EP0589112A1 - Verfahren zur Herstellung einer an tertiärem Amylmethyläther reiche Fraktion frei von Olefinen und einer an n-Pentan reiche paraffinische Fraktion - Google Patents

Verfahren zur Herstellung einer an tertiärem Amylmethyläther reiche Fraktion frei von Olefinen und einer an n-Pentan reiche paraffinische Fraktion Download PDF

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Publication number
EP0589112A1
EP0589112A1 EP9292402593A EP92402593A EP0589112A1 EP 0589112 A1 EP0589112 A1 EP 0589112A1 EP 9292402593 A EP9292402593 A EP 9292402593A EP 92402593 A EP92402593 A EP 92402593A EP 0589112 A1 EP0589112 A1 EP 0589112A1
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EP
European Patent Office
Prior art keywords
cut
weight
fraction
cyclopentene
charge
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.)
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Application number
EP9292402593A
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English (en)
French (fr)
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EP0589112B1 (de
Inventor
Patrick Sarrazin
Jean Cosyns
Alain Forestiere
Jean-Paul Boitiaux
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Publication date
Priority to FR919110625A priority Critical patent/FR2680516B1/fr
Priority to CA002076584A priority patent/CA2076584C/fr
Priority to JP22279792A priority patent/JP3198356B2/ja
Priority to ZA926311A priority patent/ZA926311B/xx
Priority to MX9204886A priority patent/MX9204886A/es
Priority to DE69217943T priority patent/DE69217943T2/de
Priority to ES92402593T priority patent/ES2101058T3/es
Application filed by IFP Energies Nouvelles IFPEN filed Critical IFP Energies Nouvelles IFPEN
Priority to EP92402593A priority patent/EP0589112B1/de
Priority to DK92402593.5T priority patent/DK0589112T3/da
Priority to US08/142,107 priority patent/US5352846A/en
Publication of EP0589112A1 publication Critical patent/EP0589112A1/de
Application granted granted Critical
Publication of EP0589112B1 publication Critical patent/EP0589112B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only

