EP3191433A1 - Procédé et installation pour la production d'hydrocarbures - Google Patents

Procédé et installation pour la production d'hydrocarbures

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Publication number
EP3191433A1
EP3191433A1 EP15766101.8A EP15766101A EP3191433A1 EP 3191433 A1 EP3191433 A1 EP 3191433A1 EP 15766101 A EP15766101 A EP 15766101A EP 3191433 A1 EP3191433 A1 EP 3191433A1
Authority
EP
European Patent Office
Prior art keywords
butene
stream
hydrocarbons
butane
effluent
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.)
Withdrawn
Application number
EP15766101.8A
Other languages
German (de)
English (en)
Inventor
Torben HÖFEL
Helmut Fritz
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.)
Linde GmbH
Original Assignee
Linde GmbH
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Filing date
Publication date
Application filed by Linde GmbH filed Critical Linde GmbH
Publication of EP3191433A1 publication Critical patent/EP3191433A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/245—Stationary reactors without moving elements inside placed in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/04—Thermal processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
    • C07C5/25—Migration of carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2767—Changing the number of side-chains
    • C07C5/277—Catalytic processes
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/40—Thermal non-catalytic treatment
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • C10G3/52—Hydrogen in a special composition or from a special source
    • 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/28—Propane and butane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • the invention relates to a method and a plant for the production of
  • Short-chain olefins such as ethylene and propylene can be prepared by steam cracking.
  • oxygenate to olefin Oxygenates to Olefins, OTO
  • oxygenates such as methanol or dimethyl ether are introduced into a reaction zone of a reactor in which a catalyst suitable for reacting the oxygenates is provided.
  • a catalyst suitable for reacting the oxygenates is provided.
  • the oxygenates are converted to ethylene and propylene.
  • the catalysts and reaction conditions used in oxygenate-to-olefin processes are known in principle to the person skilled in the art.
  • Oxygenate-to-olefin processes can be carried out with different catalysts
  • zeolites such as ZSM-5 or SAPO-34 or functionally comparable materials can be used.
  • ZSM-5 or a comparable material comparatively large ones form
  • compound plants for the production of hydrocarbons, the steam cracking process and oxygenate-to-olefin process or corresponding slit furnaces and reactors are known and described for example in WO 201 1/057975 A2 or US 2013/0172627 A1.
  • Such integrated processes are advantageous, for example, because in the oxygenate-to-olefin process, typically, only the desired short-chain olefins are typically not formed. A significant portion of the oxygenates is converted to paraffins and C4plus olefins. At the same time, not all of the furnace charge is split into short-chain olefins during steam cracking. In particular, unreacted paraffins may be present in the cracking gas of corresponding cracking furnaces. Further, typically C4plus olefins are found here, including diolefins such as butadiene. The compounds obtained are in both cases according to the used
  • a C4 fraction obtained here may, for example, after hydrogenation or separation of butadiene, again be subjected to a steam cracking and / or an oxygenate-to-olefin process.
  • the C4 fraction can be separated into predominantly olefinic and predominantly paraffinic fraction fractions.
  • the present invention is not limited to oxygenate-to-olefin processes, but can in principle be used with any catalytic process, in particular with catalytic processes in which the zeolites explained above are used as catalysts.
  • catalytic processes in which the zeolites explained above are used as catalysts.
  • other oxygenates for example other alcohols and / or ethers, can be used as an insert in corresponding catalytic processes.
  • olefinic components such as a mixture of different unsaturated C4 hydrocarbons
  • olefinic components can be used in corresponding catalytic processes.
  • OCP English Olefins Cracking Process
  • Different uses can be carried out in the context of the present invention in the same reactor or in different reactors.
  • an oxygenate-to-olefin process and another reactor may use an olefin cracking process be performed.
  • both processes, but possibly also a combined process have the goal of producing from one or more operations a product rich in propylene and possibly ethylene.
  • the illustrated catalytic processes which are distinguished in particular by the fact that the mentioned zeolites are used as catalysts and furthermore one or more catalyzer feed streams containing oxygenates and / or olefins are used, are thus carried out in a catalytic unit containing one or more corresponding reactors can have.
  • US 4,197,185 A proposes a process for the production of butane and high octane gasoline from a C4 olefin cut derived from a steam splitter unit.
