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles
    • C10G45/16—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles suspended in the oil, e.g. slurries
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/22—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with hydrogen dissolved or suspended in the oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/66—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins with moving solid particles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/04—Oxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
    • C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00212—Plates; Jackets; Cylinders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00823—Mixing elements
    • B01J2208/00831—Stationary elements
    • B01J2208/0084—Stationary elements inside the bed, e.g. baffles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00823—Mixing elements
    • B01J2208/00858—Moving elements
    • B01J2208/00867—Moving elements inside the bed, e.g. rotary mixer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
    • B01J2208/023—Details
    • B01J2208/024—Particulate material
    • B01J2208/025—Two or more types of catalyst
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature

Definitions

  • This invention relates to a system and method for treating hydrocarbon waxes; specifically it relates to a system and method for improving the color of waxes produced by a Fischer-Tropsch process.
  • Fischer-Tropsch or "Fischer Tropsch,” “F-T” or “FT”
  • FT Fischer Tropsch
  • FT hydrocarbons liquid hydrocarbons
  • the FT process is utilized to produce petroleum substitutes, typically from carbon-containing energy sources such as coal, natural gas, biomass, or carbonaceous waste streams (such as municipal solid waste) that are suitable for use as synthetic fuels, waxes and/or lubrication oils.
  • the carbon-containing energy source is first converted into a reformed gas (or synthetic gas or syngas), using a syngas preparation unit in what may be called a syngas conversion.
  • a syngas conversion is used as an input to an FT reactor having an FT catalyst to make the liquid FT hydrocarbons in a Fischer-Tropsch synthesis (or FT synthesis or FT conversion).
  • FT conversion of the syngas to liquid FT hydrocarbons takes place under appropriate operating conditions.
  • syngas preparation may involve technologies such as steam methane reforming, gasification, carbon monoxide shift conversion, acid gas removal gas cleaning and conditioning. These steps convert the carbon-containing energy source to simple molecules, predominantly carbon monoxide and hydrogen, which are the active ingredients of synthesis gas.
  • the synthesis gas w ll also inevitably contain carbon dioxide, water vapor, methane, nitrogen, impurities deleterious to catalyst operation such as sulfur and nitrogen compounds are often present in trace amounts and are removed to very low concentrations as part of synthesis gas conditioning.
  • syngas conversion step to create the syngas from natural gas, for example, methane in the natural gas reacts with steam and oxygen in a syngas preparatio unit to create syngas.
  • the syngas comprises principally carbon monoxide, hydrogen, carbon dioxide, water vapor and unconverted methane.
  • partial oxidation is used to produce the synthesis gas, typically, the syngas contains more carbon monoxide and less hydrogen than is optimal and consequently, steam is added to the react with some of the carbon monoxide in a water-gas shift reaction.
  • the water gas shift reaction can be described as:
  • the syngas is used as an input to an FT reactor having an FT catalyst to make the liquid FT hydrocarbons in a Fischer-Tropsch synthesis (or FT synthesis or FT conversion).
  • FT Fischer-Tropsch
  • the FT conversion of the syngas to liquid FT hydrocarbons takes place under appropriate operating conditions.
  • the Fischer-Tropsch (FT) reactions for the FT conversion of the syngas to the liquid FT hydrocarbons may be simplistically expressed as:
  • FT tail gases gases
  • FT water water
  • the FT tail gases typically contain CO (carbon monoxide), C0 2 (carbon dioxide), H 2 (hydrogen), light hydrocarbon molecules, both saturated and unsaturated, typically having carbon values ranging from Ci to CA, and a small amount of light oxygenated hydrocarbon molecules such as methanol.
  • FT tail gases are mixed in a faciiitv's fuel gas system for use as fuel.
  • the FT water will typically include dissolved oxygenated species, such as alcohols, and light hydrocarbons, which are typically removed prior to disposal of the FT water.
  • the FT reaction is performed in the presence of a catalyst called a Fischer-Tropsch catalyst ("FT catalyst").
  • FT catalyst a catalyst does not participate in the chemical reaction and is not consumed by the reaction itself.
  • a catalyst may participate in multiple chemical transformations. Catalytic reactions have a lower rate-limiting free energy of activation than the corresponding un-catalyzed reaction, resulting irs higher reaction rate at the same temperature.
  • the mechanistic explanation of catalysis is complex. Catalysts may affect the reaction environment favorably, or bind to the reagents to polarize bonds, e.g.
  • acid catalysts for reactions of carbonyl compounds, or form specific intermediates that are not produced naturally such as osmate esters in osmium tetroxide-catalyzed dihydroxylation of alkenes, or cause lysis of reagents to reactive forms, such as atomic hydrogen in catalytic hydrogenation, Irs addition to FT catalysts, other catalysts may also be used in other steps of an FT process.
  • the FT process results in longer-chain hydrocarbons than the feedstock, mainly n- paraffms, but with small amounts of impurities, such as branched chain material (for example, 2-rnethyl and 3-methyl derivatives), alpha olefins and oxygenates.
  • the n-paraffins have a full range of carbon numbers from Ci to well above Cioo- Lighter materials C
  • the lighter materials contain substantial amounts of alpha olefins (i.e. ethylene, propylene and 1 - butene.
  • Products of a typical FT process may include FT naphtha (which may have carbon numbers C5.
  • FT diesel which may have carbon numbers C9 to C25
  • FT wax mostly C2 0+ materia!
  • olefins and oxygenates are an unsaturated hydrocarbon with a carbon-carbon double bond.
