EP1833776A1 - Procede de production de propene a partir de propane - Google Patents

Procede de production de propene a partir de propane

Info

Publication number
EP1833776A1
EP1833776A1 EP05821810A EP05821810A EP1833776A1 EP 1833776 A1 EP1833776 A1 EP 1833776A1 EP 05821810 A EP05821810 A EP 05821810A EP 05821810 A EP05821810 A EP 05821810A EP 1833776 A1 EP1833776 A1 EP 1833776A1
Authority
EP
European Patent Office
Prior art keywords
stream
propane
gas stream
propene
separated
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Withdrawn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
EP05821810A
Other languages
German (de)
English (en)
Inventor
Otto Machhammer
Sven Crone
Götz-Peter SCHINDLER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1833776A1 publication Critical patent/EP1833776A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • 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
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
    • 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
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • 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
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation

Definitions

  • the invention relates to a process for the preparation of propene from propane.
  • Propene is obtained industrially by dehydrogenation of propane.
  • the C 2 and C 3 hydrocarbons and the high boilers of hydrogen and methane formed during the dehydrogenation are then separated off by condensation in a so-called "cold box.”
  • the liquid hydrocarbon condensate is then distilled off by distillation Column the C 2 hydrocarbons and remaining methane separated and separated in a second distillation column of the C 3 -Kohlen- hydrogen flow in a propene fraction with a high degree of purity and a propane fraction, which also contains the C 4 + hydrocarbons.
  • a disadvantage of this process is the loss of C 3 -hydrocarbons due to condensation in the "cold box.” Owing to the large amounts of hydrogen formed during the dehydrogenation and due to the phase equilibrium, larger amounts of C 3 are also produced with the hydrogen / methane exhaust gas stream Hydrocarbons, unless condensed at very low temperatures, such as working at temperatures from -20 to -60 0 C to limit the loss of C 3 hydrocarbons discharged with the hydrogen / methane exhaust stream.
  • the object of the invention is to provide an improved process for the dehydrogenation of propane to propene.
  • the problem is solved by a process for producing propene from propane with the steps
  • A) a propane-containing feed gas stream a is provided;
  • non-condensable or low-boiling gas components are separated by contacting the product gas stream c with an inert absorbent and then desorbing the gases dissolved in the inert absorbent, a C 3 hydrocarbon stream d 1 and an exhaust gas stream d 2 containing methane, ethane, ethene, Nitrogen, carbon monoxide, carbon dioxide and hydrogen;
  • the C 3 -hydrocarbon stream el is optionally fed into a first distillation zone and separated by distillation into a stream fl of propane and propene and a stream f 2 containing ethane and ethene;
  • a propane-containing feed gas stream a is provided. This generally contains at least 80% by volume of propane, preferably 90% by volume of propane. In addition, the propane-containing feed gas stream A generally still contains butanes (n-butane, iso-butane). Typical compositions of the propane-containing feed gas stream are disclosed in DE-A 102 46 119 and DE-A 102 45 585.
  • the propane-containing feed gas stream a is obtained from liquid petroleum gas (LPG).
  • LPG liquid petroleum gas
  • the propane-containing feed gas stream may be subjected to a purification distillation to remove the butanes, whereby a feed gas stream a having a very high propane content (> 95% by volume) is obtained.
  • the propane-containing feed gas stream is fed into a dehydrogenation zone and subjected to non-oxidative catalytic dehydrogenation.
  • propane is partially dehydrogenated to propene in a dehydrogenation reactor on a dehydrogenating catalyst.
  • hydrogen and small amounts of methane, ethane, ethene and C 4 + hydrocarbons are obtained.
  • carbon oxides (CO, CO 2 ), in particular CO 2 water and, to a lesser extent, inert gases in the product gas mixture of the non-oxidative catalytic, autothermal propane dehydrogenation.
  • Inert gases nitrogen
  • unreacted propane is present in the product gas mixture.
  • the non-oxidative catalytic propane dehydrogenation is carried out autothermally.
  • the reaction gas mixture of the propane dehydrogenation in at least one reaction zone additionally admixed with an oxygen-containing gas and the at least partially combusted in the reaction gas mixture hydrogen and / or hydrocarbon, whereby at least a portion of the required Dehydriereben generated in the at least one reaction zone directly in the reaction gas mixture becomes.
  • the oxygen-containing gas used is air or oxygen-enriched air having an oxygen content of up to 70% by volume, preferably up to 50% by volume.
  • a feature of the non-oxidative mode of operation over an oxidative mode of operation is that free hydrogen is still present at the outlet of the dehydrogenation zone. During oxidative dehydrogenation, no free hydrogen is formed.
  • the non-oxidative catalytic, autothermal propane dehydrogenation can in principle be carried out in all reactor types known from the prior art.
  • a comparatively detailed description of inventively suitable reactor types includes "Catalytica® ® Studies Division, Oxidative Dehydrogenation and Alternative Dehydrogenation Processes" (Study Number 4192 OD, 1993, 430 Ferguson Drive, Mountain View, California, 94043-5272, USA).