  • the process comprises polymerizing at least 90% of the isobutene in the C4 olefin cut mainly to dimers and trimers, the resulting
  • Hydrogenation polymerization mixture to n-butane, isooctane and isododecane, to supply the effluent of a corresponding hydrogenation of a separation zone to obtain a gaseous fraction and a liquid mixture, and the
  • This object is achieved by a method and a plant for the production of
  • Liquid and gaseous streams may be rich or poor in one or more components as used herein, with “rich” for a content of at least 75%, 90%, 95%, 99%, 99.5%, 99.9% or 99.99% and “poor” for a content of at most 25%, 10%, 5%, 1%, 0.1% or 0.01% may be on a molar, weight or volume basis.
  • the term “predominantly” may correspond to the definition of "rich” just mentioned, but in particular indicates a content or proportion of more than 90%.
  • Liquid and gaseous streams may also be enriched or depleted in one or more components as used herein, which terms refer to a corresponding level in a starting mixture from which the liquid or gaseous stream was obtained.
  • the liquid or gaseous stream is "enriched” if it is at least 1, 1-fold, 1, 5-fold, 2-fold, 5-fold, 10-fold, 100-fold or 1,000-fold content, "depleted” if it contains not more than 0,9 times, 0, 5 times, 0,1 times, 0,01 times or 0,001 times the content of a corresponding component, relative to the starting mixture.
  • a liquid or gaseous stream is "derived” or “formed” from another liquid or gaseous stream (also referred to as the exit stream) if it has at least some components contained in or from the exit stream.
  • a derived or formed in this sense current can from the output stream in particular by separating or branching a substream or one or more components, enriching or depleting of one or more components, chemical or physical
  • Common processes for the separation of product streams from hydrocarbon production processes involve the formation of a series of fractions based on the different boiling points of the components contained therein.
  • abbreviations are used which indicate the carbon number of the predominantly or exclusively contained hydrocarbons.
  • a "C1 fraction” is a fraction which contains predominantly or exclusively methane (and conventionally also possibly hydrogen, then also called “Cl minus fraction”).
  • a "C2 fraction” contains predominantly or exclusively ethane, ethylene and / or acetylene.
  • a “C3 fraction” contains predominantly propane, propylene, methyl acetylene and / or propadiene.
  • a "C4 fraction” contains predominantly or exclusively butane, butene, butadiene and / or butyne, it being possible for the respective isomers to be present in different proportions, depending on the source of the C4 fraction.
  • Hydrocarbons having one and two carbon atoms having one and two carbon atoms.
  • Oxygenates are typically understood as meaning ethers and alcohols.
  • methyl-ie-f-butyl ether MTBE, Engl., Methyl tertiary butyl ether
  • MTBE methyl-ie-f-butyl ether
  • TAME tertiary amyl methyl ether
  • TAEE ie / f-amyl ethyl ether
  • EBE ethyl-ie F-butyl ether
  • DIPE diisopropyl ether
  • oxygenates include, in particular, dimethyl ether (DME, dimethyl ether).
  • DME dimethyl ether
  • oxygenates are compounds which have at least one alkyl group covalently bonded to an oxygen atom.
  • the at least one alkyl group can be up to five, have up to four or up to three carbon atoms.
  • the oxygenates of interest in the present invention are
  • Alkyl groups having one or two carbon atoms are methyl groups.
  • they are monohydric alcohols and dialkyl ethers such as methanol and dimethyl ether or corresponding mixtures.
  • Coils so-called coils
  • Reaction tubes can be operated at different clearance conditions. Operated under the same or similar fission conditions
  • Reaction tubes or groups of reaction tubes, if appropriate, but also operated under uniform fission conditions tubular reactors in total, are also referred to as "cracking furnaces".
  • a cracking furnace is used in here
  • Steam splitter unit used in the context of the present invention may comprise one or more such cracking furnaces.
  • the same also applies, as already mentioned, for the catalytic unit used in the context of the present invention in which different reactors equipped with identical or different catalysts can be charged with the same or different feed streams and operated under the same or different reaction conditions.