Definitions

  • the invention relates to a process for the simultaneous production of a cut rich in tertioamyl ether (TAME) in particular) and a cut rich in n-pentane, from a C5 cut containing isopentenes, cyclopentene and cyclopentadiene.
  • TAME tertioamyl ether
  • C5 steam cracking cuts which may contain up to 15% of the mixture of 2-methyl-butene-1, 2-methyl-butene-2, 3-methyl-butene-1.
  • this cut can simultaneously contain up to 30% of diolefins in the form of isoprene, pentadiene and cyclopentadiene.
  • the C5 cuts of steam cracking differ from the C5 cuts of catalytic cracking by the presence of cyclopentadiene and cyclopentene in significant quantities (see Table 1). It has been found that, surprisingly, the use of a C5 cut of steam cracking instead of a C5 cut of catalytic cracking makes it possible to obtain an isopentene distribution even closer to the thermodynamic equilibrium conditions.
  • the olefinic compounds are not separated from the paraffinic compounds, in particular because of the high cost of separation.
  • the product obtained is a mixture of paraffins, olefins, and tertioamylalkylether (TAME, for example).
  • US Pat. No. 4,361,422 describes such a process, in which more precisely a charge constituted by a C5 cut, and more particularly a C5 cut from steam cracking, is subjected to advanced hydrogenation so as to hydrogenate the diolefins (and in particular the cyclopentadiene) and to substantially conserve the etherifiable mono-olefins.
  • the catalyst used contains 0.2 to 2% by weight of palladium on a support, for example alumina or silica, and the operation is carried out between 50 and 200 ° C, with an outlet temperature of at least 120 ° C, under a pressure of 5 to 6 bars and at an hourly liquid charge rate of 0.50 to 10 volumes per volume of catalyst.
  • the product obtained containing up to 10% alcohol is sent to the fuel pool. After adding 0.15 g / l of Pb, it has a NOM index of 87.5 to 88.
  • the invention relates to a process for the simultaneous production of a fraction rich in tertioamylalkyl ether and cyclopentene and of a paraffinic fraction rich in n-pentane, from a charge constituted by a fraction containing C5 hydrocarbons, rich in olefins and containing isopentenes, cyclopentene and cyclopentadiene, process in which the charge is subjected to an isomerizing hydrogenation by passage of said charge with hydrogen in contact with at least one supported catalyst containing at least one noble metal of GVIII , at a temperature of 20 ° C to 150 ° C, a pressure of 5 to 100 bars, the effluent obtained is then subjected to etherification by an alcohol, process in which typically the hydrogenation is carried out in the presence of 2 at 400 ppm of at least one sulfur
  • the very advanced hydrogenation stage of the section C coupe arriving via the line (4) makes it possible to supply the etherification unit (2) with a charge free from diolefins and linear olefins (5) as described in Examples 3 and 4 below.
  • the isomerization of methyl-butenes-1 carried out during this step (1) leads to the production of a large amount of methyl-2-butene-2.
  • the performances of the etherification unit (2) are improved by the use of such a cut both from the point of view of the ether yield and from the point of view of the lifetime of the catalyst.
  • This catalyst is advantageously constituted by 0.2 to 2% by weight of palladium deposited on a support, which is for example an alumina or a silica.
  • a support which is for example an alumina or a silica.
  • Another particularly interesting catalyst (described in US Pat. No. 4,490,481) consists of 0.03 to 1% by weight of gold on a support, it is resistant to sulfur.
  • the product (6) obtained in this etherification step is sent to a separation column (3) operating under a pressure of 1 to 8 bars. At the head is obtained a section essentially containing saturated molecules (7) which will constitute a better quality filler for steam cracking compared to a section still containing olefins.
  • the bottom product of column (8) consisting of a mixture of TAME and cyclopentane has, surprisingly, an improved quality compared to a mixture containing residual olefins, in particular as regards the octane numbers sought ( NOR) and motor (NAME).
  • the hydrogenation step is carried out on a cut C5 - 200 ° C which, after depentanization by line (9) in column (10), will provide a cut C5 free of diolefins and d 'linear olefins (5) to the etherification unit (2) which will be followed by a separation column (3).
  • a product C6 + (generally C6 - 200 ° C) will be drawn from column 10.
  • This cut also has a sulfur content of 10 ppm.
  • C coupe and methanol is passed from bottom to top on a fixed bed of catalyst of the ion exchange resin type in its acid form; these are crosslinked sulfonic polystyrene resins which are in the form of micro-beads from 0.15 to 0.40 mm in diameter.
  • the fixed catalyst bed is placed in a tubular reactor maintained under substantially isothermal conditions.
  • the catalyst was impregnated with methanol.
  • reactive isoamylene means the sum of 2-methyl-butene-1 and 2-methyl-butene-2.
  • the operation is carried out continuously for a hundred hours.
  • the conversion of reactive isoamylenes is 65%, but there is a gradual increase in the pressure drop in the reactor.
  • this pressure drop reaches 3 bar, the test is stopped and the catalyst discharged: the catalyst grains are agglomerated; in fact these grains are embedded in a gangue formed by the polymerization of the diolefins of the filler.
  • the same C5 cut of steam cracking is methoxylated after having been freed by selective hydrogenation of its diolefinic compounds.
  • This selective hydrogenation is carried out as follows: the raw C5 cut is passed over a fixed bed of catalyst consisting of 0.3% by weight of palladium deposited on a tetragonal gamma alumina in the form of beads; the specific surface of this alumina is 60 m2 / g.
  • the fixed catalyst bed is placed in a tubular reactor maintained under substantially isothermal conditions. Before use, the catalyst is reduced at atmospheric pressure under a stream of hydrogen at 100 ° C for 2 hours.
  • the load processing conditions are as follows: Pressure: 25 bar Temperature : 80 ° C Charge volume flow rate per catalyst volume and per hour: 5 Flow rate of hydrogen in moles per mole of hydrocarbon charge: 0.5
  • the distillate contains 38.9% olefins, which makes it unattractive to use as a steam cracker filler.
  • the same C5 cut of steam cracking gasoline is always methoxylated after having been rid of it by a thorough hydrogenation of its linear and cyclic olefins and diolefins.
  • the isoamylenes are not affected by this hydrogenation but for these products a mixture is obtained, the composition is close to that expected under thermodynamic equilibrium conditions.
  • the treatment conditions for this hydrogenation which is carried out in the same apparatus and with the same catalyst as those already described in Example 2, are as follows: Pressure: 25 bar Temperature : 120 ° C Volume flow rate of the charge per volume of catalyst and per hour: 4 Flow rate of hydrogen in moles per mole of hydrocarbon charge: 0.7
  • the TAME composition of the effluent is 22.0%, which is higher than those which resulted from the conditions described in Examples 1 (6.6% by weight) and 2 (19.8% by weight).
  • the TAME composition of the effluent is 21.6% which is higher than those which resulted from the conditions described in Examples 1 (6.6% by weight) and 2 (19.8% by weight).