  • a suitable reactor form is the fixed bed tube or tube bundle reactor.
  • the catalyst dehydrogenation catalyst and optionally special oxidation catalyst
  • the catalyst is a fixed bed in a reaction tube or in a bundle of reaction tubes.
  • Typical reaction tube internal diameters are about 10 to 15 cm.
  • a typical Dehydrierrohrbündelreaktor comprises about 300 to 1000 reaction tubes.
  • the temperature in the inside of the reaction tube usually ranges from 300 to 1200 ° C., preferably in the range from 500 to 1000 ° C.
  • the working pressure is usually between 0.5 and 8 bar, frequently between 1 and 2 bar when using a low steam dilution.
  • Typical Catalyst Exposure are from 500 to 2000 h "1 , based on the hydrocarbon used.
  • the catalyst geometry can be, for example, spherical or cylindrical (hollow or full).
  • the non-oxidative catalytic, autothermal propane dehydrogenation can also be carried out under heterogeneous catalysis in a fluidized bed, according to the Snamprogetti / Yarsintez-FBD process.
  • two fluidized beds are operated side by side, one of which is usually in the state of regeneration.
  • the working pressure is typically 1 to 2 bar, the dehydrogenation temperature usually 550 to 65O 0 C.
  • the heat required for the dehydrogenation can thereby be introduced into the reaction system by the dehydrogenation catalyst is preheated to the reaction temperature.
  • an oxygen-containing co-feed By adding an oxygen-containing co-feed can be dispensed with the preheater, and the heat required is generated directly in the reactor system by combustion of hydrogen and / or hydrocarbons in the presence of oxygen.
  • a hydrogen-containing co-feed may additionally be admixed.
  • the non-oxidative catalytic, autothermal propane dehydrogenation is preferably carried out in a tray reactor.
  • This contains one or more successive catalyst beds.
  • the number of catalyst beds may be 1 to 20, advantageously 1 to 6, preferably 1 to 4 and in particular 1 to 3.
  • the catalyst bed Th are preferably flowed through radially radially or axially from the reaction gas.
  • such a tray reactor is operated with a fixed catalyst bed.
  • the fixed catalyst beds are arranged in a shaft furnace reactor axially or in the annular gaps of concentrically arranged cylindrical gratings.
  • a shaft furnace reactor corresponds to a horde reactor with only one horde.
  • the performance of dehydrogenation in a single shaft furnace reactor corresponds to one embodiment.
  • the dehydrogenation is carried out in a tray reactor with 3 catalyst beds.
  • the amount of the oxygen-containing gas added to the reaction gas mixture is selected such that the amount of heat required for the dehydrogenation of the propane is generated by the combustion of hydrogen present in the reaction gas mixture and optionally of hydrocarbons present in the reaction gas mixture and / or of coke present in the form of coke ,
  • the total amount of oxygen fed, based on the total amount of propane is 0.001 to 0.5 mol / mol, preferably 0.005 to 0.25 mol / mol, particularly preferably 0.05 to 0.25 mol / mol.
  • Oxygen is used as the oxygen-containing gas containing inert gases, for example, air or oxygen-enriched air.
  • the hydrogen burned to generate heat is the hydrogen formed during the catalytic propane dehydrogenation and, if appropriate, the hydrogen gas additionally added to the reaction gas mixture.
  • the molar ratio H ⁇ O 2 in the reaction gas mixture immediately after the feed of the oxygen-containing gas is 1 to 10, preferably 2 to 5 mol / mol. This applies to multi-stage reactors for each intermediate feed of oxygen-containing and possibly hydrogen-containing gas.
  • the hydrogen combustion takes place catalytically.
  • the dehydrogenation catalyst used generally catalyzes both the combustion of the hydrocarbons and of hydrogen with oxygen, so that in principle no special oxidation catalyst different from this one is required.
  • the reaction is carried out in the presence of one or more oxidation catalysts which selectively catalyze the combustion of hydrogen with oxygen to water in the presence of hydrocarbons.
  • the combustion of these hydrocarbons with oxygen to CO, CO 2 and water is therefore only to a minor extent.
  • the dehydrogenation catalyst and the oxidation catalyst are present in different reaction zones.
  • the oxidation catalyst can be present in only one, in several or in all reaction zones.
  • the catalyst which selectively catalyzes the oxidation of hydrogen is arranged at the locations where higher oxygen partial pressures prevail than at other points of the reactor, in particular in the vicinity of the feed point for the oxygen-containing gas.
  • the feeding of oxygen-containing gas and / or hydrogen-containing gas can take place at one or more points of the reactor.
  • an intermediate feed of oxygen-containing gas and optionally of hydrogen-containing gas takes place before each tray of a tray reactor.
  • the feed of oxygen-containing gas and optionally of hydrogen-containing gas takes place before each horde except the first Horde.
  • behind each feed point is a layer of a specific oxidation catalyst, followed by a layer of the dehydrogenation catalyst.
  • no special oxidation catalyst is present.
  • the dehydrogenation temperature is generally 400 to HOO 0 C
  • the pressure in the last catalyst bed of the tray reactor generally 0.2 to 5 bar, preferably 1 to 3 bar.
  • the load (GHSV) is generally 500 to 2000 h "1 , in high load mode also up to 100 000 h " 1 , preferably 4000 to 16 000 h "1 .
