WO2000040527A1 - Procede ameliore pour produire des liquides aromatiques alkyles - Google Patents

Procede ameliore pour produire des liquides aromatiques alkyles Download PDF

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Publication number
WO2000040527A1
WO2000040527A1 PCT/US2000/000093 US0000093W WO0040527A1 WO 2000040527 A1 WO2000040527 A1 WO 2000040527A1 US 0000093 W US0000093 W US 0000093W WO 0040527 A1 WO0040527 A1 WO 0040527A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
zeolite
alkylation
zsm
butylbenzene
Prior art date
Application number
PCT/US2000/000093
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English (en)
Inventor
Margaret May-Son Wu
Philip Trotto
Gilbert Randy Jersey
Andrew G. Horodysky
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Mobil Oil Corporation
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 Mobil Oil Corporation filed Critical Mobil Oil Corporation
Priority to AU34692/00A priority Critical patent/AU3469200A/en
Publication of WO2000040527A1 publication Critical patent/WO2000040527A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C10M105/06—Well-defined hydrocarbons aromatic

Definitions

  • This invention relates to an improved process for alkylating aromatic compounds in the production of lubricant fluids.
  • the invention particularly relates to an improvement in the production of monoalkyl aromatic alkylates prepared by zeolite catalysis that yields an essentially colorless lubricant fluid of superior thermal stability.
  • Alkylaromatic fluids are well known in the synthetic lubricant and specialty fluid arts where fluids having good thermal and oxidative stability are required.
  • U. S. patent 4,714,794 describes monoalkylated naphthalenes as having excellent thermal and oxidative stability sufficient to allow their use as thermal medium oils.
  • U. S. patents 4,211 ,665 and 4,238,343 describe the use of alkylaromatics as transformer oils.
  • alkylaromatics of lubricant quality is carried out usually by alkylation of aromatics in the presence of an acidic Friedel-Kraft alkylation catalyst like aluminum trichloride as described in U.S. patents 4,211,665 and 4,238,343.
  • an acidic Friedel-Kraft alkylation catalyst like aluminum trichloride as described in U.S. patents 4,211,665 and 4,238,343.
  • various zeolites including intermediate pore size zeolites such as ZSM-5 and large pore size zeolites including L and ZSM-4 for alkylation of various monocyclic aromatics such as benzene is disclosed in U.S. patent 4,301 ,316.
  • the preferred form of the alkylaromatic is the mono- substituted alkylaromatic. While monoaromatics are obtained in admixture with polysubstituted alkyaromatics when conventional Friedel-Kraft catalyst are used, U.S. patent 5,034,563 teaches that a high selectivity of monoalkyl substitution can be achieved when large pore size zeolites exemplified by zeolite Y are employed as alkylation catalyst to yield lube-range alkylates. However, when the zeolite alkylation catalyst is obtained directly from a catalyst supplier and used as such the liquid alkylaromatic products produced are often colored and of poor thermal-oxidative stability.
  • a method for alkylating aromatic compounds employing zeolite catalysts to produce essentially colorless, predominantly monoalkyl aromatic fluids useful as lubricants that exhibit improved thermal oxidative stability Surprisingly, it has been found that the product color and poor thermal stability that typically results from aromatics alkylation reactions using preferably large pore acidic zeolite catalyst obtained from vendors is eliminated or substantially improved when the vendor's catalyst is pretreated to lower moisture content, hydration water content and absorbed-oxygen content before the alkylation reaction.
  • the catalyst pretreatment step of the invention can be carried out by heating the catalyst in an inert atmosphere, preferably in contact with an inert gas purge stream or in vacuo, for a time sufficient to remove entrained water, water of hydration and absorbed oxygen.
  • the time required depends on the vigor of the pretreatment step which can range from temperatures between 50°C and 500°C under subatmospheric, atmospheric or supraatmospheric pressure.
  • the alkylation process of the invention involves the alkylation of aromatic compound(s) with olefins as alkylating agent in contact with pretreated solid, acidic zeolite catalyst particles to produce thermally stable and essentially colorless aromatic compound(s) that are predominantly monoalkylated and useful as lubricant fluids.