  • Oxygenates mean compounds such as alcohols, aldehydes, ketones and carboxyhc acids that have an oxygen-containing group as a termination group (in the case of alcohols, carboxylic acids and aldehydes), or contained within (in the case of ketones) a predominantly paraffinic carbon/hydrogen chain.
  • the olefins may react with oxygen via a process that leads to the production of aldehydes and ketones associated with an undesirable odor.
  • Pure paraffin hydrocarbons are transparent and colorless as a liquid and colorless to white (Sayboit 30) as a solid.
  • Untreated FT wax tends to be colorless to light yellow (liquid), white to off-white (solid) and the color tends to deteriorate in storage.
  • Olefins in FT waxes are unstable with respect to oxygen, if an olefin becomes an oxygenated compound, it may become rancid and may cause problems with color or odor in the FT wax.
  • a. fixed bed FT reactor is used with a synthetic gas (“syngas") made from a feedstock
  • the amount of impurities, such as olefins and oxygenates, contained in the untreated FT wax may depend on the catalyst used.
  • use of an iron-based catalyst with a syngas in a fixed bed FT reactor may result in the an FT wax having up to about 20% olefins and oxygenates
  • use of the same elements, except with a typical cobalt-based catalyst may result in the FT wax having up to only about less than 3% olefins and about less than 0.1 % oxygenates
  • Hydrogenation can be used to remove impurities such as olefins and oxygenates from FT wax.
  • trickle bed reactors packed with catalyst, have been used for FT wax hydrogenation. Hydrogen and wax are generally added as inputs at the top of the reactor and products are collected at or near the bottom of the reactor. These systems work with a constant flow of FT wax and they work well when the FT wax is heavily contaminated, such as in the case of when a fixed bed FT reactor is used with iron-based catalysts to produce FT products.
  • the trickle bed reactors operate at high temperatures and high pressures and are, accordingly, expensive.
  • the size of the catalyst particles used in beds with trickle bed hydrogenation reactors is generally larger than one millimeter in diameter, to avoid a high pressure drop through the reactor.
  • the trickle bed reactors often require between 20 and 50 molecules of hydrogen for every one molecule of hydrogen consumed during the process. Hydrogen is generally collected, compressed and recycled.
  • oils of plant or animal origin differ considerably from FT waxes. Hydrogenation is sometimes used for plant or animal oi!s to address other issues not presented with FT waxes, such as adding a desired texture.
  • the concerns in the edible oil industry are different from concerns with respect to an FT wax. As an example, in edible oils, trans-oiefms can be a concern. Trans-olefins are not present in FT waxes. In FT waxes, the concerns focus on alpha olefins,
  • a starting hydrogen demand is a ratio of the double bonds present to the total carbon present in an oil.
  • edible oils are triglycerides of Qo to C20 fatty acids, each fatty acid having between zero and four double bonds. Therefore, a typical chemical hydrogen demand for an edible oil would likely be between 0.002 and 0.006 kg-mois kg.
  • an FT wax might have a carbon number of 20 (C20) or above and three percent of such molecules on average have a single double-bond, yielding a typical chemical hydrogen demand of 0.0001 kg-mols kg.
  • the chemical hydrogen demand is substantially higher than is the case for a Fischer Tropsch wax.
  • Methods in one of more embodiments of the present disclosure for hydrogenating a Fischer-Tropsch (“FT") wax include placing the FT wax at a low temperature up to a predetermined level within a low-temperature hydrogenation reactor having a mixing sub-system and a vent at the top and containing hydrogenating catalyst particles, , leaving a vapor space above the predetermined level.
  • FT Fischer-Tropsch
  • the method also includes adding a hydrogen gas under pressure into the low-temperature hydrogenation reactor, bringing the low-lemperature hydrogenation reactor up to a pre-deterniined operating pressure, The method further includes mixing the input FT wax, the hydrogen gas and the hydrogenation catalyst particles together using the mixing subsystem under operating conditions including a low temperature and the pre-determined operating pressure to create a mixture, thus permitting the FT wax to become hydrogenated, and stopping the mixing to allow the hydrogenation catalyst particles to settle for a period of time, and removing the hydrogenated FT wax with residual hydrogenating catalyst particles from the low-temperature hydrogenation reactor.
  • a method for hydrogenating a Fischer-Tropsch (“FT") wax includes the steps of (1) placing an input FT wax, at a low temperature of below about 200° C, up to a predetermined level within a low- temperature, low-pressure hydrogenation reactor, having a mixing sub-system comprising a hollow shaft gas impeller system, having a vent at the top and containing hydrogenation catalyst particles, leaving a vapor space above the predetermined level; (2) adding hydrogen gas under pressure to the low-temperature low-pressure hydrogenation reactor, bringing the low-temperature low-pressure hydrogenation reactor up to a pre-determined low f operating pressure of below about 100 psig; (3) mixing the input FT wax, the hydrogen gas and the hydrogenation catalyst particles together using the mixing subsystem under operating conditions including a low temperature and the pre-determined operating pressure to create a mixture, thus permitting the FT wax to become hydrogenated; (4) depressurizing the low-temperature low-pressure hydrogenation reactor; (5) flushing the hydrogen gas from
  • a system for hydrogenating an FT wax includes hydrogenation reactor for FT wax, designed for low temperature conditions and a pre-determined operating pressure.
  • the hydrogenation reactor for FT wax has a mixing sub-system, a vent at the top for excess hydrogen, a first inlet to allow input of hydrogen gas under pressure, and a second inlet to allow input of the FT wax.
  • the mixing subsystem is suitable for mixing the FT wax at a low temperature and the pre-determined operating pressure with a plurality of hydrogenation catalyst particle and hydrogen gas to produce a mixture.