  • a preferred catalyst which selectively catalyzes the combustion of hydrogen contains oxides and / or phosphates selected from the group consisting of the oxides and / or phosphates of germanium, tin, lead, arsenic, antimony or bismuth.
  • Another preferred catalyst which catalyzes the combustion of hydrogen contains a noble metal of VIII. And / or I. Maury.
  • the dehydrogenation catalysts used generally have a carrier and an active composition.
  • the carrier is usually made of a heat-resistant oxide or mixed oxide.
  • the dehydrogenation catalysts preferably contain a metal oxide which is selected from the group consisting of zirconium dioxide, zinc oxide, aluminum oxide, silicon dioxide, titanium dioxide, magnesium oxide, lanthanum oxide, cerium oxide and mixtures thereof as support.
  • the mixtures can be physical minerals. or mixed chemical phases such as magnesium or zinc-aluminum oxide mixed oxides.
  • Preferred supports are zirconia and / or silica, particularly preferred are mixtures of zirconia and silica.
  • the active composition of the dehydrogenation catalysts generally contain one or more elements of VIII. Subgroup, preferably platinum and / or palladium, more preferably platinum.
  • the dehydrogenation catalysts may comprise one or more elements of main group I and / or II, preferably potassium and / or cesium.
  • the dehydrogenation catalysts may contain one or more elements of III. Subgroup including the lanthanides and actinides, preferably lanthanum and / or cerium.
  • the dehydrogenation catalysts may contain one or more elements of III. and / or IV.
  • Main group preferably one or more elements from the group consisting of boron, gallium, silicon, germanium, tin and lead, particularly preferably tin.
  • the dehydrogenation catalyst contains at least one element of the VIII. Subgroup, at least one element of the I. and / or IL main group, at least one element of III. and / or IV. Main group and at least one element of III. Subgroup including the lanthanides and actinides.
  • all dehydrogenation catalysts can be used which are described in WO 99/46039, US Pat. No. 4,788,371, EP-A 705,136, WO 99/29420, US Pat. No. 5,220,091, US Pat. No. 5,430,220, US Pat. No. 5,877,369, EP 0 117 146, DE-A 199 37 106 DE-A 199 37 105 and DE-A 199 37 107 are disclosed.
  • Particularly preferred catalysts for the above-described variants of the autothermal propane dehydrogenation are the catalysts according to Examples 1, 2, 3 and 4 of DE-A 199 37 107.
  • the autothermal propane dehydrogenation is preferably carried out in the presence of steam.
  • the added water vapor serves as a heat carrier and supports the gasification of organic deposits on the catalysts, whereby the coking of the catalysts counteracted and the service life of the catalysts is increased.
  • the organic deposits are converted into carbon monoxide, carbon dioxide and possibly water.
  • the dehydrogenation catalyst can be regenerated in a manner known per se.
  • the reaction gas mixture steam can be added or from time to time an oxygen-containing gas at elevated temperature over the catalyst bed and the deposited carbon are burned off. Dilution with water vapor shifts the equilibrium to the products of dehydration.
  • the catalyst is reduced after regeneration with a hydrogen-containing gas.
  • a gas mixture which generally has the following composition: 5 to 95% by volume of propane, 1 to 40% by volume of propene, 0 to 10% by volume of methane, ethane, ethene and C. 4 + hydrocarbons, 0 to 15% by volume of carbon dioxide, 0 to 5% by volume of carbon monoxide, 0 to 5% by volume of steam and 1 to 30% by volume of hydrogen and 1 to 50% by volume Inert gases (especially nitrogen).
  • the product gas stream b when leaving the dehydrogenation zone is generally under a pressure of 1 to 5 bar, preferably 1.5 to 3 bar, and has a temperature in the range of 400 to 700 0 C.
  • the product gas stream b can be separated into two partial streams, with a partial stream being returned to the autothermal dehydrogenation, in accordance with the cycle gas method described in DE-A 102 11 275 and DE-A 100 28 582.
  • steam is first separated from the product gas stream b, a product gas stream c depleted of water vapor being obtained.
  • the separation of water vapor is carried out by condensation by cooling and optionally compressing the product gas stream b and can be carried out in one or more cooling and optionally compression stages.
  • the product gas stream b is cooled to a temperature in the range from 0 to 80 ° C., preferably from 10 to 65 ° C.
  • the product gas stream can be compressed, for example to a pressure in the range of 5 to 50 bar.
  • the non-condensable or low-boiling gas constituents such as hydrogen, oxygen, carbon monoxide, carbon dioxide, nitrogen and the low-boiling hydrocarbons (methane, ethane, ethene) in an absorption / desorption cycle by means of a high-boiling absorbent from the C 3 - hydrocarbons separated, whereby a stream dl is obtained, which contains the C 3 - hydrocarbons and also small amounts of ethane and ethene, and an exhaust stream d2 is obtained, which contains the non-condensable or low-boiling gas components.
  • the non-condensable or low-boiling gas constituents such as hydrogen, oxygen, carbon monoxide, carbon dioxide, nitrogen and the low-boiling hydrocarbons (methane, ethane, ethene) in an absorption / desorption cycle by means of a high-boiling absorbent from the C 3 - hydrocarbons separated, whereby
  • the gas stream b is contacted with an inert absorbent, the Cs hydrocarbons and also small amounts of C 2 hydrocarbons are absorbed in the inert absorbent and a loaded with C 3 hydrocarbons absorbent and the other gas inventory - Parts containing exhaust gas d2 are obtained.