  • vapor column feed streams here refers to one or more liquid and / or gaseous streams which are fed to one or more cracking furnaces. Also, streams obtained by a corresponding steam cracking process, as explained below, may be recycled to one or more cracking furnaces and thus reused as vapor column feed streams.
  • Suitable steam column feed streams are a variety of hydrocarbons and hydrocarbon mixtures of ethane to gas oil up to a boiling point of typically 600 ° C.
  • a steam gap feed stream can thus comprise exclusively so-called "fresh use”, ie an insert which is provided externally and, for example, made out of the system one or more petroleum fractions, natural gas and / or natural gas condensates is obtained.
  • a steam column feed stream may additionally or exclusively comprise one or more so-called “recycle streams”, ie streams which are generated in the plant itself and returned to a corresponding cracking furnace.
  • a steam gap feed stream may also be a mixture of one or more
  • the steam column feed stream is at least partially reacted in the respective cracking furnace and leaves the cracking furnace as so-called "raw gas", the
  • post-treatment steps include first treating the raw gas, for example, by quenching, cooling and drying, whereby a "cracking gas" is obtained.
  • the raw gas is already referred to as cracking gas.
  • steam cracking product stream is used for this purpose.
  • Catalytic units fed feed streams which are referred to herein as “catalytic feed streams”.
  • the catalytic feed stream (s) are reacted in the catalytic unit in one or more reactors into one or more product streams, referred to herein as “catalyst product streams”.
  • the mentioned "cracking conditions" in a cracking furnace include, inter alia, the partial pressure of the furnace insert, which can be influenced by the addition of different amounts of steam and the pressure set in the cracking furnace, the residence time in Cracking furnace as well as the temperatures and temperature profiles used in this.
  • the furnace geometry and furnace design also plays a role.
  • the term "cracking severity" has been used to characterize the fission conditions.
  • the gap resolution can be described by the ratio of propylene to ethylene (P / E) or by the ratio of methane to propylene (M / P) in the cracked gas on a weight basis (kg / kg).
  • the conversion or conversion of each considered component of the furnace insert can be specified as a measure of the gap sharpness.
  • a description of the resolution of the gap via the reaction of key components such as n-butane and isobutane is well suited.
  • the present invention combines the above-described measures for the use of hydrocarbons having four carbon atoms from a
  • the present invention is directed to a process for producing hydrocarbons comprising, in a catalytic unit using one or more catalytic streams containing oxygenates and / or olefins, an n-butane, isobutane, 1-butene, 2-butene, Isobutene and hydrocarbons containing more than four and / or less than four carbon atoms
  • the catalytic unit comprises, as explained above, one or more reactors charged with one or more feed streams, referred to herein as catalysis feed streams.
  • the present invention is suitable for use with oxygenate-to-olefin processes and / or the so-called olefin cracking process and others Method.
  • the one or more used in a corresponding catalytic unit is suitable for use with oxygenate-to-olefin processes and / or the so-called olefin cracking process and others Method.
  • the one or more used in a corresponding catalytic unit is suitable for use with oxygenate-to-olefin processes and / or the so-called olefin cracking process and others Method.
  • Reactors preferably have zeolites as catalysts. As explained, these catalysts may be in particular of the SAPO or ZSM type.
  • the catalytic unit used in the context of the present invention is thus set up for a corresponding catalytic process.
  • the method contemplates generating a vapor gap product stream in a vapor column unit using one or more vapor column feed streams.
  • the steam cracking process used in the context of the present invention can be carried out using the same or different steam cracking conditions in one or more cracking furnaces, as basically known.
  • the steam column feed streams used in steam cracking can be mildly cleaved to increase the yield of value products. Harsher cracking conditions can be used in particular to achieve the highest possible conversion.
  • Catalysis product stream a skeletal isomerization feed stream containing 1-butene, 2-butene, and isobutene is obtained, wherein at least predominantly isobutane is converted to n-butane by skeletal isomerization, and thereafter at least in part as the or one of the vapor column feed streams is used.
  • An essential aspect of the present invention is therefore, a
  • the skeletal isomerization feed stream containing 1-butene, 2-butene and isobutene and at least containing isobutane can also be produced by, inter alia, still adding to the steam cracking product stream
  • Isobutene is reacted by hydrogenation to isobutane. This can then be detected in the skeletal isomerization feed stream of skeletal isomerization be subjected.
