WO1991009826A1 - Procede de preparation d'octenes - Google Patents

Procede de preparation d'octenes Download PDF

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Publication number
WO1991009826A1
WO1991009826A1 PCT/GB1990/002011 GB9002011W WO9109826A1 WO 1991009826 A1 WO1991009826 A1 WO 1991009826A1 GB 9002011 W GB9002011 W GB 9002011W WO 9109826 A1 WO9109826 A1 WO 9109826A1
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WO
WIPO (PCT)
Prior art keywords
butene
weight
catalyst
process according
per cent
Prior art date
Application number
PCT/GB1990/002011
Other languages
English (en)
Inventor
Ramzi Yanni Saleh
Joel Robert Livingston
Georges Marie Karel Mathys
Original Assignee
Exxon Chemical Patents Inc.
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 Exxon Chemical Patents Inc. filed Critical Exxon Chemical Patents Inc.
Publication of WO1991009826A1 publication Critical patent/WO1991009826A1/fr

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Classifications

    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/10—Catalytic processes with metal oxides
    • 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
    • C07C2521/12—Silica and alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel

Definitions

  • PROCESS FOR THE PREPARATION OF OCTENES This invention relates to the production of octenes by dimerizing of butenes.
  • Octenes are useful for conversion by the oxo alcohol process into the corresponding nonyl alcohols which are used inter alia in the manufacture of plasticisers, lubricating oil additives, detergents and defoamers.
  • mixtures of isomeric octenes are customarily used but it is important that the mixture shall contain a blend of isomers giving rise to the desired properties in the final product.
  • n- Octenes for example, contain no side chain methyl groups, methyl-heptenes contain 1 side chain methyl group; dimethyl- hexenes contain 2 side chain methyl groups; and trimethyl- pentenes contain 3 side chain methyl groups.
  • a mixture of isomeric octenes having an average of 1.6 to 2.0 side chain methyl groups per molecule is widely regarded as especially suitable for conversion into nonyl alcohols for use in plasticisers.
  • 3658935 (Pine) describes a process for dimerising or co-dimerising an impure feed mixture containing n-butene propylene or mixtures thereof contaminated with impurities by passage over a nickel oxide catalyst. Hydrogen is added to the feed to lengthen the life of the nickel oxide catalyst and improve the proportion of desired dimers in the product.
  • the co- dimerizing is conducted at 140 to 300oF under a pressure from about 150 psi to 1000 psi.
  • 1069296 discloses the production of dimers from olefins such as butene by contact with a catalyst containing aluminum and nickel ions on a silica support at temperatures up to 400oC.
  • British Specification No. 1215943 discloses the dimerizing of olefins including butenes by contact with the same kind of catalyst which is activated in a slightly different manner.
  • the catalyst used in these specifications differs from those used in the two United States Patents referred to above, and in the present invention, by including only a small proportion of nickel and aluminum.
  • East German Specification No. 1060037 describes inter alia the dimerizing of a mixture of butenes over a catalyst based on amorphous alumina silicate containing a small proportion of nickel oxide.
  • the operating temperature was only about 100oC, but temperatures as high as 180oC are disclosed with other olefin starting materials.
  • Such known methods for dimerising butene to octenes suffer from one or more disadvantages, e.g. the blend of isomeric octenes obtained does not give the desired properties in the nonyl alcohols or their derivatives; the total conversion of butene into octene per pass over the catalyst used is too low (e.g. less than 50 per cent); and the nickel oxide catalyst is susceptible to the presence of poisons such as oxygenated compounds or organic sulphur and nitrogen compounds, in the butene feed. Such poisons are often difficult to avoid unless expensive purification procedures are used.
  • the present invention provides an improved process for the production of a mixture of isomeric octenes having an average of 1.6 to 2.0 side chain methyl groups per molecule.
  • the new process gives a high conversion rate per pass. While it can be operated with pure or substantially pure butene feed, it can also be used with feeds of typical commercial purity and, with only slight modification, with feeds containing appreciable amounts of sulphur-containing catalyst poisons.
  • a mixture of isomeric octenes having an average of 1.6 to 2.0 side chain methyl groups per molecule and containing not more than 8 per cent by weight of octenes having 3 side chain methyl groups per molecule is made by a process which comprises contacting an n-butene, for example in the form of a mixture containing at least 20 per cent by weight of an isomeric mixture of n- butenes and not more than 80 per cent by weight of saturated hydrocarbons, and preferably not more than 1.5 per cent by weight of isobutene, at a temperature between about 150oC and 275oC and in the supercritical state with a nickel oxide (NiO) catalyst containing 5 to 30 per cent by weight, preferably 20 to 30 per cent by weight, of NiO on a silica- alumina support containing 10 to 45 per cent by weight of AI 2 O 3 and having at least a surface area of 100 m 2 /g, preferably between 100 to 450 m 2 /g
  • the catalyst only has a life of less than 3 days corresponding to a weight ratio of product to catalyst of up to about 20. Under the conditions of the present invention, however, using the said feed and catalyst, the weight ratio of product to catalyst rises to over 600.
  • the catalyst can tolerate, under the specified operating conditions, the presence of small amounts of sulphur-containing compounds, such as organic sulphides or thiophenes, e.g. 1 to 40 ppmw, and preferably less than 20 or more preferably less than 10 ppmw in the butene feed without substantial deactivation over several days of operation.
  • sulphur-containing compounds such as organic sulphides or thiophenes, e.g. 1 to 40 ppmw, and preferably less than 20 or more preferably less than 10 ppmw in the butene feed without substantial deactivation over several days of operation.
  • the new process can be operated even with butene feeds containing larger amounts of sulphur provided that a small amount of a nitrogen-containing compound is present in, or is added to, the feed.
  • the presence of such nitrogen-containing compound apparently prevents the sulphur in the feed from binding to the nickel oxide and deactivating it.
  • the butene feed contains from 20 to 200 ppm, especially 20 to 40 ppm, of sulphur
  • the effect of such sulphur is counteracted by adding to the butene feed from 50 to 2000 ppm of a nitrogen-containing organic compound.