  • These are mainly carbon oxides, hydrogen, inert gases and C 2 hydrocarbons and methane.
  • the C 3 hydrocarbons are released from the absorbent again.
  • Inert absorbent used in the absorption stage are generally high-boiling non-polar solvents in which the separated C 3 hydrocarbon mixture has a significantly higher solubility than the other gas components to be separated.
  • the absorption can be carried out by simply passing the stream c through the absorbent. But it can also be done in columns or in rotational absorbers. It can be used in cocurrent, countercurrent or cross flow.
  • Suitable absorption columns include plate columns having bubble, centrifugal and / or sieve trays, columns with structured packings, for example sheet metal packings with a specific surface area of 100 to 1000 m 2 / m 3 as Mellapak ® 250 Y, and packed columns.
  • Suitable absorbents are relatively non-polar organic solvents, for example C 4 -C 1S aliphatic acyl, naphtha or aromatic hydrocarbons, such as the paraffin distillation medium fractions, or bulky group ethers, or mixtures of these solvents, which may contain a polar solvent such as 1,2- Dimethyl phthalate may be added.
  • Suitable absorbents are furthermore esters of benzoic acid and phthalic acid with straight-chain Q-Cs-alkanols, such as n-butyl benzoate, methyl benzoate, ethyl benzoate, phthalate, diethyl phthalate, and so-called heat transfer oils, such as biphenyl and diphenyl ether, their chlorinated derivatives and triaryl alkenes.
  • a suitable absorbent is a mixture of biphenyl and diphenyl ether, preferably in the azeotropic composition, for example, the commercially available Diphyl ®. Often, this solvent mixture contains dimethyl phthalate in an amount of 0.1 to 25 wt .-%.
  • Suitable absorbents are also butanes, pentanes, hexanes, heptanes, octanes, nonanes, decanes, undecanes, dodecanes, tridecanes, tetradecanes, pentadecanes ne, hexadecane, heptadecane and octadecane or fractions obtained from refinery streams containing as main components the said linear alkanes.
  • the loaded absorbent is heated and / or expanded to a lower pressure.
  • the desorption may also be by stripping, usually with steam, or in a combination of relaxation, heating and stripping in one or more process steps.
  • the desorption can be carried out in two stages, wherein the second desorption stage is carried out at a lower pressure than the first desorption stage and the desorption gas of the second stage is returned to the absorption stage. The absorbent regenerated in the desorption stage is returned to the absorption stage.
  • the desorption step is carried out by relaxation and / or heating of the loaded absorbent.
  • the desorption step is additionally stripped with steam.
  • the separation D is generally not completely complete, so that in the C 3 - hydrocarbon stream dl - depending on the type of separation - still small amounts or even traces of other gas constituents, in particular the low-boiling hydrocarbons, may be present.
  • the exhaust gas stream d2 may, if appropriate after cooling, for example in an indirect heat exchanger, be passed through a membrane, which is usually designed as a tube, which is permeable only to molecular hydrogen.
  • the thus separated molecular hydrogen can, if necessary, at least partially used in the dehydrogenation or else be supplied to another utilization, for example, be used for generating electrical energy in fuel cells e.
  • the exhaust gas flow d2 can be burned.
  • the gas flow d 1 is cooled, wherein it can additionally be compressed in one or more further compression stages.
  • the el stream may still contain small amounts of C 2 - hydrocarbons.
  • an aqueous condensate stream e2 and possibly small amounts of an exhaust gas stream e3 can be obtained.
  • the watery Condensate flow e2 generally accumulates when steam is stripped in step D to desorb the dissolved gases.
  • the compression can again be done in one or more stages.
  • a total pressure of from 1 to 29 bar, preferably from 1 to 10 bar is compressed to a pressure in the range from 12 to 30 bar.
  • a cooling stage in which the gas flow to a temperature in the range of 15 to
  • the gas stream d 1 can also be cooled and fed to the first distillation zone in gaseous form, preferably when the desorption of the dissolved gases in the process part D is effected only by expansion and heating and is not also stripped with steam.
  • the gaseous or liquid C 3 hydrocarbon stream el is fed into a first distillation zone and separated by distillation into a stream containing the C 3 hydrocarbons propane and propene and a stream f 2 containing the C 2 hydrocarbons ethane and ethene ,
  • the C 3 -hydrocarbon stream el is generally fed into a C2 / C3 separating column with typically 20 to 80 theoretical plates, for example about 60 theoretical plates. This is generally operated at a pressure in the range of 10 to 30 bar, for example at about 20 bar, and a reflux ratio of 2 to 30.
  • the bottom temperature is generally from 40 to 100 0 C, for example about 6O 0 C, the head temperature of -20 to 1O 0 C, for example, about 10 0 C.
  • a stream of propane and propene is obtained as the bottom draw stream with an ethanol / ethene content of generally ⁇ 5000 ppm, preferably ⁇ 1000 ppm, more preferably ⁇ 500 ppm.
  • the stream f2 which is preferably obtained as a top draw stream, may still contain certain amounts of propane and propene and be recycled to the separation thereof in the absorption stage.