  • isobutene is extremely unsuitable for use in a steam cracking process because of its thermal stability and therefore can only be used there poorly in conventional processes.
  • a corresponding skeletal isomerization feed stream can be obtained by, among other things, hydrogenating all the olefins present.
  • Hydrocarbons it may be included that, as explained in the introduction, at least 75%, 90% or more of such hydrocarbons are removed. Preferably, corresponding hydrocarbons are substantially completely removed, ie in particular at least 95%, and if appropriate also at least 99% or more.
  • the method proposed in the context of the present invention is particularly efficient, since the isobutene, which is actually unsuitable for steam cracking, is also used here in the form of isobutane, which is subsequently converted to n-butane, and thus, like all other components, as steam column feed stream or
  • Steam gap streams of steam splitting can be supplied. In this way it is also possible to maximize the product amount of butadiene formed in the steam cracking since the cleavage conditions in the absence of isobutene can be largely adjusted towards maximum butadiene production.
  • the process of the present invention contemplates using at least a portion of the catalytic product stream to form a separation feed stream from which the hydrocarbons are greater than four and / or less than four
  • Trennabstroms Carbon atoms to obtain a n-butane, isobutane, 1-butene, 2-butene and isobutene rich Trennabstroms at least for the most part be separated.
  • a corresponding Trennnicstrom can next to the
  • Catalysis product stream or a part thereof in principle, another stream to be fed, for example, or at least part of the
  • Hydrocarbons having more than four and / or less than four carbon atoms can be separated again in the form of individual fractions, provided as products and / or recycled to the catalytic unit and / or the steam-splitting unit. Details are not explained here for the sake of clarity. With particular advantage comprises a method according to the invention that under
  • Skeletal isomerization feed stream can be used. It is particularly advantageous if, using at least part of the separation effluent, a distillation feed stream is formed from which the n-butane and 2-butene are at least predominantly separated to obtain a distillation effluent low in n-butane and 2-butene. A corresponding distillative separation facilitates the subsequent processing of the
  • a particularly advantageous process using a corresponding distillation comprises forming a hydroisomerization feed stream using at least a portion of the separation effluent in which the 1-butene is at least predominantly hydroisomerized to 2-butene to give a hydroisomerization effluent. At least part of the
  • Hydroisomerization effluent may then be used in the formation of the
  • Distillation feed stream can be used.
  • a corresponding distillation feed stream can be used.
  • Hydroisomerization facilitates the separation of isobutene, which is then, as mentioned, for hydrogenation and skeletal isomerization, of the linear butenes, which need not necessarily be subjected to an appropriate treatment, considerably:
  • the boiling point of isobutene at atmospheric pressure is -6.9 ° C, that of 1-butene at -6.47 ° C. A distillative separation is thus virtually impossible.
  • the boiling point of the 2-butenes, however, is significantly higher than this, namely at 3.7 ° C for c / s-2-butene and 0.9 ° C for frans-2-butene.
  • a hydrogenation feed stream is advantageously formed in which at least the isobutane is at least predominantly hydrogenated to isobutane to yield a hydrogenation effluent.
  • the hydrogenation effluent obtained is at least partly formed in the formation of the
  • a stream is formed which is further
  • Steam gap feed stream can be used.
  • the further vapor column feed stream may be passed into the same or a different cracking furnace than the vapor column feed stream formed above or using the skeletal isomerization feedstream, as described above.
  • a vapor gap product stream is formed containing hydrocarbons having four carbon atoms, including butadiene, and hydrocarbons having more than four and / or less than four carbon atoms.
  • a corresponding stream can also be processed in a separation unit associated with the catalytic unit.
  • Steam cracking product stream recovered from butadiene and hydrocarbons having more than four and / or less than four carbon atoms residual stream which is used at least in part in the generation of the skeletal isomerization feed stream.
  • a corresponding residual stream may for example be subjected to a hydrogenation before a distillative separation or hydroisomerization.
  • a plant which is set up for the production of hydrocarbons is likewise the subject of the invention.
  • a corresponding plant comprises a catalytic unit adapted to use one of n-butane, isobutane, 1-butene, 2-butene, isobutene and hydrocarbons having more than four and one or more catalytic streams containing oxygenates and / or olefins / or less than four carbon atoms to produce rich catalytic product stream, as well as a
  • a vapor column unit configured to generate a vapor gap product stream using one or more vapor column feed streams.