  • an apparatus for hydrogenating FT wax includes a hydrogenation reactor shell designed for low temperature and low pressure operating conditions and having a vent at the top for excess hydrogen, a First inlet in the hydrogenation reactor shell to allow hydrogen gas to enter the hydrogenation reactor shell under a low pressure, a second inlet suitable for an FT wax. a third inlet to allow input of hydrogen gas and an outlet to allow egress of a fluid including hydrogenated FT wax.
  • the apparatus further includes a mixing mechanism inside the hydrogenation reactor shell, suitable for mixing a mixture comprised of hydrogenation catalyst particles with the FT wax and the hydrogen gas to facilitate hydrogenating the FT wax.
  • Fie 1 is a block diagram, of a system in accordance with one or more embodiments of the present disclosure.
  • FIG, 2 is a more detailed representation of a low-temperaiure, Sow-pressure reactor and catalyst filter in accordance with one or more embodiments of the present disclosure
  • FiG. 3 is a block diagram of a system in accordance with one or more embodiments of the present disclosure
  • FIG. 4 is a flowchart for a process in accordance with one or more embodiments of the present disclosure, through a filtration step;
  • FIG. 5 is a flowchart for a process in accordance with one or more embodiments of the present disclosure, through a step separating the hydrogenated FT wax into two or more products.
  • the term "low-pressure" with respect to a hydrogenation reactor means below about 350 psig. While pressures above this level are still in the scope of this disclosure, the pressure is typically limited to be below a pressure at which (given the anticipated temperatures and selected metallurgy) the flange rating jumps from ANSI Class 300 to ANSI Class 600, in order to keep costs low,
  • the term "low-temperature" with respect to a hydrogenation reactor means under about 280° C. Ideally, in a 'low temperature" hydrogenation reactor, the temperature of the FT wax within the hydrogenation reactor would he high enough so that the wax is liquid, but low enough that hydrocracking of the FT wax is not significan
  • raw with respect to a wax means a wax that has not been chemically treated.
  • sweet natural gas means natural gas from which any- excess sulfur or sulfur compounds such as H 2 S has been previously removed.
  • FT Fischer-Tropsch
  • FT products means hydrocarbon products produced from an FT reactor.
  • FT wax means a wax made using a Fischer Tropsch process.
  • the terms "reformed gas” or “syngas” means the effluent from a syngas conversion unit, such as (without limitation) a steam methane reformer, autothermal reformer, hybrid reformer, or partial oxidation reactor.
  • Steam methane reformers do not use oxygen as part of the process; autothermal reformers do. Both use reformer catalysts.
  • Hybrid reformers are a combination of steam methane reforming, as a first step, and an autothermal reforming with oxidaiion as a second step.
  • Partial oxidation reactors are similar to autothermal reformers, but do not include the use of a reformer catalyst. Partial oxidation reactors operate in accordance with the following equation:
  • hydrogenation means a reduction reaction thai results in an addition of hydrogen (usually as H 2 ). If an organic compound is hydrogenated, it becomes more"saturated.” Hydrogenation has many applications, but most people are familiar with the reaction as the one used to make liquid oils into semi-solid and soiid fats. Hydrogenation is a form of hydrotreating, which also includes many other treatments. For example, hydrogenation may be done without hydrocracking, which is another form of hydrotreating, but hydrocracking includes hydrogenation.
  • FlG. 1 is a block diagram, of a Fischer-Tropsch ("FT") wax hydrogenation system in accordance with one or more embodiments of the present disclosure.
  • An input wax 10 and hydrogen gas (H?) IS are introduced into a low-temperature, Sow-pressure hydrogenation reactor 20 through first and second inlets 11, 16.
  • the low-temperature, low-pressure hydrogenation reactor 20 contains hydrogenation caiaiyst particles 22,
  • the input wax 10 fills the Sow-temperature, low-pressure hydrogenation reactor 20 containing the hydrogenation catalyst particles 22 to a desired volume, leaving a vapor space 26 above the top 29 of the input wax lOand the hydrogenation catalyst particSes 22.
  • the hydrogenation catalyst particles 22 may have been placed within the low-temperature, low-pressure hydrogenation reactor 20 through a catalyst inlet (not separately depicted in FIG. 1) of the low-temperature, low-pressure hydrogenation reactor 20.
  • the input wax 1 comprises a Fischer-Tropsch ("FT') wax, which may be raw, and preferably, an FT wax produced by using a synthetic gas (“syngas”) with a fixed bed FT reactor and a cobalt-based FT catalyst to turn the syngas into FT products.
  • the input wax 10 may comprise in part olefins and oxygenates.
  • the input wax 10 may be transported from an FT wax source, such as an FT plant, via, for example, a tanker truck or a flowline.
  • the hydrogen gas IS is added under pressure into the low- temperature, low-pressure hydrogenation reactor 20 after the input wax is in place.
  • the addition of the hydrogen gas IS pressurizes the interior of the low-temperature, low-pressure hydrogenation reactor 20 to the desired operating pressure.
  • the hydrogen gas 15 may be delivered to the low-temperature, low-pressure hydrogenation reactor 20, for example, via tanker truck, tanks or via a flowline or from a hydrogen flowline.
  • the first iniet il for the input wax 10 and a second inlet 16 for the hydrogen gas 15 may be placed anywhere on the low- temperature, low-pressure hydrogenation reactor 20, but it may be preferable to place both the first inlet 11 and the second inlet 16 in the lower half of the low-temperature, low-pressure hydrogenation reactor 20, to improve mixing, in other embodiments, the wax inlet and/or the hydrogen iniet may be placed at the top of the low-temperature, low-pressure hydrogenation reactor 20or at other locations.