  • n-Butenes suitable for use in the present invention are commercially available from petroleum refinery operations.
  • butenes should not contain more than 1.5% of isobutenes, because isobutene tends to form products with a high degree of branching.
  • the butenes consist substantially entirely of 1-butene, cis-2- butene and/or trans-2-butene.
  • the presence of fully saturated hydrocarbons in the feed is not in general detrimental, but if the proportion rises above about 80 per cent by weight the process becomes uneconomic.
  • the presence of olefins containing more than 4 carbon atoms per molecule should likewise be avoided because they reduce the selectivity of the reaction to produce octenes.
  • the nickel oxide on silica-alumina catalyst used in the present invention is known and has been described in, for example, United States Patent 2581228. It may be made by treating a calcined silica-alumina gel with a solution of a water-soluble nickel salt, and then with an agent to precipitate the nickel on the gel, e.g. as the hydroxide or carbonate. The silica-alumina gel with the nickel hydroxide or carbonate precipitated thereon is then filtered off and dried and calcined. The proportion of NiO is chosen to provide essentially what is equivalent to a monolayer of the NiO on the silica-alumina support. Smaller or larger amounts of NiO reduce catalyst activity.
  • the proportion of alumina is chosen to provide a high conversion rate combined with acceptable catalyst life. Too little alumina allows rapid catalyst deactivation, while too much gives poor conversion rates. It has been found that the temperature of the calcination not only affects catalyst life but also can dramatically affect the isomer distribution in the mixture of octenes obtained in the new process.
  • the catalyst is calcined at 500 to 700°C so that a mixture containing a large proportion of octenes having an average of 1.6 to 2.0 side chain methyl groups per molecule is obtained.
  • the reaction temperature must be at least 150° C in order to achieve the required conversion rate and average number of methyl groups per molecule. However, if the temperature is too high, the proportion of side chain methyl groups increase, and it is therefore desirable to use a reaction temperature below about 275° C.
  • the contact temperature is in the range of 175 to 225° C, and it is especially preferred to operate at a temperature in the range of 180 to 200° C.
  • the pressure in the reaction zone must be sufficient to keep the butenes in the supercritical state at the operating temperature. In practice this requires a pressure in the range of about 50 to 200 bars, preferably about 70 bars.
  • the feed rate of the octene mixture should be such as to ensure a liquid hourly weight feed rate from 0.4 to 1.8, preferably 0.6 to 0.7 h -1 . Above this feed rate the butene conversion falls to unacceptable levels and the number of side chain methyl groups per octene molecule falls below 1.6.
  • the butene feed contains more than about 5 ppm of sulphur, derived from mercaptans, disulphides, hydrogen sulphide and the like, the poisoning effect of the sulphur can be counteracted by adding to the feed from 50 to 2,000 ppm of a nitrogen-containing compound.
  • Suitable nitrogen-containing compounds are aliphatic and saturated heterocyclic primary, secondary and tertiary amines containing 1 to 12 carbon atoms, e.g. mono-, di- or tri- ethyl- amine or a saturated heterocyclic amine such as pyrrollidine. It is believed that such nitrogen-containing compounds are effective because they prevent the sulphur- containing poisons in the butene feed from becoming bound to the nickel oxide catalyst and deactivating it. It is surprising that the nitrogen-containing compounds have this effect because at lower temperatures than those used in the present invention, such compounds are themselves regarded as catalyst poisons.
  • the process of the present invention does not require special apparatus and can be operated in any reactor configuration which is capable of promoting intimate contact between the butene feed and the catalyst.
  • the process can be operated batchwise, semi-batchwise, or continuously. Continuous operation in a fixed bed reactor is preferred.
  • the process of the present invention produces minor amounts of C 5-7 and C 9- 16 olefins. Of these the most important are the dodecenes, which in some cases are produced in a weight proportion as high as half that of the octenes. It is usually economically worthwhile to isolate and separate such by-product olefins.
  • Examples 1-24 illustrate the invention: Examples 1-24
  • butene feed in these Examples was a commercial product which contained the following major ingredients and impurities:
  • the butene mixture was passed over a 28 weight per cent NiO catalyst on a silica-alumina support containing 75 weight per cent silica and 25 weight per cent alumina, in the form of 3 mm tablets at a temperature in the range 185 to 195° C at a liquid hourly weight feed rate of about 0.6 to 1.6.
  • the pressure in the reaction zone was maintained at 70 bars.
  • W.W.H. is the liquid hourly weight feed rate, in the case of the batch examples 44-61 this is defined as the inverse of the feed weight divided by the catalyst weight multiplied by the reaction time.
  • CATLIFE, W prod /W cat is the length of each experimental run measured as the ratio of weight product produced to weight of catalyst used.
  • Conversion is the percentage of butene feedstock reacted.
  • Selectivity is the ratio of a specific product to the amount of butene feedstock reacted.
  • Yield is selectivity x conversion.
  • the butene feed in these Examples contained the following major ingredients and impurities:
  • the autoclave was evacuated/N 2 -purged three times, then charged with a known amount of high purity (>99%) butene. This step was followed by heating the autoclave to the set temperature for predetermined length of time with continuous stirring. The butene/catalyst weight ratio and heating time corresponded to the space velocity indicated in Table 4 below.
  • the autoclave was cooled to ⁇ 5oC, vented to the air, and the liquid product was analysed by gas chromatography. The following results were obtained:
  • Pentanethiol and diethyl disulfide are reported as sulfur.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Préparation d'un mélange d'octènes isomériques possédant en moyenne 1,6 à 2,0 groupes méthyles à chaîne latérale, en dimérisant du n-butène par contact avec un catalyseur d'oxyde de nickel sur un support composé de dioxyde de silicium-oxyde d'aluminium à une température supérieure à 150 °C à un rythme d'alimentation en poids de liquide par heure allant de 0,4 à 1,8 h-1.
PCT/GB1990/002011 1990-01-05 1990-12-21 Procede de preparation d'octenes WO1991009826A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP90300159 1990-01-05
EP90300159.2 1990-01-05