  • a corresponding plant is characterized by means which are adapted to produce using the catalytic product stream at 1-butene, 2-butene and isobutene poor and at least isobutane skeletal isomerization feed stream, in this isobutane at least for the most part To implement skeletal isomensification to n-butane, and then at least in part to use as the or one of the vapor column feed streams.
  • skeletal isomensing can be performed using
  • Alumina catalysts in which ⁇ -alumina as adsorbent, as
  • Catalyst support and / or can be used as a catalyst itself can be made.
  • Activated and / or steam-treated alumina for example, can also be used here, as indicated in US Pat. No. 3,558,733.
  • titanium- or boron-containing compounds in particular in combination with .eta. Or .gamma.-alumina, as described in US Pat. No. 5,321,195 A and US Pat. No. 5,659,104.
  • Other compounds which can be used are halogenated aluminum oxides, as disclosed, for example, in US Pat. No. 2,417,647, Bauxite or zeolites.
  • microporous structured as disclosed, for example, in US Pat. No. 2,417,647, Bauxite or zeolites.
  • Molecular sieves are known, for example, from EP 0 523 838 A1, EP 0 501 577 A1 and EP 0 740 957 A1. The latter can also form active phases of catalysts.
  • Alumina-based catalysts are generally used in the presence of water at temperatures of 200 to 700 ° C and pressures of 0.1 to 2 MPa, in particular at temperatures of 300 to 570 ° C and pressures of 0.1 to 1 MPa used. Further reaction conditions for skeletal isomension can be found in the cited references.
  • Hydrocarbon mixtures are known from the prior art numerous catalytic processes, which can also be used in the context of the present invention.
  • Hydrogenation catalysts have as the hydrogenation-active component one or more elements of the 6th, 7th or 8th subgroup of the Periodic Table in
  • Catalyst properties such as lifetime, resistance to certain catalyst poisons, selectivity or regenerability affect.
  • the hydrogenation and hydroisomerization catalysts often contain the active component on supports, for example mordenites, zeolites, Al 2 O 3 modifications, Si0 2 modifications and others.
  • a corresponding stream is typically passed through a hydroisomerization reactor in the presence of a hydroisomerization catalyst.
  • the hydroisomerisation reactor is typically designed as a fixed bed reactor.
  • thermodynamic equilibrium is at these lower temperatures on the side of the internal olefins, here 2-butene.
  • FIG. 1 shows a plant according to an embodiment of the invention in FIG.
  • FIG. 2 shows a plant according to an embodiment of the invention in FIG.
  • a catalytic unit is denoted by 1 and a vapor column unit by 2.
  • a system according to an embodiment of the invention is shown schematically simplified and designated 100 in total.
  • the catalytic unit 1 are here one or more, oxygenates and / or olefins containing catalytic feed streams, here designated a, fed.
  • the catalytic unit 1 may comprise one or more reactors operated with a zeolite catalyst.
  • the catalytic unit can additionally be charged with further streams, as not illustrated here.
  • a catalytic product stream b is generated in the illustrated example. This is fed as a separation feed stream to a separation unit 3, in which from the catalytic product stream b a depleted of hydrocarbons having more than four and / or less than four carbon atoms or rich in hydrocarbons having four carbon atoms e, here referred to as separation effluent is obtained.
  • separation effluent is obtained from the catalytic product stream b a depleted of hydrocarbons having more than four and / or less than four carbon atoms or rich in hydrocarbons having four carbon atoms e.
  • hydrocarbons having five or more and / or hydrocarbons having three and fewer carbon atoms or other corresponding fractions can also be processed in a corresponding facility and / or obtained as products.
  • the Trennabstrom e is in the illustrated example with another, explained below stream n, here referred to as residual current, combined, creating a
  • Hydrogenation feed stream is generated, which is supplied to a hydrogenation unit 4.
  • a hydrogenation unit 4 preferably all unsaturated hydrocarbons of the streams e and n are converted to corresponding saturated hydrocarbons. Also only partial hydrogenation is possible.
  • a stream is recovered, referred to herein as the hydrogenation effluent.
