Solid anti-friction devices – materials therefor – lubricant or se – Lubricants or separants for moving solid surfaces and... – Organic sulfur compound – wherein the sulfur is single bonded...
Reexamination Certificate
2000-07-14
2003-10-07
Gupta, Yogendra N. (Department: 1751)
Solid anti-friction devices, materials therefor, lubricant or se
Lubricants or separants for moving solid surfaces and...
Organic sulfur compound, wherein the sulfur is single bonded...
C508S389000, C508S390000, C508S391000, C184S001500, C252S070000
Reexamination Certificate
active
06630430
ABSTRACT:
This invention relates to a oil-soluble compositions of matter useful as detergent components in hydrocarbon oils useful for a wide range of purposes, including without limitation general lubricants, lubricating oils for internal combustion engines, cutting fluids, emulsions, and dispersions.
More particularly, the invention relates to oil-soluble linear alkylbenzenes comprising alkyl chains having between about 18 and 30 carbon atoms in which the alkylbenzenes have a low dialkylate content and unique isomer distribution, including their sulfonate and other water soluble and solubilizable derivatives.
BACKGROUND
The chemical structure and use of linear alkylbenzenes and their derivatives, including their sulfonate derivatives, in the manufacture of detergents is well known. Generally, linear alkylbenzenes are produced by an alkylation reaction (according to one of any well known processes for producing such materials) in which the net result is the appendage of a hydrocarbyl radical to a benzene ring. The source of the hydrocarbyl radical may be a branched or a linear olefin, either an internal olefin or an alpha olefin, and in practice a mixture of linear olefins is typically used, which mixture comprises various olefins having different numbers of carbon atoms per molecule. For the manufacture of detergents, the range of carbon numbers (the number of carbon atoms per molecule of an olefin used) of an olefin mixture used in the alkylation reaction is typically in the range of between about 8 and 15 (inclusive) carbon atoms per molecule, which molecules are sometimes collectively referred to by those in the art as the “detergent range”.
Alkylation of benzene using olefins in the detergent range leads to a reaction product mixture which contains alkylated benzenes having hydrocarbyl radicals of different chain length appended to a benzene ring, and also contains position isomers of these alkylation products. Thus, a reaction mixture from the alkylation of benzene using detergent range olefins is often complex in makeup.
Of the possible position isomers referred to above, it has been recently discovered that detergents prepared from alkylbenzenes having the benzene ring located at the 2-position on the hydrocarbyl radical possess enhanced detergency and other beneficial properties over the other isomers produced in the alkylation. This is believed in part to be true because the hydrocarbon chain that is appended to the ring extends a greater distance in space in isomers having a phenyl group in the 2-position than the other position isomers, thus providing a molecule having a more volumetrically exposed hydrocarbon chain portion over other position isomers. Among other things, this increased exposure provides increased availability for interaction with hydrophobic materials which are sought to be solubilized in an aqueous medium, when the alkylbenzene also includes a hydrophilic moiety, such as a sulfonate group bonded to the benzene ring.
Surprisingly, more than one source of information in the prior art mentions that a high 2-phenyl isomer content in alkylbenzenes-derived detergent materials is undesirable. For example, U.S. Pat. No. 3,342,888 mentions at column 2, line 37 et seq. that a high 2-phenyl isomer content is associated with poor sudsing characteristics. U.S. Pat. No. 3,387,056 mentions at column 2, lines 21-24 that a lower 2-phenyl isomer content improves the product. U.S. Pat. No. 3,509,225 mentions at column 1, lines 59-62 that the 2-phenyl isomer is objectionable for use in commercial detergent products because of its relatively low water solubility. However, quite the opposite has been found to be true for the compositions according to this invention, and it has now been deemed desirable to provide alkylbenzenes having extremely high amounts of the 2-phenyl isomer alkylation reaction products.