  • the low-temperature, low-pressure hydrogenation reactor 20 also includes a stirrer 24 or other type of mixing mechanism in its interior. The purpose of the stirrer is to keep the catalyst particles in suspension and to mix the hydrogen with the input wax 10.
  • FIG. 2 A more detailed view of a low-temperature, low-pressure hydrogenation reactor 20 that may be used in accordance with one or more embodiments of the present disclosure is depicted in FIG. 2.
  • the maximum size of the hydrogenation catalyst particles 22 used should generally be no greater than about 250 microns, so that the hydrogenation catalyst particles 22 may be suspended within the input wax 10 in the low-temperature, low-pressure hydrogenation reactor 20. if comparing the same volume of hydrogenation catalyst, hydrogenation catalyst particles with a smaller size will provide a greater surface area, meaning one can use less hydrogenation catalyst to treat a particular volume of wax.
  • Examples of the hydrogenation catalyst particles 22 that may be used in accordance with one or more embodiments of the present disclosure include edible oil hydrogenation catalysts, such as skeletal nickel catalysts or palladium-containing catalysts.
  • the hydrogenation catalyst particles 22 may comprise a single type of catalyst particles or may comprise a cataiyst mixture of two or more types of catalyst particles.
  • At least one of the types of catalyst particles in the catalyst mixture would be suitable for hydrogenation.
  • one or more other types of catalyst particles making up the catalyst mixture could have other (non-hydrogenation) functions, such as oligomerization, isomerization, or cracking.
  • a process might include a first step of oligomerization performed under a nitrogen-containing atmosphere with typical conditions of a low temp (about 150° C.) and moderate pressure (about 150 psig), followed by a second step of hydrogenation as previously described.
  • a process might include simultaneously isomerizing and hydrogenating the FT wax at conditions as previously described for hydrogenation.
  • a process might include a first step of hydroeracking (which includes hydrogenation) at temperatures above 300" C. (for example, 350° C.) with hydrogen at a pressure of 350-350 psig, followed by a second step of finishing hydrogenation at previously described hydrogenation conditions.
  • the stirrer 24 mixes the hydrogen 15 and input wax 10 with the hydrogenation catalyst particles 22 within the low-temperature, low-pressure hydrogenation reactor 20 under operating conditions to form a slurry or mixture.
  • the stirrer 24 may comprise for example a gas induction impeller, having a motor arid gear box 17 and a sealing mechanism 18 or a liquid pump around with an eductor, to efficiently mix hydrogen 15 with the input wax 10 and hydrogenation catalyst particles 22.
  • Other mixing or stirring mechanisms may also be used. For example, see US Patent No. 7,815,1 6, entitled “Magnetic Seal Assembly," and gas induction reactors available from Omega Kemix Pvt. Ltd:
  • stirrer in accordance with one or more embodiments of the present disclosure includes a separate device to circulate hydrogen IS to a sparger, although this option may be more expensive than previously mentioned alternatives.
  • the hydrogen IS in a hydrogenation reaction process, as the hydrogen IS is mixed as part of the slurry with the hydrogenation catalyst particles 22 and the input wax 10, the hydrogen IS saturates carbon double bonds of the olefins and the carbon-oxygen bonds of the oxygenates within the input wax 10 to form paraffins and water.
  • the hydrogenation reaction process of the present disclosure may be performed in a batch mode, in a semi-batch mode (having staged additions of ingredients and removal of product) or, in one or more embodiments, may be performed in a continuous mode.
  • a typical operating temperature for the low-temperature, low-pressure hydrogenation reactor 20 ranges from about 100" to about 280° C, preferably, from about 150° to about 250° C, and more preferably from about 200" to about 230' C. Ideally, the temperature range selected would be high enough that the input wax 10 is in a liquid form, but low enough that any hydroeracking that might incidentally take place is limited to a desired, very low level or avoided. [00S0J
  • a typical operating pressure for the Sow-temperature, low-pressure hydrogenation reactor 20 range from about 0 psig to about 350 psig, preferably from about 50 psig to about 350 psig, and more preferably from about 250 psig to about 350 psig. Although the low operating pressure may provide a significant cost advantage, higher pressures couid be also used, with equipment designed to handle the high pressures.
  • a hydrogen gas vent 28 allows excess hydrogen to pass from the vapor space 26 in the low-temperature, low-pressure hydrogenation reactor 20 to a flowline to a desired destination.
  • the hydrogen gas vented from the low- temperature, low-pressure hydrogenation reactor 20 may be sent to a burner for downstream process heating, recycled such as via a compressor or to a flare for disposal.
  • the hydrogenated wax 25, passes through a reactor outlet 24 of the low-temperature, low-pressure hydrogenation reactor 20.
  • the hydrogenated wax 25 passing through the reactor outlet 24 may contain some hydrogenation catalyst particles 22 that have not settled out, such as fine hydrogenation catalyst particles.
  • the hydrogenated wax 25 passes via a first hydrogenated wax flowline to a catalyst filter 30.
  • the catalyst filter 30 removes hydrogenation catalyst particles 22 from the hydrogenated wax 25,
  • a back-flush fluid 32 enters the catalyst filter 30.
  • the backflush fluid and removed catalyst particles 36 is recycled via a backflush flowline to a third inlet in the low-temperature, low- pressure hydrogenation reactor 20.
  • the back-flush fluid 32 comprises the input wax 10 to the hydrogenation reactor, and the third inlet is the same as the first inlet.
  • a filtered hydrogenated wax 35 may pass through a second hydrogenated wax flowline to a filtered hydrogenated wax storage tank 40 or other storage container.