  • the separation effluent in the illustrated example typically still contains all of the hydrocarbons having four carbon atoms generated in the catalytic unit 1, or derived from the catalytic feed stream (s) a and not reacted in the catalytic unit 1, especially n-butane, isobutane, 1 - Butene, 2-butene and isobutene, the hydrogenation effluent contains only or predominantly the corresponding saturated hydrocarbons, d. H. n-butane and isobutane.
  • Skeletal isomerization feed stream f is fed to an isomerization unit 5 in which the isobutane contained in the skeletal isomerization feed stream f is converted to n-butane. A obtained in the skeletal isomerization unit 5
  • skeletal isomerization effluent predominantly or exclusively contains n-butane and is fed as vapor column feed stream g to the steam splitter unit 2.
  • the steam gap feed stream g i.
  • substantially pure n-butane in the vapor column unit 2 in one or more cracking furnaces, possibly also together with other streams, which are performed in the same or different cracking furnaces processed.
  • a steam cracking product stream h is obtained which, as explained, contains hydrocarbons having four carbon atoms, including butadiene, and hydrocarbons having more than four and / or less than four carbon atoms.
  • This steam cracking product stream h is fed to a further separation unit 6, in which initially with the removal of hydrocarbons having more than four and / or less than four carbon atoms, as illustrated here with the streams i and k, a stream I is obtained which predominantly hydrocarbons with four
  • Carbon atoms, including butadiene are conducted in the example shown in a butadiene separation unit 7, where the containing butadiene is separated to a large extent and executed as a current m from the system.
  • a remaining, low-butadiene residual stream, here denoted by n, can be combined with the above-explained hydrogenation feed stream or the separating effluent e forming it and fed into the hydrogenation unit 4.
  • a sharp splitting for maximizing ethylene
  • mild splitting for propylene maximization
  • FIG. 2 schematically shows a plant according to a further embodiment of the invention, designated overall by 200.
  • a separation effluent e of the separation unit 3 is optionally one
  • a collecting stream can be formed from the separation effluent e and the above-mentioned low-butadiene residual stream n, which is also referred to herein as hydroisomerization feed stream.
  • Hydroisomerization unit 8 the separation effluent e and the residual stream n can also be performed in the form of a distillation feed stream o directly to a distillation unit 9, the hydroisomerization 8 is therefore optional.
  • Hydroisomerization unit 8 used in this is the in the
  • Distillation feed stream o is included. As explained, a distillative separation in the distillation unit 9 is facilitated in this way.
  • a distillation effluent p is obtained from the distillation feed stream o by separating butane and 2-butene, or the predominant fraction thereof in the form of the stream s.
  • the distillation effluent p if no Hydroisomer Deutschensaku 8 is provided, 1 -butene, otherwise not. Further, the distillation effluent contains p isobutene and isobutane.
  • the distillation effluent p is fed as a hydrogenation feed stream to a hydrogenation unit, here denoted by 4 as in FIG. 1. In the hydrogenation unit, if in the
  • Hydrogenation feed stream p present 1-butene reacted to 1-butane, also carried out a conversion of isobutene to isobutane.
  • One obtained in the hydrogenation unit 4 Hydrogenation effluent therefore contains either a mixture of substantially n-butane and isobutane or substantially pure isobutane.
  • the hydrogenation effluent is then treated as a skeletal isomerization feed stream q
  • a stream containing essentially butane and 2-butene is also obtained, which can also be fed as a (further) steam gap feed stream s to a steam splitter unit, and here to a same or different cracking furnace as the steam splitter feed stream r.

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  • Oil, Petroleum & Natural Gas (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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Abstract

L'invention concerne un procédé pour produire des hydrocarbures, comprenant les étapes consistant à produire, dans une unité de catalyse (1), par utilisation d'un ou plusieurs flux utiles de catalyse (a) contenant des oxygénates et/ou des oléfines, un flux de produit de catalyse (b) riche en n-butane, en isobutane, en 1-butène, en 2-butène, en isobutène et en hydrocarbures comportant plus de quatre et/ou moins de quatre atomes de carbone, puis à produire, dans une unité de séparation en phase vapeur (2), par utilisation d'un ou plusieurs flux utiles de séparation en phase vapeur (g, r, s), un flux de produit de séparation en phase vapeur (h). Selon l'invention, par utilisation du flux de produit de catalyse (b) est produit un flux utile d'isomérisation de squelette (f, q) pauvre en 1-butène, en 2-butène et en isobutène et contenant au moins de l'isobutane, dans lequel l'isobutane est converti au moins en majeure partie en n-butane par isomérisation de squelette, et qui est ensuite employé au moins en partie en tant qu'au moins l'un des flux utiles de séparation en phase vapeur (g, r). L'invention porte aussi sur une installation (100, 200) correspondante.