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP92402593A 1991-08-23 1992-09-21 Verfahren zur Herstellung einer an tertiärem Amylmethyläther reichen Fraktion frei von Olefinen und einer an n-Pentan reichen paraffinischen Fraktion Expired - Lifetime EP0589112B1 (de)

Priority Applications (10)

Application Number Priority Date Filing Date Title
FR919110625A FR2680516B1 (fr) 1991-08-23 1991-08-23 Procede de production d'une coupe riche en tertioamylalkylether exempte d'olefines et d'une coupe paraffinique riche en n-pentane.
JP22279792A JP3198356B2 (ja) 1991-08-23 1992-08-21 ３級アミルアルキルエーテルに富みオレフィン類を含まない溜分とｎ−ペンタンに富むパラフィン溜分の製造法
ZA926311A ZA926311B (en) 1991-08-23 1992-08-21 Process for the production of an olefin-free tert.amyl alkyl ether-rich fraction and a n-pentane rich paraffin fraction
CA002076584A CA2076584C (fr) 1991-08-23 1992-08-21 Procede de production d'une coupe riche en tertioamylalkylether exempte d'olefines et d'une coupe paraffinique riche en n-pentane
MX9204886A MX9204886A (es) 1991-08-23 1992-08-24 Proceso para la produccion de un corte rico en tercioamilalquileter exent0 de olefinas y de un corteparafinico rico en n-pentano.
ES92402593T ES2101058T3 (es) 1991-08-23 1992-09-21 Procedimiento de produccion de una fraccion rica en tertioamilatileter exenta de olefinas y de una fraccion parafinica rica en n-pentano.
DE69217943T DE69217943T2 (de) 1991-08-23 1992-09-21 Verfahren zur Herstellung einer an tertiärem Amylmethyläther reichen Fraktion frei von Olefinen und einer an n-Pentan reichen paraffinischen Fraktion
EP92402593A EP0589112B1 (de) 1991-08-23 1992-09-21 Verfahren zur Herstellung einer an tertiärem Amylmethyläther reichen Fraktion frei von Olefinen und einer an n-Pentan reichen paraffinischen Fraktion
DK92402593.5T DK0589112T3 (da) 1991-08-23 1992-09-21 Fremgangsmåde til fremstilling af en oleinfri tertioamylethyletherrig fraktion og en N-pentanrig paraffinfraktion
US08/142,107 US5352846A (en) 1991-08-23 1993-10-28 Process for the production of an olefin-free tert, amyl alkyl ether-rich fraction and a n-pentane rich paraffin fraction

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR919110625A FR2680516B1 (fr) 1991-08-23 1991-08-23 Procede de production d'une coupe riche en tertioamylalkylether exempte d'olefines et d'une coupe paraffinique riche en n-pentane.
EP92402593A EP0589112B1 (de) 1991-08-23 1992-09-21 Verfahren zur Herstellung einer an tertiärem Amylmethyläther reichen Fraktion frei von Olefinen und einer an n-Pentan reichen paraffinischen Fraktion