  • the filtered, hydrogenated wax 35 may be considered a product. However, the filtered, hydrogenated wax 35 might have too wide a distribution of carbon numbers to be appropriate for typical applications. Accordingly, it may be desirable to split the filtered, hydrogenated wax 35 into two or more products with properties conforming to market requirements, in the embodiment illustrated in FIG. 1, the filtered hydrogenated wax 35 is split into two products, a first wax product 70, which may have a medium melting point, and a second wax product 80, which may have a high melting point, in one or more embodiments of the present disclosure, the congeal point for the first wax product 70 may be about 60 " C, while the congeal poirsi for the second wax product ⁇ 0 may he about 95 " C.
  • the filtered hydrogenated wax 35 passes through a third hydrogenated wax flowline optionally to a heater 50, where the filtered hydrogenated wax 35 is pre-heaied in preparation for a short path distillation step, in other embodiments, the temperature of the filtered hydrogenated wax 35 may be such that additional heating is not required. For example, if the temperature of the filtered wax is already at about 200-250" C, then the heating step may not be needed, in FIG.
  • the heated, filtered hydrogenated wax 55 may pass through a fourth hydrogenated wax flowline to a short path distillation system 60, where the heated, filtered hydrogenated wax 55 is separated into the first wax product 70, having a medium melting point, and the second wax product 80, having a high melting point.
  • a vacuum system (not separately depicted) maintains a Sow absolute pressure within the short path distillation system 60.
  • other vacuum distillation methods or additional short path distillation stages may be used to separate the heated, filtered hydrogenated wax 55 into two or more wax products.
  • three or more wax products are made.
  • a non-condensable gas 62 passes through a port in the short path distillation system 60 and into a vacuum flowline 65 to the vacuum system.
  • the short path distillation system at vacuum conditions keeps required temperatures as low as possible and the residence time at elevated temperature as short as possible. This avoids secondary reactions (such as cracking) which may cause the quality of the FT wax products to deteriorate.
  • the second wax product 80 (having the high melting point) may require a second pass hydrogenalion, which could employ the same equipment as the first pass hydrogenalion process described above. This is simple to implement as the process may be conducted as a batch operation and consequently the same equipment could process alternate batches of raw wax and batches of heavy wax in campaigns.
  • the short path distillation system may comprise a plurality of wiped film evaporators and/or short path distillation units or a combination of both.
  • the short path distillation system may include a wiped film evaporator, followed by two short path distillation units in series,
  • FIG. 2 presents a more detailed representation of a low-temperature, low-pressure hydrogenation reactor 200 and a catalyst filter 230 in accordance with one or more embodiments of the present disclosure.
  • the FT wax enters the catalyst filter 230 from an FT wax flowline 202 and through first valve 203 as a back-flush fluid.
  • the FT wax leaves the catalyst filter 230 carrying recovered hydrogenation catalyst particles, through a second valve 234 and a back-flush flowline 233 and enters the low- temperature, low-pressure hydrogenation reactor 200.
  • the low-temperature, low-pressure hydrogenation reactor 200 includes at least one baffle 208 to enhance mixing.
  • the iow- temperature, low-pressure hydrogenation reactor 200 also includes a catalyst inlet 209, which can be used to load the catalyst or to add make-up catalyst, and a third valve 204.
  • the low- temperature, low-pressure hydrogenation reactor 200 preferably already contains a plurality of hydrogenation catalyst particles 222.
  • the FT wax 210 fills a voidage 227, which comprises space (or porosity) between the hydrogenation catalyst particles 222 within the low-temperature, low-pressure hydrogenation reactor 200 until a desired level 221 is reached, leaving a vapor space 226 inside the Sow-temperature, low-pressure hydrogenation reactor 220.
  • hydrogen gas can be added under pressure through a hydrogen inlet 216, and a fourth valve 205.
  • the addition of the hydrogen gas pressurizes the interior of the low-temperature, low-pressure hydrogenation reactor 200 to a desired operating pressure.
  • the vapor space 226 would contain hydrogen gas.
  • a hollow-shaft gas induction impeller 224 having a hollow shaft 212, an impeller blade 213, a motor and gear box 217 and a sealing mechanism 218stirs the FT wax, the hydrogen gas and the hydrogenation catalyst particles 222, creating a mixture and allowing a hydrogenation reaction to take place, under operating conditions of a temperature between about 80° C. and about 280" C. and a pressure selected between about atmospheric pressure and about 350 psi.
  • Hydrogen from the vapor space 226 enters one or more ports 223 of the gas induction impeller 224, and passes through the hollow shaft 212 and out of one or more outlets 214 preferably in the impeller blade 213, As the gas induction impeller 224 turns and mixes the hydrogen gas with the FT wax and the hydrogenation catalyst particles, the mixing facilitates dissolving the hydrogen gas into a mixture 201.
  • the surface area of the hydrogenation catalyst particles 222 facilitates the transfer of hydrogen to molecules of the olefins and oxygenates of the FT wax 2 ⁇ 0 at the molecular level.
  • the hydrogen gas terras bubbles, which rises through the mixture 201 to the vapor space 226, from which the hydrogen gas enters the hollow shaft 212.
  • a vent (not depicted in FIG. 2), at or near the top of the low-temperature, low-pressure hydrogenation reactor 220 allows excess hydrogen to escape, at times, through a vent flowline. For example, excess hydrogen may escape through the vent flowline intermittently or at the end of a
  • a heel 229 comprised of hydrogenated wax and catalyst particles is depicted as having been left in the low-temperature, low-pressure hydrogenation reactor 200, as the top of the heel 229 may be below the entry into the dip tube 227. In other embodiments, a heel may not be present. In a typical operation, the heel may be about 10% of the volume of the FT wax from a particular batch, but this may vary, in embodiments having a batch operation, the heel 229 may be mixed with and processed with the next batch of FT wax and hydrogen introduced into the low-temperature, low-pressure hydrogenation reactor 200.