  • the process part F can also be omitted, especially if the stream dl or el has only a low content of C 2 hydrocarbons.
  • the C 3 -hydrocarbon stream el or fl is fed into a second distillation zone and separated by distillation into a stream gl containing propene and a stream g 2 containing propane.
  • the hydrocarbon stream fl is generally fed into a C3 separating column ("C3 splitter") typically having 80 to 150 theoretical plates, for example about 100 theoretical plates, which is generally at a pressure in the range from 10 to 30 bar, for example at about 20 bar, and a reflux ratio of 2 - 40 is operated, the bottom temperature is generally from 40 to 100 0 C, for example about 68 0 C, the head temperature of 30 to 60 0 C, for example about 6O. 0 C.
  • C3 splitter typically having 80 to 150 theoretical plates, for example about 100 theoretical plates, which is generally at a pressure in the range from 10 to 30 bar, for example at about 20 bar, and a reflux ratio of 2 - 40 is operated
  • the bottom temperature is generally from 40 to 100 0 C, for example about 68 0 C
  • the head temperature of 30 to 60 0 C, for example about 6O. 0 C.
  • C 3 - rectifying column can also contain two 3 -Trennkolonnen be used C, wherein the first column at a higher pressure, for example 25 bar, and the second column at a lower pressure, for example 18 bar, is operated (2- The head take-off of the first column is liquefied in the sump heater of the second column and the bottom take-off of the first column is fed into the second column Vapor compression possible.
  • the stream g2 and a fresh propane stream can be fed into a third distillation zone in which a stream containing C 4 + hydrocarbons is separated off by distillation and the feed gas stream a having a very high propane content is obtained.
  • the recycled stream g2 is vaporized before it enters the third distillation zone.
  • a refrigerant flow can be generated, which can be used for cooling elsewhere, for example, for cooling at the top of the column C2 / C3 separation column.
  • the invention is further illustrated by the following example.
  • the fresh propane stream 1 contains about 98 wt .-% propane, about 2 wt .-% butane.
  • the fresh propane stream 1 is mixed with the propane recycle stream 24 from the C3 splitter 37 and fed to the C3 / C4 separation column 30.
  • the C3 / C4 separation column 30 which has 40 theoretical stages and at 10 bar operating pressure and a reflux Ratio of 0.41 is operated, a high boiler stream 4 is separated and thus obtained a propane stream 3 with a butane content of only 0.01 wt .-%.
  • the propane stream 3 is preheated to 45O 0 C, enters the dehydrogenation zone 31 and is subjected to an autothermal dehydrogenation.
  • an oxygen-containing gas 6 and water vapor 5 are fed into the dehydrogenation zone 31.
  • the conversion of the dehydrogenation is based on propane, 50%, the selectivity of the propene formation is 90%.
  • 5% cracking products and 5% carbon oxides are formed by total combustion.
  • the water concentration in the outlet gas of the dehydrogenation zone is about 6 wt .-%, the residual oxygen content in the outlet gas is 0 wt .-%, the outlet temperature of the product gas mixture is 600 0 C.
  • the product gas stream 7 is cooled and in the compressor 32, starting from a Pressure of 2.0 bar in 3 stages to a pressure of 15 bar compressed. After the first and the second compressor stage is cooled to 55 ° C in each case.
  • aqueous condensate 9 which is discharged from the process.
  • the compressed and cooled gas stream 8 is brought in the absorption column 33 with tetradecane 21 as an absorbent in contact.
  • the unabsorbed gases are withdrawn as exhaust gas stream 11 via the top of the column, the absorbent laden with the C 3 hydrocarbons is taken off via the bottom of the column and fed to the desorption column 34.
  • the C 3 hydrocarbons are desorbed by depressurization to a pressure of 4 bar and stripping with high-pressure steam fed to stream 13, a stream 14 of regenerated absorbent and a stream 12 of C 3 hydrocarbons and water vapor being obtained ,
  • the regenerated absorbent 14 is supplemented with fresh absorbent 22 and returned to the absorption column 33.
  • the gas is cooled to 45 ° C, with further absorbent 14 condensed out.
  • an aqueous phase is obtained, which is separated in a phase separator and discharged as stream 15 from the process.
  • the stream 12 is compressed in two stages to a pressure of 16 bar and cooled to a temperature of 40 0 C. In this case, a small waste gas stream 18, a wastewater stream 17 and a liquid C 3 -hydrocarbon stream 16 accumulate.
  • liquid C 3 -hydrocarbon stream 16 is in a C2 / C3 separation column 36 with 30 theoretical stages at 16 bar and a reflux ratio of 47 overhead a C 2 hydrocarbon stream 20, which also contains certain amounts of C 3 -hydrocarbons, separated.
  • the stream 20 is recycled to the absorption column 33, where contained in the stream 20 C ß hydrocarbons are separated.
  • the bottom temperature in the C2 / C3 separating column 36 is 41 0 C, the head temperature -5 ° C.
  • the residual ethane content of the bottom draw stream 19 is 0.01% by weight.
  • the bottom draw stream 19 is fed to a propane / propene separation column with 120 theoretical plates, which is operated at 16 bar with a reflux ratio of 21.
  • the bottom temperature is 46 ° C, the head temperature 38 ° C.
  • At the top of a propene stream 23 is obtained with a purity of 99.5 wt .-% propene.
  • the bottom draw stream 24 contains about 98.5% by weight of propane and is recycled to the dehydrogenation zone 31.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Abstract

