EP0210514B1 - 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
EP0210514B1
EP0210514B1 EP86109588A EP86109588A EP0210514B1 EP 0210514 B1 EP0210514 B1 EP 0210514B1 EP 86109588 A EP86109588 A EP 86109588A EP 86109588 A EP86109588 A EP 86109588A EP 0210514 B1 EP0210514 B1 EP 0210514B1
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EP
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Prior art keywords
hydrogenation
catalyst
process according
tert
alkyl
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EP86109588A
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German (de)
English (en)
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EP0210514A2 (fr
EP0210514A3 (en
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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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    • 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 optionally other saturated aliphatic or aromatic hydrocarbons, the tert-alkyl alkyl ethers being largely retained.
  • 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 unleaded Gasoline should be added.
  • EP 49 803 discloses the hydrogenation of a pyrolysis gasoline fraction in which metals from subgroup VIII of the periodic table of the elements on zeolitic supports are used as catalysts. Because of their regular structure, zeolites have passages and pores with discrete diameters depending on the type; pore diameters of 3-12 ⁇ are suitable for the process of EP 49 803. Zeolites are generally acidic in character.
  • tert-alkyl alkyl ethers on acidic catalysts which include acidic cation exchangers and also mordenites, zeolites, various Al2O3 modifications, various SiO2 modifications and others, already from 90 ° C reaction temperature in alkanols and tert. -Alkenes are split back.
  • oligomeric tertiary alkenes can also be cleaved on acidic catalysts, for example those mentioned.
  • a catalyst which is a hydrogenation-active Component on a catalyst carrier with a specific surface area of more than 50 m2 / g and a pore diameter of predominantly ⁇ 1000 nm has, the catalyst carrier being neutral or doped with (earth) alkali compounds.
  • 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 g / l catalyst.
  • the other metals mentioned which are not among the platinum metals can also be used in bound form.
  • Substances can be used as carrier material for the hydrogenation catalysts to be used according to the invention, the specific surface area of which is> 50 m2 / g catalyst, but especially> 100 m2 / g catalyst and the pore diameter of which is predominantly ⁇ 1000 nm, but especially ⁇ 200 nm.
  • Such substances can be, for example, neutral aluminum silicates, diatomaceous earth, Al2O3, coal, etc. if they meet the above conditions. Kieselguhr and Al2O3 are particularly suitable.
  • carrier materials such as SiO2 or acidic aluminum silicates are suitable if they are doped with alkali or alkaline earth compounds.
  • concentration of alkali or alkaline earth compounds is 0.01-1, preferably 0.02-0.2 equivalents of alkali / alkaline earth metal per liter of catalyst in question.
  • the above-mentioned neutral carriers can also be given such a doping.
  • the hydrogenation according to the invention is possible both in the trickle phase and in the liquid or gaseous phase and is generally carried out at a temperature of 50-200 ° C., preferably 80-180 ° C., particularly preferably 100-150 ° C.
  • the hydrogen partial pressure is generally set at 1-100 bar, preferably 2-40 bar, particularly preferably 5-30 bar.
  • Pure hydrogen, technical hydrogen or hydrogen-containing residual gas present in petrochemical plants can be used as hydrogen.
  • the hydrogen content is 70-100%, in many cases also about 80 to about 90%.
  • the impurities present in technical hydrogen and in hydrogen-containing residual gases are, for example, nitrogen, methane or ethane.
  • the amount of hydrogen is adjusted in the process according to the invention so that the degree of remaining unsaturation corresponds to the desired value.
  • the reaction temperature and / or the residence time in the hydrogenation reactor are also used in a manner known to the person skilled in the art; it is often possible to work with an excess of hydrogen which is removed after the hydrogenation reaction or is operated as a cycle gas.
  • the remaining degree of unsaturation is measured by the bromine number in g Br2 / 100 g hydrocarbon mixture. Bromine numbers over 50, even over According to the invention, 70 g Br2 / 100 g hydrocarbon mixture can be pressed over all conceivable intermediate values down to values of less than 5, even down to ⁇ 0.01 g Br2 / 100 g hydrocarbon mixture.
  • the content of tert-alkyl alkyl ether is obtained.
  • Preservation means, for example, the maintenance of at least 90% of the original ether content, in many cases more than 96% of the ether.
  • the catalyst load in the process according to the invention is 1-5 l of the material used per l catalyst and hour for working in the liquid and trickle phases.
  • the catalyst load is 2-3 l / l catalyst and hour.
  • the heat of reaction generated can be dissipated by cooling the reactor or by the sensible heat of the reaction product. To avoid temperature peaks, the feed can be diluted by returning some of the hydrogenated product to the feed.
  • 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 alkanols.
  • Particularly suitable gasoline cuts are those which, due to their C number range, are suitable for suitable for later use in petrol.
  • Examples of such tertiary alkyl alkyl ethers in such mixtures are those derived from tertiary C4-C4 alkenes and C1-C4 alcohols.
  • the ethers of the tertiary C4-C Alk alkenes with methanol in particular those of the tertiary C5-C6 alkenes with methanol.
  • excess hydrogen is optionally separated off with accompanying substances such as methane, ethane or nitrogen and other low boilers as residual gas.
  • the hydrogenation product according to the invention which is present after the removal of a residual gas can be used as a gasoline additive.
  • 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 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
  • the present invention is illustrated by the following examples.
  • Conventional hydrogenation apparatuses are used here (FIGS. 1, 2 and 3).
  • the experimental setup was basically the same for the hydrogenations; the only difference was the direction of flow through the hydrogenation reactor, which was set from bottom to top in the case of liquid phase hydrogenation and from top to bottom in the cases of gas phase and trickle phase hydrogenation.
  • the starting material for all experiments described below was a C5-C6 hydrocarbon fraction from a pre-hydrogenated 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). This consisted of a thermostatted double jacket with the following dimensions: inner diameter 25 mm and length 750 mm.
  • 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) (about 80 vol .-% H2, about 20 vol .-% CH4) was added to the feed before the preheater (3).
  • the hydrogenated product reached the separator (6) via the cooler (5).
  • the amount of exhaust gas (8) was 200 Nl / h.
  • a circuit line (9) was additionally used to recirculate part of the H2 residual gas (8) obtained 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 feed material 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)