  • the alkylation reaction between the aromatic compound and the alkylating agent is carried out in the presence of a pretreated zeolite having a pore size of at least 5 to permit the relatively bulky alkylated product to be released from the catalytic site within the zeolite pore.
  • Large pore size pretreated zeolite catalysts are the most useful catalysts for the purpose although less highly constrained intermediate pore size zeolites may also be used.
  • the large pore size zeolite are zeolites such as faujasite, synthetic faujasites (zeolite X and Y), zeolite L, ZSM-4, ZSM-18, ZSM-20, mordinite and offretite which are characterized by the presence of a 12-membered oxygen ring system in the molecular structure as described in Chen et al, "Shape- Selective Catalysis in Industrial Applications", Chemical Industries Vol. 36, Marcel Dekker Inc., New York, 1989.
  • the large pore zeolites may also be characterized by a "Constraint Index" of not more than 2, in most cases not more than 1.
  • Zeolite beta is included in this class although it may have a "Constraint Index" approaching the upper limit of 2.
  • Constraint Index is described in U.S. patent 4,016,218 together with values for typical zeolites and the significance of the Index is described in U.S. patent 4,816,932 to which reference is made for a description of the test procedure and its interpretation.
  • a highly useful large pore zeolite for the production of monoalkylated aromatics of the invention is pretreated zeolite Y in the ultrastable form, usually referred to as USY.
  • Zeolite USY or zeolite Y, unpretreated by the method of this invention is a material of commerce, available in large quantities as a catalyst for the cracking of petroleum.
  • Zeolite Y may be bound with silica, alumina, silica-alumina or other metal oxides. It may have a S ⁇ -to-A ⁇ O ratio of from 3-500, and be partially exchanged with rare earth elements, with ammonium cation or other cations.
  • zeolite USY Large pore zeolites also include Zeolite X, zeolite L, ZSM-4, ZSM-18, ZSM-20, mordenite and Offretite.
  • Zeolite MCM-22 is also a useful catalyst for this reaction.
  • MCM-22 is described in U. S. Patent 4,954,325 to M. K. Rubin and P. Chu.
  • Zeolite catalysts of the invention such as the preferred zeolite Y, are article of commerce and may be obtained from catalyst manufactures. As so obtained they can be used as catalyst for aromatics alkylation to produce lube range alkylates with high selectivity for mono-alkylates as described in U. S. patent 5,034,563.
  • the lube alkylate of such a process using zeolite catalyst obtained directly from the catalyst suppliers often is colored and exhibits very poor thermal oxidative stability. This limitation of the alkylation process is overcome by the catalyst pretreatment step of the present invention.
  • the pretreatment step of the present invention flows from the inherent discovery that zeolite aromatic alkylation catalysts that are low in moisture content, water-of-hydration content and absorbed-oxygen content consistently produce lube alkylates that have improved color and excellent oxidative and thermal stability. These catalysts produce these unexpected improved results while maintaining high productivity of lubes rich in monoalkylated aromatics of preferred viscometrics.
  • Commercially obtained zeolite aromatics alkylation catalyst have been found to be relatively rich in moisture content, water-of-hydration content and absorbed-oxygen content. Reducing the moisture content, water-of-hydration content and absorbed- oxygen content of commercially obtained zeolite catalyst by the pretreatment step of the invention has been found to yield a superior lube product.
  • Zeolite alkylation catalyst is pretreated by heating the solid catalyst particles for a time sufficient to lower the catalyst water content, water-of-hydration and absorbed oxygen content.
  • the solid catalyst is heated in a vessel in bulk form but it is within the scope of the present invention to suspend the catalyst in an otherwise unreactive and inert liquid, with or without stirring, to enhance heat transfer to the solid catalyst and accelerate the pretreatment step. Vapor of the inert liquid may be removed periodically to carry off water vapor and oxygen from the catalyst.
  • the zeolite alkylation catalyst is pretreated preferably by heating the solid catalyst in an inert gaseous environment at a temperature and for a time sufficient to lower the catalyst water content, water-of-hydration and absorbed oxygen content.