  • the hydrogenated wax (with the hydrogenated catalyst particles the hydrogenated wax may be carrying) passes through a fifth valve 231 and into the catalyst filter 230.
  • the catalyst filter 230 is a single candle style filter. In alternate embodiments, the catalyst filter may comprise more than a single candle-style filter. In alternate embodiments, other the catalyst filter may comprise other types of filters.
  • the hydrogenated wax passes through the candle filter 232, which recovers the hydrogenated catalyst particles.
  • the filtered hydrogenated wax passes through a sixth valve 239 and a filtered hydrogenated wax flowline 237 to storage (not depicted in FIG. 2).
  • fresh FT wax can be used as a back-flush fluid to return the recovered hydrogenated catalyst particles to the low-temperature, low-pressure hydrogenation reactor 200.
  • FIG. 2 is one exampl of low-temperature, low-pressure hydrogenation reactor 200 that may be used with the present invention, many other types of low-temperature, low- pressure hydrogenation reactors, with different means for stirring or otherwise mixing the hydrogen gas, the inlet wax and the catalyst particles may also be used,
  • FlG. 3 is a biock diagram of one or more embodiments in accordance with the present disclosure.
  • An input FT wax is sent from tankers (not depicted) via a raw wax flowline 300 to a raw wax inlet 302 for a raw wax storage tank 301.
  • the input FT wax is an FT wax produced using a natural gas feedstock to create a syngas and a fixed bed FT reactor and a cobalt-based FT catalyst to turn the syngas to FT products, including the input FT wax.
  • other feedstocks could be used to create the syngas.
  • the input FT wax may contain one or more olefins and/or oxygenates with double carbon bonds.
  • the input FT wax is sent from a raw wax outlet 304 in the raw wax storage tank 301 through a first input flowline 305 to a first hydrogenator inlet 322 of a batch hydrogenator 320.
  • the batch hydrogenator 320 contains catalyst particles (not depicted), which has been added through the first hydrogenator inlet 322, the second hydrogenator inlet 323 or a separate catalyst inlet (not depicted).
  • the input FT wax is added into the batch hydrogenator 320 until a desired volume is reached, leaving a vapor space (not depicted) within the batch hydrogenator 320 above the top of the input FT wax and the catalyst particles.
  • the batch hydrogenator 320 may treat 5000 gallons of input FT wax in a single batch.
  • the batch hydrogenator 320 also includes a stirrer (not depicted) or other type of mixing mechanism in its interior to mix the input FT wax, the hydrogen and the catalyst particles.
  • the FT wax may be at a desired operating temperature when it enters the batch hydrogenator (with or without heating prior to entering the batch hydrogenator) or the batch hydrogenator 320may include a heating element, such as a jacket, to bring the FT wax to the desired operating temperature.
  • a heat exchanger 370 may be used to heat the FT wax to the desired operating temperature.
  • a fresh hydrogen gas feed is introduced under pressure from a hydrogen flowline 306 through a second hydrogenator inlet 323 in the batch hydrogenator 320, increasing the pressure of the batch hydrogenator 320 to a desired operating pressure,
  • a mixing system within the batch hydrogenator 320 mixes the hydrogen and input FT wax with the catalyst particles, creating a wax/catalyst /hydrogen mixture.
  • the mixing system may comprise, for example, a hollow-shaft gas induction impeller.
  • a hydrotreating reaction specifically, a hydrogenating reaction takes place, wherein the hydrogen reacts with the input FT wax to saturate the carbon double bonds of the olefins and break the carbon-oxygen bond of the oxygenates to form paraffins and water
  • a typical operating temperature for the batch hydrogenator 320 ranges from about 150° to about 280° C.
  • a typical operating pressure for the hatch hydrogenator 320 ranges from about 50 psi to about 350 psi.
  • the hydrogenating reaction is slightly exothermic (i.e., heat-creating).
  • Circulating some of the wax/cataiyst//hydrogen mixture through the (optional) external heat exchanger 370, as in FIG. 3, may be used heat (as previously mentioned) or, in some embodiments, to cool the wax/catalyst /hydrogen mixture and return the wax/catalyst /hydrogen mixture to the batch hydrogenator 320.
  • the cooling media may be a closed loop thermal fluid that stays above the melting point of the wax and in turn is to be indirectly water cooled.
  • a cooling jacket may be used on the batch hydrogenator 320.
  • a portion of the wax/catalyst /hydrogen mixture may be removed from the batch hydrogenator 320 through a first hydrogenator outlet 325 into a first mixture flowline 371, which carries the wax/catalyst /hydrogen mixture to a heat exchanger inlet 372, The portion of the wax/catalyst /hydrogen mixture passes through the heat exchanger inlet 372 into a heat exchanger 370, where the portion of the wax/catalyst /hydrogen mixture is heated (or, in alternate embodiments, is cooled).
  • the heated (or, in alternate embodiments, cooled) portion of the wax/catalyst /hydrogen mixture is returned to the batch hydrogenator 320 by passing through a heat exchanger outlet 374, a second mixture flowline 375 and a third hydrogenator inlet 326.
  • a hydrogenator gas vent 324 of the batch hydrogenator 320 may allow excess hydrogen to pass from the vapor space though a first vent gas flowline 328 to a desired destination.
  • the vented excess hydrogen may be sent to a burner for downstream process heating or to a flare for disposal.