L'invention concerne un procédé de production de propène à partir de propane, qui consiste A) à préparer un flux de gaz d'apport (a) contenant du propane, B) à introduire le flux de gaz d'apport (a) contenant du propane et un flux de gaz oxygéné dans une zone de déshydrogénation puis à soumettre le propane à une déshydrogénation autothermique, catalytique, non oxydative pour former du propène, un flux de gaz produit (b), contenant du propane, du propène, du méthane, de l'éthane, de l'éthène, de l'azote, du monoxyde de carbone, du dioxyde de carbone, de la vapeur d'eau et de l'hydrogène, étant obtenu, C) à refroidir le flux de gaz produit (b) puis à séparer la vapeur d'eau par condensation, un flux de gaz produit (c) appauvri en vapeur d'eau étant obtenu, D) à séparer des constituants gazeux non condensables ou à bas point d'ébullition par mise en contact du flux de gaz produit (c) avec un absorbant inerte puis par désorption des gaz dissous dans cet absorbant inerte, un flux d'hydrocarbure en C<SUB>3</SUB> (d1) et un flux de gaz résiduaires (d2), contenant du méthane, de l'éthane, de l'éthène, de l'azote, du monoxyde de carbone, du dioxyde de carbone et de l'hydrogène, étant obtenu, E) à refroidir et à comprimer le flux d'hydrocarbure en C<SUB>3</SUB> (d1), un flux d'hydrocarbure en C<SUB>3</SUB> liquide (e1) étant obtenu, F) à introduire le flux d'hydrocarbure en C<SUB>3</SUB> liquide (e1) dans une première zone de distillation puis à le séparer par distillation en un flux (f1) de propane et de propène et un flux (f2) contenant de l'éthane et de l'éthène et G) à introduire le flux (f1) dans une seconde zone de distillation puis à le séparer par distillation en un flux produit (g1) de propène et un flux (g2) de propane, le flux (g2) étant ramené au moins partiellement à la zone de déshydrogénation.
EP05821810A 2004-12-22 2005-12-20 Procede de production de propene a partir de propane Withdrawn EP1833776A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004061772A DE102004061772A1 (de) 2004-12-22 2004-12-22 Verfahren zur Herstellung von Propen aus Propan
PCT/EP2005/013700 WO2006069674A1 (fr) 2004-12-22 2005-12-20 Procede de production de propene a partir de propane