  • the pretreatment is carried out in a vessel employing a moisture-free inert gas purge stream such as nitrogen or Group VIII gases of the Periodic Table to remove water vapor and oxygen from the vessel.
  • a moisture-free inert gas purge stream such as nitrogen or Group VIII gases of the Periodic Table to remove water vapor and oxygen from the vessel.
  • the pretreatment may be carried out by heating the catalyst in vacuo in a closed vessel.
  • Zeolite alkylation catalyst can be pretreated by the process of the invention in a fixed bed, fluid bed or batchwise. Rather than employing a vessel, the solid catalyst particles can be transported through a column containing an inert liquid at an appropriate temperature or the solid can be carried through a heated or inert liquid-containing column by gas ebullition.
  • the catalyst water content, water-of-hydration and absorbed oxygen content of the zeolite catalyst particles can be effectively lowered by heating the catalyst at a temperature between 50°C and 250°C, but preferably at a temperature of 100°C.
  • One-half hour to twenty-four hours is a sufficient time to heat the catalyst, usually 1 -5 hours; however, at a preferred temperature of 100°C in a vessel in the presence of a nitrogen purge stream four hours of heating has been found sufficient to pretreat the catalyst particles sufficiently to catalyze the preparation of a superior lube product.
  • the alkylation process of the invention is carried out by contacting the aromatic compound, alkylating agent and pretreated zeolite catalyst in a suitable alkylating reaction zone which may be a fixed catalyst bed, fluid bed or stirred reactor vessel.
  • Alkylating conditions include temperature between 50°C and 300°C, pressure from 0.2 to 250 atmospheres, fixed bed feed weight hourly space velocity from 0.1 hr "' ' to 10hr ⁇
  • Useful alkylatable aromatic hydrocarbons for the present invention include benzene, toluene, biphenyl, o,m,p-xylene, hemimellitene, pseudocumene, ethylbenzene, n-propylbenzene, cumene, n-butylbenzene, isobutylbenzene, sec- butylbenzene, tert-butylbenzene, p-cymene, biphenyl, diphenylmethane, triphenyl methane, 1 ,2-diphenylethane and similarly alkyl substituted naphthalenes and anthracenes; also derivatives of aromatic hydrocarbons including phenol, hindered phenols such as 2,6-dimethyl phenol, catechol, acylphenol such as acetylphenol, carbonate esters such as phenyl methyl or ethyl carbonate and diphenyl carbonate, alkylphenol such as
  • the zeolite catalyst pretreatment process of the present invention, the alkylation step and the properties of the lubricant fluids prepared by the process of the present invention are described in the following nonlimiting Examples 2-5 and compared with alkylation control Example 1 carried out without a zeolite catalyst pretreatment step.
  • EXAMPLE 1 (control - no catalyst pretreatment) Alkylation Charge diphenylether (260gms,1.5 mole), 1 -hexadecene (112gms,0.5 mole) and 11.3 gms (0.3wt%) of solid, calcined Ultrium x5210x1 catalyst particles (40% zeolite USY, alpha value 199, unit cell size 24.688 ) into a 500cc round bottom flask equipped with a magnetic stirrer, a thermocouple, a nitrogen-vacuum line and a sampling tube. Evacuate the system with vacuum to remove air and refill with nitrogen. Repeat this procedure for a total of three times and leave under nitrogen atmosphere. Heat the reaction mixture with stirring to 200°C.
  • Conversion of 1 -hexadecene is typically greater than 98%.
  • the lube product is colorless and has a hot-tube test rating at 305°C of 1-2.
  • Example 3 is a duplication of Example 2 and produces the same result, thus establishing reproducibility of the process of the invention.
  • Example 4 is the same as Example 2 except 1 wt% of a crushed MCM- 22/AI2O3 zeolite catalyst is used.
  • the product basestock had a hot-tube test rating at
  • Example 5 is the same as control Example 1 , except 1 wt% of a crushed MCM- 22/AI2O3 zeolite catalyst is used.
  • the product basestock has a hot-tube test rating at
  • Examples 1 , 2 and 3 show that pretreatment of catalyst and feed improved the lube product quality.
  • Examples 4 and 5 show that pretreatment of catalyst and feed improved the product quality achieved by MCM-22 catalyst.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 no pre- catalyst & catalyst & catalyst & no pretreatment feeds were feeds were feeds were treatment pretreated pretreated pretreated