  • a hydrogenated FT wax (which likely contains some catalyst particles) passes through a second hydrogenator outlet 327 of the batch hydrogenator 320 and through a first hydrogenated wax flowline 332 into a catalyst filter 330 via a filter inlet 333.
  • the catalyst filter 330 removes catalyst particles from the hydrogenated FT wax, creating a filtered hydrogenated FT wax.
  • a first backflush fluid with removed catalyst particles is recycled out of the catalyst filter via a first backflush outlet 334.
  • the first backflush fluid with removed catalyst particles is sent via a first backflush flowline 335 to a fourth hydrogenator inlet 329 in the batch hydrogenator 320, where the first backflush fluid with removed catalyst particles can be mixed with the next batch of raw FT wax and hydrogen to be treated.
  • the filtered hydrogenated FT wax may pass from the catalyst filter 330 through a filter outlet 336 via a first filtered wax flowline 337 to a second tank inlet 342 of a hydrogenated wax storage tank 340 or other storage container.
  • a second backflush that comprises filtered hydrogenated FT wax may be sent from the hydrogenated wax storage tank 340 to a second filter inlet 338 of the catalyst filter 330 via a second backtlush outlet 344 and a second backtlush flowline 345.
  • the filtered hydrogenated FT wax 335 passes through a hydrogenated wax storage tank outlet 346 and a second filtered wax flowline 348 to an optional heater 350 via a heater inlet 352.
  • the heater 350 heats the filtered hydrogenated FT wax, creating a heated, filtered hydrogenated FT wax.
  • the heated, filtered hydrogenated FT wax passes from the heater 3S0 via a heater outlet 354 and through a third filtered wax flowline 355 to a degasser 390, which removes a vent gas from the heated, filtered, hydrogenated FT wax, creating a de-gassed, heated, filtered, hydrogenated FT wax.
  • the vent gas leaves the degasser 390 through a degasser vent 394 and passes through a vent flowline 395 to a vacuum system (not depicted in FiG. 3) or other desired location.
  • the degassed, heated, filtered, hydrogenated FT wax flows through a fifth filtered wax flowline 398 to a short path distillation system 360, where the de-gassed, heated, filtered, hydrogenated FT wax is separated into a first wax product and second wax product, each of which are sent via a first distillation system outlet 365 and a second distillation system outlet 367 to separate storage (not depicted in FiG. 3) via separate first and second product f!owlines 372, 382.
  • a distillation vent gas passes through a short-path distillation vent 363 and via a connection flowline 364 into the vent flowline 395 to the vacuum system or other desired location.
  • FJG. 4 is a flowchart for a process in accordance with one or more embodiments of the present disclosure. Unless already in place from a previous operation, hydrogenating catalyst particles are placed 405 within a low-temperature, low-pressure hydrogenation reactor having a mixing sub-system and a vent at the top for excess hydrogen.
  • An input FT wax at a desired temperature is placed 410, up to a predetermined level, within the low-temperature, low-pressure hydrogenation reactor, leaving a vapor space above the predetermined level
  • Hydrogen gas is added 415 usi er pressure, bringing the low-temperature, low-pressure hydrogenation reactor up to a desired operating pressure.
  • the input FT wax, the hydrogen gas and the hydrogenating catalyst particles are mixed 420 together to create a mixture using the mixing subsystem.
  • the mixing is intended to suspend the hydrogenating catalysi panicles in the mixture and to disperse bubbles of hydrogen gas throughout the mixture.
  • the mixing subsystem may comprise, for example, a hollow-shaft gas induction impeller.
  • the mixing preferably continues until a hydrogenating reaction has taken place within the mixture.
  • Typical operating conditions for the hydrogenation reactor include a temperaiure between about 80° C. and about 280" C. and a pressure selected between about atmospheric pressure and about 350 psi.
  • the mixing is stopped 425 to allow the hydrogenating caialyst particles io settle from the mixture,
  • a hydrogenated FT wax which may include non-settled ("residual") hydrogenating catalyst particles, is removed 430 through an outlet from the low-temperature, low-pressure hydrogenation reactor.
  • the hydrogenated FT wax and the residual hydrogenating catalysi particles are passed 435 through a catalyst filter to remove the residual hydrogenating catalyst particles arid to create a filtered hydrogenated FT wax.
  • the filtered hydrogenated wax may be stored 440 prior to further processing or transportation.
  • [0966J FiG. 5 is a flowchart for a process in accordance with one or more embodiments of the present disclosure.
  • Hydrogenation catalyst particles are placed 505 within a low- temperature, low-pressure hydrogenation reactor having a mixing sub-system and a vent at the top for excess hydrogen.
  • Step 505 may be skipped if sufficient hydrogenation catalyst particles are already in place, for example in a heel left from a previous operation.
  • An input FT wax at a desired temperature is placed 510, up to a predetermined level, within the low- temperature, low-pressure hydrogenation reactor, leaving a vapor space above the predetermined level.
  • the FT wax may be heated before placed within the low- temperature, low-pressure hydrogenation reactor, in one or more embodiments, the FT wax is heated to the desired temperaiure after being placed in the low-temperature, low-pressure hydrogenation reactor, such as through use of a heat exchanger system.
  • Hydrogen gas under pressure is added SIS to the low-temperature, low-pressure hydrogenation reactor, bring the low-temperature, low-pressure hydrogenation reactor up to a desired operating pressure, Under operating conditions including a low temperature and a low pressure, the input FT wax, the hydrogen gas and the hydrogenating catalyst particles are mixed 520 together to create a mixture using the mixing subsystem.
  • typical operating conditions for the hydrogenaiion reactor include a temperature between about 80° C, and about 280" C. and a pressure selected between about atmospheric pressure and about 350 psi.