Claims (9)

  1. Procédé d'hydrogénation d'hydrocarbures oléfiniques en mélanges avec des éthers de tertio-alkyle et d'alkyle et, le cas échéant, d'autres hydrocarbures aliphatiques saturés, naphténiques ou aromatiques, dans lequel les éthers sont largement maintenus intacts, caractérisé en ce qu'on utilise un catalyseur qui possède un composant doué d'activité d'hydrogénation fixé sur un support de catalyseur ayant une surface spécifique de plus de 50 m²/g et un diamètre des pores principalement inférieur à 1000 nm, le support du catalyseur étant neutre ou dopé avec des composés alcalins (alcalino-terreux).
  2. Procédé suivant la revendication 1, caractérisé en ce que le composant doué d'activité d'hydrogénation consiste en au moins un métal noble du 8ème sous-groupe du Système Périodique des Eléments, en particulier le platine et/ou le palladium et en ce que la concentration en métal noble s'élève à 1-50 g/l de catalyseur, en particulier à 5-20 g/l de catalyseur.
  3. Procédé suivant la revendication 1, caractérisé en ce que le composant doué d'activité d'hydrogénation est le cobalt, le nickel, le molybdène ou des mélanges de ces métaux sous la forme élémentaire ou sous la forme combinée et en ce que la concentration du composant doué d'activité d'hydrogénation, exprimée en métal, s'élève à 200-800 g/l, notamment à 300-700 g/l de catalyseur.
  4. Procédé suivant les revendications 1 à 3, caractérisé en ce qu'on utilise comme matière de support des silicates d'aluminium, du kieselguhr, du charbon, de l'alumine, en particulier du kieselguhr et de l'alumine, dont la surface spécifique est supérieure à 50 m²/g de catalyseur et dont le diamètre des pores est inférieur à 1000 nm.
  5. Procédé suivant les revendications 1 à 4, caractérisé en ce que la surface spécifique du support de catalyseur est supérieure à 100 m²/g.
  6. Procédé suivant les revendications 1 à 5, caractérisé en ce que le diamètre des pores des supports de catalyseur est principalement inférieur à 200 nm.
  7. Procédé suivant les revendications 1 à 6, caractérisé en ce que la matière de support ou le catalyseur est dopé avec des composés alcalins ou alcalinoterreux, la concentration étant de 0,01 à 1 équivalent de métal alcalin/alcalino-terreux par litre de catalyseur.
  8. Procédé suivant les revendications 1 à 7, caractérisé en ce que l'hydrogénation est effectuée à une température de réaction de 50 à 200°C, en particulier à 80-180°C et sous une pression partielle d'hydrogène moléculaire de 1 à 100 bars, en particulier de 2 à 40 bars.
  9. Procédé suivant les revendications 1 à 8, caractérisé en ce qu'on utilise comme charge des mélanges d'hydrocarbures qui contiennent les éthers méthyliques de l'isobutène et/ou des tertio-amylènes et/ou des tertio-hexènes, en particulier des fractions d'essence de pyrolyse qui contiennent des éthers méthyliques de tertio-amylènes et/ou de tertio-hexènes.
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
DE19853526443 DE3526443A1 (de) 1985-07-24 1985-07-24 Verfahren zur hydrierung olefinischer kohlenwasserstoffe in tert.-alkyl-alkylether enthaltenden kohlenwasserstoffgemischen
DE3526443 1985-07-24

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

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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

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

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5028665A (en) * 1989-01-09 1991-07-02 The Dow Chemical Company Polymer hydrogenation catalysts
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
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
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
JP4829308B2 (ja) * 2005-11-10 2011-12-07 ユーオーピー エルエルシー オレフィン類の選択的水素化方法

Citations (1)

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Publication number Priority date Publication date Assignee Title
DE1667194A1 (de) * 1967-02-27 1972-03-16 Melle Benzons Saint Leger Les Hydrierkatalysator und Verfahren zur Herstellung desselben

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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
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1667194A1 (de) * 1967-02-27 1972-03-16 Melle Benzons Saint Leger Les Hydrierkatalysator und Verfahren zur Herstellung desselben

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Publication number Publication date
DE3526443A1 (de) 1987-02-05
EP0210514A2 (fr) 1987-02-04
EP0210514A3 (en) 1988-08-17
DE3677556D1 (de) 1991-03-28
US4950820A (en) 1990-08-21

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