EP0210514A2 - Hydrogénation d'hydrocarbures oléfiniques dans des mélanges d'hydrocarbures contenant des éthers t-alcoyl-alcoyl - Google Patents

Hydrogénation d'hydrocarbures oléfiniques dans des mélanges d'hydrocarbures contenant des éthers t-alcoyl-alcoyl Download PDF

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Publication number
EP0210514A2
EP0210514A2 EP86109588A EP86109588A EP0210514A2 EP 0210514 A2 EP0210514 A2 EP 0210514A2 EP 86109588 A EP86109588 A EP 86109588A EP 86109588 A EP86109588 A EP 86109588A EP 0210514 A2 EP0210514 A2 EP 0210514A2
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EP
European Patent Office
Prior art keywords
hydrogenation
catalyst
alkyl
tert
active component
Prior art date
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EP86109588A
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German (de)
English (en)
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EP0210514A3 (en
EP0210514B1 (fr
Inventor
Bernhard Dr. Schleppinghoff
Horst Dipl.-Ing. Reinhardt
Hans-Joachim Dr. Krämer
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Erdoelchemie GmbH
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Erdoelchemie GmbH
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Publication of EP0210514A3 publication Critical patent/EP0210514A3/de
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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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds

Definitions

  • the present invention relates to a process for the hydrogenation of olefinic hydrocarbons which are in a mixture with tert-alkyl alkyl ethers and, if appropriate, other saturated aliphatic or aromatic hydrocarbons, the tert-alkyl alkyl ethers being largely retained, and to the use of these Hydrogenating mixtures.
  • tertiary alkyl alkyl ethers the best known of which are methyl tertiary butyl ether (MTBE) and tertiary amyl methyl ether (TAME), can be added to the motor spirit.
  • MTBE methyl tertiary butyl ether
  • TAME tertiary amyl methyl ether
  • Such ethers are generally prepared by etherification of tertiary alkenes in gasoline cuts and other suitable starting materials with lower alkanols on acidic catalysts, such as cation exchangers, sulfuric acid and other acidic catalysts.
  • the resulting ether-containing reaction mixtures contain even larger amounts of olefinic hydrocarbons, which impair the quality of these mixtures as gasoline additives, especially if they are to be added to unleaded gasoline.
  • tert-alkyl alkyl ethers on acidic catalysts which in addition to acidic cation exchangers also include mordenites, zeolites, various A1 2 0 3 modifications, various Si0 2 modifications and others, from a reaction temperature of 90 ° C. in Alkanols and tert-alkenes are cleaved back.
  • oligomeric tertiary alkenes can also be cleaved over acidic catalysts, for example those mentioned.
  • Elements of the 6th, 7th or 8th subgroup of the Periodic Table of the Elements are suitable as the hydrogenation-active component.
  • the platinum metals especially platinum and / or palladium, very particularly palladium, are used in a concentration of 1-50 g / l catalyst, especially 5-20 gll catalyst.
  • the other metals mentioned which are not among the platinum metals can also be used in bound form.
  • Substances whose specific surface area) is 50 m 2 / g catalyst, but particularly) 100 m 2 / g catalyst and whose pore diameter is predominantly ⁇ 1000 nm, but particularly predominantly ⁇ 200 nm, can be used as carrier material for the hydrogenation catalysts to be used according to the invention.
  • Such substances can, for example, be predominantly neutral aluminum silicates, kieselguhr, A1 2 0 3 , coal, etc. if they meet the above conditions. Kieselguhr and A1 2 0 3 are particularly suitable.
  • the hydrogen partial pressure is generally set at 1-100 bar, preferably 2-40 bar, particularly preferably 5-30 bar.
  • Suitable starting materials for the process according to the invention are those which contain tert-alkyl alkyl ethers in addition to olefinic, paraffinic, naphthenic or aromatic hydrocarbons and, if appropriate, minor amounts of diolefins.
  • Such mixtures are obtained, for example, when gasoline cuts, for example from a steam cracker, a fluid catalyst cracker (FCC) or from dehydrogenation plants are reacted with lower alkanes.
  • Particularly suitable gasoline cuts are those which, owing to their C number range, are suitable for later use in gasoline.
  • tert-alkyl ethers in such mixtures those are mentioned, for example, the tertiary C 4 -C S alkenes and C l -C 4 alcohols derived.
  • excess hydrogen is optionally separated off with accompanying substances such as methane, ethane or nitrogen and other low boilers as residual gas.
  • the hydrogenation mixture obtainable according to the invention can also be separated in such a way that a gasoline cut without a tert-alkyl alkyl ether is obtained in a distillation column, from which the residual gas still has to be removed, a pure ether, for example TAME, is obtained as a side stream and small amounts of higher boilers, such as higher ethers and oligomers, remain in the swamp.
  • a pure ether for example TAME
  • the starting material for all experiments described below was a C 5 -C 6 hydrocarbon fraction from a prehydrogenated pyrolysis gasoline, which had been subjected to etherification with methanol and consequently contained tert-amyl methyl ether (TAME) and tert-hexyl methyl ether.
  • This feed material had the following characteristic compositional characteristics:
  • FIG. 1 hydrogenation in the trickle phase
  • FIG. 2 gas phase hydrogenation
  • FIG. 3 hydrogenation in the liquid phase
  • the feed material was transported from a graduated insert vessel (1) by means of a piston pump (2) via the preheater (3) into the hydrogenation reactor (4).
  • the hydrogenation catalyst 250 ml was arranged as a fixed bed and was enclosed up and down by a pack of ceramic balls (each 50 mm long).
  • the hydrogen (7) (approx. 80 vol. XH 2 , approx. 20 vol. X CH 4 ) was metered into the feed before the preheater (3).
  • the hydrogenated product reached the separator (6) via the cooler (5).
  • the amount of exhaust gas (8) (predominantly H 2 and CH 4 ) was 200 Nl / h.
  • a circuit line (9) was additionally used to recirculate part of the residual H 2 gas (8) accumulating in the separator (6) to the fresh hydrogen (7).
  • the preheater (3) was also used as an evaporator and the cooler (5) was also used as a condenser.
  • the hydrogenation reactor (4) was flown from below. Valves and measuring and control devices known to the person skilled in the art are not shown in FIGS. 1, 2 and 3.
  • reaction pressure was adjusted to 2 bar at 100 ° C reactor temperature and to 5 bar at 150'C reactor temperature.
  • the amount of circulating gas in the gas phase hydrogenation was 500 Nl / h.
  • the mode of action of the hydrogenation was assessed for the reactor temperatures of 100 and 150 ° C. after the hydrogenation of the alkenes in the feedstock by the bromine number and the TAME content.
  • the catalysts used for the hydrogenation are listed in Table 1.
  • the results for the particular hydrogenation depending on the catalysts listed in Table 1 are summarized in Table 2.