  • the pressure is preferably so limited to allow use of ANSI 300 flanges, but higher pressures could be used.
  • the mixing stops and the low-temperature, low-pressure hydrogenaiion reactor is depressurized 525.
  • An inert gas, such as nitrogen, is added 530 to the low- temperature, low-pressure hydrogenaiion reactor at a lo pressure, preferably about 50 psig, to flush the hydrogen gas from the low-temperature, low-pressure hydrogenaiion reactor.
  • the hydrogenaiion catalyst particles are allowed S3S to settle for a pre-determined time,
  • the hydrogenated FT wax which may include residual hydrogenaiion catalyst particles, is removed 540 from the low-temperature, low-pressure hydrogenaiion reactor. A heel of settled catalyst particles and some hydrogenated FT wax may be left within the low- temperature, low-pressure hydrogenaiion reactor.
  • the hydrogenated FT wax and residual hydrogenaiion catalyst particles are passed 545 through a catalyst filter to remove the residual hydrogenaiion catalyst particles and to create a filtered hydrogenated FT wax.
  • the filtered hydrogenated FT wax may be stored 550 if further processing is not immediately desired. When further processing is desired, the stored, filtered hydrogenated FT wax is released 555 from storage.
  • the filtered hydrogenated FT wax may be heated 560 in order to help the filtered hydrogenated FT wax to flow.
  • the filtered hydrogenated FT wax next passes to a degasser, where the heated, filtered hydrogenated FT wax is de-gassed 570.
  • the gas removed from the filtered hydrogenated FT wax passes through a degasser vent to a vacuum system, or other desired location.
  • gas leaving the degasser is cooled in a condenser or cold trap, which recovers some light liquids with the non- condensable material passing to a first stage of the vacuum system.
  • the discharge from the first stage vacuum pump goes to flare or other suitable location.
  • the de-gassed, filtered hydrogenated FT wax is separated 580 into at least two FT wax products, including a lower melting point FT wax product and a higher melting point FT wax product.
  • the separation may be accomplished using a short path distillation unit or by other separation systems.
  • the lower melting point FT wax product is sent 582 to storage.
  • the higher melting point FT wax product is sent 584 to the low-temperature, low-pressure hydrogenaiion reactor for additional hydrogenaiion.
  • the higher melting point FT wax product is sent to storage, in alternate embodiments, the higher melting point FT wax product is sent to a second low temperature, low pressure hydrogenation reactor for additional hydrogenaiion.
  • the de-gassed, filtered, hvdrogenated FT wax is separated into at least three FT wax products,

Abstract

Cette invention concerne un procédé d'hydrogénation d'une cire Fischer-Tropsch ("FT") consistant à placer des particules de catalyseur d'hydrogénation dans un réacteur d'hydrogénation à basse température comportant un sous-système de mélange et un évent à son sommet pour évacuer l'hydrogène en excédent, à introduire la cire FT à basse température jusqu'à un niveau prédéfini dans le réacteur d'hydrogénation à basse température, à laisser un espace de vapeur au-dessus dudit niveau prédéfini, à ajouter l'hydrogène à la pression souhaitée dans le réacteur d'hydrogénation à basse température, à mélanger la cire FT introduite, le gaz hydrogène et les particules du catalyseur d'hydrogénation pour former un mélange à l'aide du sous-système de mélange et à continuer à mélanger jusqu'à ce que la cire FT soit hydrogénée, à arrêter de mélanger pour laisser les particules du catalyseur d'hydrogénation se décanter, et à retirer une cire FT hydrogénée et des particules de catalyseur d'hydrogénation résiduelles du réacteur d'hydrogénation à basse température. La cire FT hydrogénée peut être filtrée et soumise à une distillation sous vide. D'autres modes de réalisation sont également décrits.
PCT/US2014/052052 2013-08-21 2014-08-21 Procédés, systèmes, et appareils pour l'hydrogénation à basse température d'une cire fischer-tropsch WO2015027043A1 (fr)

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EP14837199.0A EP3036210A4 (fr) 2013-08-21 2014-08-21 Procédés, systèmes, et appareils pour l'hydrogénation à basse température d'une cire fischer-tropsch
US14/904,122 US20160168486A1 (en) 2013-08-21 2014-08-21 Methods, systems, and apparatuses for low-temperature, fischer-tropsch wax hydrogenation
CA2918834A CA2918834C (fr) 2013-08-21 2014-08-21 Procedes, systemes, et appareils pour l'hydrogenation a basse temperature, d'une cire fischer-tropsch

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US61/868,509 2013-08-21

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WO2017037177A1 (fr) * 2015-09-04 2017-03-09 Shell Internationale Research Maatschappij B.V. Procédé pour préparer des paraffines et des cires
EP3342842A1 (fr) * 2017-01-03 2018-07-04 Total Marketing Services Procédé de déparaffinage et désaromatisation d'hydrocarbure dans un bioréacteur à boues liquides

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CN107325838B (zh) * 2017-08-04 2019-01-25 赛鼎工程有限公司 一种费托合成粗产品的分离方法
CN109749841B (zh) * 2019-01-30 2021-07-09 四川锐恒润滑油有限公司 一种润滑油基础油提取精制系统及工艺
CN114196434B (zh) * 2022-02-18 2022-06-03 东营市东泽化工科技有限公司 一种轻芳烃加氢改造设备

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US20160168486A1 (en) 2016-06-16
CA2918834A1 (fr) 2015-02-26
WO2015027043A4 (fr) 2015-04-30
EP3036210A1 (fr) 2016-06-29
CA2918834C (fr) 2019-08-20

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