Publications (1)

Publication Number Publication Date
EP1833776A1 true EP1833776A1 (fr) 2007-09-19

Family

ID=35976684

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05821810A Withdrawn EP1833776A1 (fr) 2004-12-22 2005-12-20 Procede de production de propene a partir de propane

Country Status (15)

Country Link
US (1) US20080207975A1 (fr)
EP (1) EP1833776A1 (fr)
JP (1) JP2008524289A (fr)
KR (1) KR20070089244A (fr)
CN (1) CN101087740B (fr)
AU (1) AU2005321540A1 (fr)
BR (1) BRPI0519387A2 (fr)
CA (1) CA2591204A1 (fr)
DE (1) DE102004061772A1 (fr)
EA (1) EA010745B1 (fr)
MX (1) MX2007006995A (fr)
MY (1) MY147177A (fr)
NO (1) NO20072874L (fr)
TW (1) TW200639147A (fr)
WO (1) WO2006069674A1 (fr)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005010586A1 (de) * 2005-03-08 2006-09-14 Basf Ag Verfahren zur Herstellung von Propen aus Propan
MY153923A (en) * 2008-07-30 2015-04-15 Lummus Technology Inc High energy reduction in a propane dehydrogenation unit by utilizing a high pressure product splitter column
DE102010022775A1 (de) 2010-06-04 2011-12-08 Uhde Gmbh Verfahren und Vorrichtung zur Beseitigung von NOx und N2O
US9051230B2 (en) * 2011-04-20 2015-06-09 Uop Llc Processes for producing propylene from paraffins
CA2860773C (fr) 2012-01-13 2020-11-03 Siluria Technologies, Inc. Procede de separation de composes hydrocarbones
DE102012003741A1 (de) 2012-02-28 2013-08-29 Thyssenkrupp Uhde Gmbh Verfahren zur Rückgewinnung von Kohlenwasserstoffen aus Polyolefinanlagen und dafür geeignete Vorrichtung
US9670113B2 (en) 2012-07-09 2017-06-06 Siluria Technologies, Inc. Natural gas processing and systems
WO2014089479A1 (fr) 2012-12-07 2014-06-12 Siluria Technologies, Inc. Procédés et systèmes intégrés pour la conversion de méthane en de multiples produits hydrocarbonés supérieurs
CN104148101B (zh) * 2013-05-13 2016-12-28 中国科学院大连化学物理研究所 一种甲烷无氧直接制烯烃的方法及其催化剂
WO2015081122A2 (fr) 2013-11-27 2015-06-04 Siluria Technologies, Inc. Réacteurs et systèmes destinés au couplage oxydatif du méthane
CN110655437B (zh) 2014-01-08 2022-09-09 鲁玛斯技术有限责任公司 乙烯成液体的系统和方法
CA3148421C (fr) 2014-01-09 2024-02-13 Lummus Technology Llc Couplage oxydatif d'implementations methaniques pour la production d'olefines
WO2015160967A1 (fr) * 2014-04-15 2015-10-22 The Trustees Of Columbia University In The City Of New York Systèmes, procédés et supports pour extraire des informations et une image d'affichage à partir de deux images capturées
EP3029018A1 (fr) * 2014-12-05 2016-06-08 Linde Aktiengesellschaft Procédé et installation de production de propylène
US10793490B2 (en) 2015-03-17 2020-10-06 Lummus Technology Llc Oxidative coupling of methane methods and systems
US20160289143A1 (en) 2015-04-01 2016-10-06 Siluria Technologies, Inc. Advanced oxidative coupling of methane
FI126341B (en) * 2015-09-18 2016-10-14 Neste Oyj Method for separating and purifying renewable propane
EP4071131A1 (fr) 2016-04-13 2022-10-12 Lummus Technology LLC Appareil et procédé d'échange de chaleur
US10787402B2 (en) 2016-04-15 2020-09-29 Sabic Global Technologies B.V. Separation of off gases from C3 hydrocarbons in propane dehydrogenation process
CN106588548B (zh) * 2016-11-21 2019-05-17 中石化宁波工程有限公司 一种烯烃分离方法
HUE064375T2 (hu) 2017-05-23 2024-03-28 Lummus Technology Inc Metán oxidatív csatolási folyamatainak integrálása
US11091412B2 (en) * 2017-09-04 2021-08-17 China Petroleum & Chemical Corporation Process for producing ethylene
CN109678635B (zh) * 2017-10-19 2022-03-15 中国石油化工股份有限公司 一种饱和烃裂解气分离系统和富乙烷/丙烷饱和烃的利用方法
PL3873876T3 (pl) * 2018-11-02 2023-12-27 Shell Internationale Research Maatschappij B.V. Wytwarzanie etylenu przez odwodornienie oksydacyjne etanu
EP3715320A1 (fr) * 2019-03-27 2020-09-30 Siemens Aktiengesellschaft Procédé de génération d'un produit gazeux
CN110108091B (zh) * 2019-04-10 2020-08-21 大连理工大学 Star丙烷脱氢的氢气分离膜内嵌改进的深冷液化系统