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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)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
EP86109588A 1985-07-24 1986-07-14 Hydrogénation d'hydrocarbures oléfiniques dans des mélanges d'hydrocarbures contenant des éthers t-alcoyl-alcoyl Expired - Lifetime EP0210514B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3526443 1985-07-24
DE19853526443 DE3526443A1 (de) 1985-07-24 1985-07-24 Verfahren zur hydrierung olefinischer kohlenwasserstoffe in tert.-alkyl-alkylether enthaltenden kohlenwasserstoffgemischen

Publications (3)

Publication Number Publication Date
EP0210514A2 true EP0210514A2 (fr) 1987-02-04
EP0210514A3 EP0210514A3 (en) 1988-08-17
EP0210514B1 EP0210514B1 (fr) 1991-02-20

Family

ID=6276612

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86109588A Expired - Lifetime EP0210514B1 (fr) 1985-07-24 1986-07-14 Hydrogénation d'hydrocarbures oléfiniques dans des mélanges d'hydrocarbures contenant des éthers t-alcoyl-alcoyl

Country Status (3)

Country Link
US (1) US4950820A (fr)
EP (1) EP0210514B1 (fr)
DE (2) DE3526443A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0378104A3 (fr) * 1989-01-09 1992-01-02 The Dow Chemical Company Catalyseur d'hydrogénation de polymères
CN1051478C (zh) * 1996-08-21 2000-04-19 中国石化齐鲁石油化工公司 烯烃醚化催化剂及其制法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4013711A1 (de) * 1990-04-28 1991-10-31 Erdoelchemie Gmbh Verfahren zur herstellung von hochoktanigen, olefinarmen kraftstoffen und kraftstoffkomponenten
US5600045A (en) * 1993-12-02 1997-02-04 The Dow Chemical Company Process for conversion of crude hydrocarbon mixtures
DE19756369A1 (de) 1997-12-18 1999-07-01 Bayer Ag Verfahren zur Hydrierung aromatischer Polymere
US6548721B1 (en) * 2001-05-22 2003-04-15 Uop Llc Hydrotreating olefin stream with complete destruction of oxygenates
CN101300213B (zh) * 2005-11-10 2011-05-11 环球油品公司 烯烃的选择性加氢方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA248010A (fr) * 1925-03-24 The Gulf Refining Company Production de chlorure d'aluminium
US3077733A (en) * 1959-08-17 1963-02-19 Phillips Petroleum Co Method of making jet fuel and use thereof
US3098106A (en) * 1959-12-07 1963-07-16 Exxon Research Engineering Co Production of rocket fuel
FR93716E (fr) * 1967-02-27 1969-05-09 Melle Bezons Catalyseurs d'hydrogenation et leur procede de preparation.
FR1560586A (fr) * 1968-02-02 1969-03-21
US3549720A (en) * 1969-07-22 1970-12-22 Catalysts & Chem Inc Selective hydrogenation of acetylenes and catalyst therefor
US3679762A (en) * 1970-06-08 1972-07-25 Catalysts & Chem Inc Selective hydrogenation of acetylenes
FR2097016B1 (fr) * 1970-07-27 1973-05-25 Inst Francais Du Petrole
GB1361671A (en) * 1971-01-06 1974-07-30 Bp Chem Int Ltd Process for the production of gaseous olefins from petroleum distillate feedstocks
US4224458A (en) * 1979-01-31 1980-09-23 Allied Chemical Corporation Process for homogeneous hydrogenation of polycyclic aromatic hydrocarbons
DE3038117A1 (de) * 1980-10-09 1982-05-13 EC Erdölchemie GmbH, 5000 Köln Hydrierte kohlenwasserstoffgemiche, verfahren zu ihrer herstellung, ihre verwendung und treibstoffe, enthaltend diese hydrierten kohlenwasserstoffgemische
US4546204A (en) * 1983-11-07 1985-10-08 Imperial Chemical Industries Australia Limited Process for the manufacture of methyl t-butyl ether
US4558168A (en) * 1985-06-19 1985-12-10 Air Products And Chemicals, Inc. Production of high purity butene-1 from an n-butane feedstock

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0378104A3 (fr) * 1989-01-09 1992-01-02 The Dow Chemical Company Catalyseur d'hydrogénation de polymères
CN1051478C (zh) * 1996-08-21 2000-04-19 中国石化齐鲁石油化工公司 烯烃醚化催化剂及其制法

Also Published As

Publication number Publication date
DE3677556D1 (de) 1991-03-28
US4950820A (en) 1990-08-21
EP0210514A3 (en) 1988-08-17
DE3526443A1 (de) 1987-02-05
EP0210514B1 (fr) 1991-02-20

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