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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)

Abstract

L'invention concerne des liquides aromatiques essentiellement monoalkylés utilisés comme lubrifiants et manifestant une meilleure stabilité vis-à-vis de l'oxydation thermique; ils sont fabriqués au moyen de l'alkylation d'aromatiques d'oléfine en utilisant un catalyseur industriel à zéolite, de préférence à pores larges, qui a été prétraité pour baisser le taux d'humidité, la teneur en eau d'hydratation et la teneur en oxygène absorbé avant de passer à la réaction d'alkylation.
PCT/US2000/000093 1999-01-06 2000-01-06 Procede ameliore pour produire des liquides aromatiques alkyles WO2000040527A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU34692/00A AU3469200A (en) 1999-01-06 2000-01-06 Improved process for producing alkylated aromatic fluids

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US22601499A 1999-01-06 1999-01-06
US09/226,014 1999-01-06

Publications (1)

Publication Number Publication Date
WO2000040527A1 true WO2000040527A1 (fr) 2000-07-13

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AU (1) AU3469200A (fr)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7074737B2 (en) 2003-12-23 2006-07-11 Supresta U.S. Llc Alkylation of triphenylphosphate
US9963403B2 (en) 2014-10-27 2018-05-08 Exxonmobil Chemical Patents Inc. Process and apparatus for the conversion of hydrocarbons
US11130720B2 (en) 2018-03-23 2021-09-28 Uop Llc Processes for methylation of aromatics in an aromatics complex
US11130719B2 (en) 2017-12-05 2021-09-28 Uop Llc Processes and apparatuses for methylation of aromatics in an aromatics complex
US11208365B2 (en) 2016-12-20 2021-12-28 Uop Llc Processes and apparatuses for methylation of aromatics in an aromatics complex

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5034563A (en) * 1990-04-06 1991-07-23 Mobil Oil Corporation Naphthalene alkylation process
US5770782A (en) * 1996-02-08 1998-06-23 Huntsman Petrochemical Corporation Process and system for alkylation of aromatic compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5034563A (en) * 1990-04-06 1991-07-23 Mobil Oil Corporation Naphthalene alkylation process
US5770782A (en) * 1996-02-08 1998-06-23 Huntsman Petrochemical Corporation Process and system for alkylation of aromatic compounds

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7074737B2 (en) 2003-12-23 2006-07-11 Supresta U.S. Llc Alkylation of triphenylphosphate
US9963403B2 (en) 2014-10-27 2018-05-08 Exxonmobil Chemical Patents Inc. Process and apparatus for the conversion of hydrocarbons
US10011538B2 (en) 2014-10-27 2018-07-03 Exxonmobil Chemical Patents Inc. Method of making aromatic hydrocarbons
US11208365B2 (en) 2016-12-20 2021-12-28 Uop Llc Processes and apparatuses for methylation of aromatics in an aromatics complex
US11130719B2 (en) 2017-12-05 2021-09-28 Uop Llc Processes and apparatuses for methylation of aromatics in an aromatics complex
US11130720B2 (en) 2018-03-23 2021-09-28 Uop Llc Processes for methylation of aromatics in an aromatics complex

Also Published As

Publication number Publication date
AU3469200A (en) 2000-07-24

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