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2930752A (en) * 1952-06-12 1960-03-29 Socony Mobil Oil Co Inc Process for stripping of absorption liquids
US4695662A (en) * 1986-04-04 1987-09-22 Uop Inc. Light paraffin dehydrogenation process
US4788371A (en) * 1987-12-30 1988-11-29 Uop Inc. Catalytic oxidative steam dehydrogenation process
US5220091A (en) * 1992-02-26 1993-06-15 Phillips Petroleum Company Alkane dehydrogenation
US5344805A (en) * 1993-05-03 1994-09-06 Phillips Petroleum Company Platinum and tin-containing catalyst and use thereof in alkane dehydrogenation
CN1035762C (zh) * 1994-11-23 1997-09-03 大庆石油学院 丙烷均相氧化脱氢及丙烯氧化制取丙烯酸的方法及其装置
US5877369A (en) * 1997-10-23 1999-03-02 Phillips Petroleum Company Hydrocarbon conversion catalyst composition and processes therefor and therewith
DE19756292C2 (de) * 1997-12-10 1999-10-28 Mannesmann Ag Katalysator zur Umwandlung paraffinischer Kohlenwasserstoffe in korrespondierende Olefine
DE19937107A1 (de) * 1999-08-06 2001-02-08 Basf Ag Katalysator mit bimodaler Porenradienverteilung
NO316512B1 (no) * 2000-01-25 2004-02-02 Statoil Asa Fremgangsmate og reaktor for autoterm dehydrogenering av hydrokarboner
DE10028582A1 (de) * 2000-06-14 2001-12-20 Basf Ag Verfahren zur Herstellung von Acrolein oder Acrylsäure oder deren Gemischen aus Propan
DE10211275A1 (de) * 2002-03-13 2003-09-25 Basf Ag Verfahren der kontinuierlichen heterogen katalysierten partiellen Dehydrierung
DE10245585A1 (de) * 2002-09-27 2004-04-08 Basf Ag Verfahren zur Herstellung von wenigstens einem partiellen Oxidations- und/oder Ammoxidationsprodukt des Propylens

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006069674A1 *

Also Published As

Publication number Publication date
EA200701051A1 (ru) 2007-12-28
CN101087740B (zh) 2010-09-22
KR20070089244A (ko) 2007-08-30
CA2591204A1 (fr) 2006-07-06
BRPI0519387A2 (pt) 2009-01-20
NO20072874L (no) 2007-09-17
EA010745B1 (ru) 2008-10-30
CN101087740A (zh) 2007-12-12
TW200639147A (en) 2006-11-16
JP2008524289A (ja) 2008-07-10
AU2005321540A1 (en) 2006-07-06
US20080207975A1 (en) 2008-08-28
MX2007006995A (es) 2007-07-04
DE102004061772A1 (de) 2006-07-06
WO2006069674A1 (fr) 2006-07-06
MY147177A (en) 2012-11-14

Similar Documents

Publication Publication Date Title
EP1833776A1 (fr) Procede de production de propene a partir de propane
EP1824803B1 (fr) Procede de fabrication de propene a partir de propane
EP1682468B1 (fr) Procede de fabrication de 1-butene
EP1453778B1 (fr) Procede pour produire du 1,2-dichloroethane
EP1858831A2 (fr) Procede de production de propene a partir de propane
EP1831134B1 (fr) Procede de production de butadiene a partir de n-butane
EP1836146B1 (fr) Procede de production de propene a partir de propane
EP2897927B1 (fr) Procédé de production de butadiène par élimination de l&#39;oxygène de flux d&#39;hydrocarbures en c4
WO2008009648A1 (fr) Procédé de fabrication d&#39;isopropanol et de 2-butanol à partir des alcanes correspondants
DE102005000798A1 (de) Verfahren zur Herstellung von Propen aus Propan
EP1678105B1 (fr) Procede de fabrication du 1-butene
WO2009074574A1 (fr) Procédé pour produire de l&#39;isopropanol et du 2-butanol à partir d&#39;alcanes adéquats
EP1404647A1 (fr) Procede de production de nitriles insatures a partir d&#39;alcanes
DE102005012291A1 (de) Verfahren zur Herstellung von Propen aus Propan
WO2003089407A1 (fr) Procede de preparation de nitriles insatures
DE10217844A1 (de) Verfahren zur Herstellung von ungesättigten Nitrilen aus Alkanen
WO2003029171A1 (fr) Procede de production de composes aromatiques alkyles

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20070723

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASF SE

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20101216