EP15766101.8A 2014-09-11 2015-09-11 Procédé et installation pour la production d'hydrocarbures Withdrawn EP3191433A1 (fr)

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EP14184470.4A EP2995599A1 (fr) 2014-09-11 2014-09-11 Procédé et système de fabrication d'hydrocarbures
PCT/EP2015/070893 WO2016038213A1 (fr) 2014-09-11 2015-09-11 Procédé et installation pour la production d'hydrocarbures

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EP (2) EP2995599A1 (fr)
CN (1) CN106715364A (fr)
CA (1) CA2959460A1 (fr)
RU (1) RU2017106926A (fr)
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EP3784643A1 (fr) 2018-04-27 2021-03-03 SABIC Global Technologies B.V. Procédé pour n-butaniser une charge de départ de butane produit sur le terrain vers des craqueurs thermiques

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Publication number Priority date Publication date Assignee Title
US2417647A (en) 1943-11-04 1947-03-18 Robert H Hasler Nonicing propeller
US3558733A (en) 1969-07-30 1971-01-26 Phillips Petroleum Co Olefin isomerization process with alumina of controlled water content
FR2401122A1 (fr) * 1977-08-26 1979-03-23 Inst Francais Du Petrole Procede pour la conversion des coupes c4 olefiniques de vapocraquage en isooctane et en butane
GB9103989D0 (en) 1991-02-26 1991-04-10 Shell Int Research Process for the conversion of a feedstock comprising linear olefins
DE69229980T2 (de) 1991-06-05 2000-01-05 Equistar Chem Lp Verfahren zur Isomerisierung von geradlinigen Olefinen in Isoolefine
US5281753A (en) 1992-04-21 1994-01-25 Engelhard Corporation Process for the selective hydrogenation and isomerization of hydrocarbons
FR2695636B1 (fr) 1992-09-15 1994-12-02 Inst Francais Du Petrole Procédé pour l'isomérisation des oléfines.
FR2716879B1 (fr) 1994-03-01 1996-05-31 Inst Francais Du Petrole Procédé pour l'isomérisation des oléfines.
FR2733701B1 (fr) 1995-05-04 1997-06-13 Inst Francais Du Petrole Procede de pretraitement selectivant de tamis moleculaire et procede d'isomerisation squelettale des olefines lineaires avec le tamis pretraite
FR2755130B1 (fr) 1996-10-28 1998-12-11 Inst Francais Du Petrole Nouveau procede de production d'isobutene et de propylene a partir de coupes d'hydrocarbures a quatre atomes de carbone
FR2802921B1 (fr) 1999-12-24 2002-08-23 Inst Francais Du Petrole Production d'isobutene de haute purete et de propylene a partir de coupes d'hydrocarbures a quatre atomes de carbone
US6420619B1 (en) 2001-01-25 2002-07-16 Robert J. Gartside Cracked gas processing and conversion for propylene production
US7576251B2 (en) 2005-04-15 2009-08-18 Abb Lummus Global Inc. Process for the double bond hydroisomerization of butenes
AU2010318050B2 (en) 2009-11-10 2013-12-12 Shell Internationale Research Maatschappij B.V. Process and integrated system for the preparation of a lower olefin product
US20130172627A1 (en) 2011-12-28 2013-07-04 Shell Oil Company Process for preparing lower olefins

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TW201615598A (zh) 2016-05-01
CA2959460A1 (fr) 2016-03-17
WO2016038213A1 (fr) 2016-03-17
EP2995599A1 (fr) 2016-03-16
CN106715364A (zh) 2017-05-24
RU2017106926A (ru) 2018-10-11

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