Detergents useful as components in hydrocarbon oils are often possessive in general of the same properties as detergents useful in aqueous media, that is, their molecules contain both a hydrophilic and a hydrophobic portion. However, in many applications it may be beneficial to employ alkylbenzenes having longer hydrocarbon chains on the benzene ring than those found in conventional detergents, for example to enhance solubility in hydrocarbon oils, or to provide increased compatibility and chemical inertness with respect to other components of the formulation, depending upon the intended use. The production of sulfonates by reaction with, e.g., SO
3
, is well known to those skilled in the art. See, for example, the article “Sulfonates” in Kirk-Othmer “Encyclopedia of Chemical Technology”, Second Edition, Vol. 19, pp. 291 et seq. published by John Wiley & Sons, N.Y. (1969). Other descriptions of neutral and basic sulfonate salts and techniques for making them can be found in the following U.S. Pat. Nos. 2,174,110; 2,174,506; 2,174,508; 2,193,824; 2,197,800; 2,202,781; 2,212,786; 2,213,360; 2,228,598; 2,223,676; 2,239,974; 2,263,312; 2,276,090; 2,276,097; 2,315,514; 2,319,121; 2,321,022; 2,333,568; 2,333,788; 2,335,259; 2,337,552; 2,347,568; 2,366,027; 2,374,193; 2,383,319; 3; 312,618; 3,471,403; 3,488,284; 3,595,790; and 3,798,012. These and all other patents, books, excerpts, articles, and literature cited herein are hereby incorporated by reference for their disclosures.
Although the prior art is replete with prior art concerning the use of alkylbenzene based detergents in hydrocarbon based oils such as motor oils, hydraulic fluids, cutting fluids, etc., none have thus far provided commercially quantities of an alkylbenzene based detergent component in which the hydrocarbon tails of the molecule have carbon numbers of any integral value in the range of between about 16 and 30 carbon atoms per molecule, in which the 2-phenyl isomer content is greater than about 50%, at prices low enough to render such materials economically viable from the end user perspective. Thus I have recognized that a need exists for a method of linear alkylbenzene (“LAB”) production having high substrate olefin conversion, high selectivity to 2-phenyl isomer LAB, and employing a catalyst having long lifetimes and easy handling, by which high 2-phenyl isomer content and low dialkylate content can be achieved in materials having relatively long hydrocarbon tails attached to a benzene ring in a linear alkylbenzene based detergent.
The present invention employs a mordenite catalyst in the production of long-tail linear alkylbenzenes. The particular mordenites useful in this invention may in one form of the invention be mixed with a different catalyst that does not afford high 2-phenyl isomer LAB production, to provide essentially any desired percentage content of 2-phenyl isomer in the range of about 20-82% (on a weight basis) in the finished product by adjusting the amounts of each catalyst. In this way, LAB may be produced having a higher 2-phenyl isomer content than would be produced using the non-mordenite catalyst of this invention.
Thus, in one broad respect, this invention is a process for the production of linear alkylbenzenes which comprises contacting benzene and an olefin having about 8 to about 30 carbons in the presence of a mixed catalyst bed to form linear alkylbenzenes, wherein the mixed catalyst bed comprises fluorine-containing mordenite and a second, solid linear alkylbenzene alkylation catalyst, wherein the second alkylation catalyst has a selectivity to the 2-phenyl isomer of the linear alkylbenzenes less than the selectivity of the fluorine-containing mordenite.
In another broad respect, this invention is a process for the production of linear alkylbenzenes, comprising:
dehydrogenating a paraffin to form an olefin;
sending a feed stream of benzene and the olefin through a conduit to a linear alkylbenzenes alkylation reactor containing a fluorine-containing mordenite and a second alkylation catalyst, wherein the second alkylation catalyst has a selectivity to the 2-phenyl isomer of the linear alkylbenzenes less than the selectivity of the fluorine-containing mordenite;
reacting the
Anantaneni Prakasa R.
Smith George A.
Gupta Yogendra N.
Hamlin D. G.
Huntsman Petrochemical Corporation
Whewell Christopher J.
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