Publications (2)

Publication Number Publication Date
EP0589112A1 true EP0589112A1 (de) 1994-03-30
EP0589112B1 EP0589112B1 (de) 1997-03-05

Family

ID=26132423

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92402593A Expired - Lifetime EP0589112B1 (de) 1991-08-23 1992-09-21 Verfahren zur Herstellung einer an tertiärem Amylmethyläther reichen Fraktion frei von Olefinen und einer an n-Pentan reichen paraffinischen Fraktion

Country Status (10)

Country Link
US (1) US5352846A (de)
EP (1) EP0589112B1 (de)
JP (1) JP3198356B2 (de)
CA (1) CA2076584C (de)
DE (1) DE69217943T2 (de)
DK (1) DK0589112T3 (de)
ES (1) ES2101058T3 (de)
FR (1) FR2680516B1 (de)
MX (1) MX9204886A (de)
ZA (1) ZA926311B (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5689013A (en) * 1995-09-12 1997-11-18 Neste Ot Process for preparing tertiary alkyl ethers from an olefinic hydrocarbon feedstock
US6620982B1 (en) * 1998-10-07 2003-09-16 Equistar Chemicals, Lp Method of producing purified cyclopentane
CN104557398B (zh) * 2013-10-28 2017-08-11 中国石油化工股份有限公司 碳五生产丙烯的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0035935A1 (de) * 1980-03-10 1981-09-16 Institut Français du Pétrole Hydrierung und Verätherung einer ungesättigten C5-Kohlenwasserstofffraktion zum Verbessern der Oktanzahl und Vermindern des Monoolefingehaltes
US4490481A (en) * 1982-03-15 1984-12-25 Ste Francaise Des Produits Pour Catalyse Chez Institut Francais Du Petrole Supported palladium-gold catalyst, and its manufacture
EP0190964A1 (de) * 1985-02-04 1986-08-13 Institut Français du Pétrole Verfahren zur Herstellung von 2-Methylbuten-2 aus einem olefinischen C5-Schnitt, der 2-Methylbuten-1 und wenigstens ein n-Penten enthält

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4193770A (en) * 1977-12-22 1980-03-18 Gulf Canada Limited Preparation of gasoline containing tertiaryamyl methyl ether
US5136108A (en) * 1991-09-13 1992-08-04 Arco Chemical Technology, L.P. Production of oxygenated fuel components

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0035935A1 (de) * 1980-03-10 1981-09-16 Institut Français du Pétrole Hydrierung und Verätherung einer ungesättigten C5-Kohlenwasserstofffraktion zum Verbessern der Oktanzahl und Vermindern des Monoolefingehaltes
US4490481A (en) * 1982-03-15 1984-12-25 Ste Francaise Des Produits Pour Catalyse Chez Institut Francais Du Petrole Supported palladium-gold catalyst, and its manufacture
EP0190964A1 (de) * 1985-02-04 1986-08-13 Institut Français du Pétrole Verfahren zur Herstellung von 2-Methylbuten-2 aus einem olefinischen C5-Schnitt, der 2-Methylbuten-1 und wenigstens ein n-Penten enthält

Also Published As

Publication number Publication date
CA2076584C (fr) 2005-10-18
DE69217943T2 (de) 1997-09-04
CA2076584A1 (fr) 1993-02-24
EP0589112B1 (de) 1997-03-05
ZA926311B (en) 1994-02-21
US5352846A (en) 1994-10-04
FR2680516B1 (fr) 1994-09-02
DK0589112T3 (da) 1997-08-04
JP3198356B2 (ja) 2001-08-13
JPH05238962A (ja) 1993-09-17
MX9204886A (es) 1993-04-01
DE69217943D1 (de) 1997-04-10
ES2101058T3 (es) 1997-07-01
FR2680516A1 (fr) 1993-02-26

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