Publications (1)

Publication Number Publication Date
WO1991009826A1 true WO1991009826A1 (fr) 1991-07-11

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EP (1) EP0509003A1 (fr)
JP (1) JPH05504948A (fr)
CA (1) CA2073178A1 (fr)
WO (1) WO1991009826A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003031539A1 (fr) * 2001-10-12 2003-04-17 Fortum Oyj Composant d'essence oxygenee et procede de production
WO2005080302A1 (fr) * 2004-02-14 2005-09-01 Oxeno Olefinchemie Gmbh Procede pour produire des olefines avec 8 a 12 atomes de carbone
EP2181081A1 (fr) * 2007-08-24 2010-05-05 Neste Oil Oyj Procédé d'oligomérisation d'oléfines

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014151253A (ja) * 2013-02-06 2014-08-25 Jx Nippon Oil & Energy Corp オレフィン低重合方法およびそれに用いる触媒

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2642467A (en) * 1950-05-11 1953-06-16 Phillips Petroleum Co Production of high octane fuel components
US3658935A (en) * 1970-06-08 1972-04-25 Exxon Research Engineering Co Dimerization and codimerization process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2642467A (en) * 1950-05-11 1953-06-16 Phillips Petroleum Co Production of high octane fuel components
US3658935A (en) * 1970-06-08 1972-04-25 Exxon Research Engineering Co Dimerization and codimerization process

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003031539A1 (fr) * 2001-10-12 2003-04-17 Fortum Oyj Composant d'essence oxygenee et procede de production
WO2005080302A1 (fr) * 2004-02-14 2005-09-01 Oxeno Olefinchemie Gmbh Procede pour produire des olefines avec 8 a 12 atomes de carbone
EP2181081A1 (fr) * 2007-08-24 2010-05-05 Neste Oil Oyj Procédé d'oligomérisation d'oléfines
EP2181081A4 (fr) * 2007-08-24 2011-01-05 Neste Oil Oyj Procédé d'oligomérisation d'oléfines

Also Published As

Publication number Publication date
JPH05504948A (ja) 1993-07-29
CA2073178A1 (fr) 1991-07-06
EP0509003A1 (fr) 1992-10-21

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