Processes for making alkylbenzenesulfonate surfactants and...

Details Processes for making alkylbenzenesulfonate surfactants and... Processes for making alkylbenzenesulfonate surfactants and...

2000-01-07

2003-08-05

Ogden, Necholus (Department: 1751)

Cleaning compositions for solid surfaces, auxiliary compositions

Cleaning compositions or processes of preparing

For cleaning a specific substrate or removing a specific...

C510S424000, C510S426000, C510S428000, C510S492000

Reexamination Certificate

active

06602840

ABSTRACT:

FIELD OF THE INVENTION
The present invention is in the field of processes for making alkylbenzenesulfonate surfactants. The processes herein include a combination of two essential steps, delinearization and alkylation. The delinearization step selected herein introduces particular types of limited branching into an aliphatic hydrocarbon having ten or more, but no more than about 16, carbon atoms. The hydrocarbon includes olefin having a hydrocarbon chain length suitable for detergent manufacture, e.g., C
10
-C
14
, or a corresponding paraffin. The second essential step is an alkylation step having an internal isomer selectivity of from 0 to no more than about 40 in which the hydrocarbon is used to monoalkylate benzene catalytically with an alkylation catalyst. Such alkylation catalysts preferably comprise an at least partially crystalline porous zeolite-containing solid, the zeolite having moderate acidity and intermediate pore size. Preferred alkylation catalysts include certain at least partially dealuminized acidic nonfluoridated mordenites. The processes herein further comprise sulfonating, neutralizing and incorporating the resulting modified alkylbenzenesulfonate surfactants into consumer products. The invention relates also to the products of the processes, including modified surfactants and consumer cleaning products containing them.
BACKGROUND OF THE INVENTION
Historically, highly branched alkylbenzenesulfonate surfactants, such as those based on tetrapropylene (known as “ABS” or “TPBS”) were used in detergents. However, these were found to be very poorly biodegradable. A long period followed of improving manufacturing processes for alkylbenzenesulfonates, making them as linear as practically possible (“LAS”). The overwhelming part of a large art of linear alkylbenzenesulfonate surfactant manufacture is directed to this objective. Large-scale commercial alkylbenzenesulfonate processes in use in the U.S. today are directed to linear alkylbenzenesulfonates. However, linear alkylbenzenesulfonates are not without limitations; for example, they would be more desirable if improved for hard water and/or cold water cleaning properties.
In the petroleum industry, various processes have more recently been developed, for example for producing low viscosity lube oil, which the inventors have now discovered provide new insight on how to delinearize hydrocarbons to a limited and controlled extent. Such deliberate delinearization, however, is not a feature of any current commercial processes in the different field of alkylbenzenesulfonate surfactant manufacture for consumer products. This is not surprising, in view of the overwhelming volume of LAS surfactant art teaching toward linear compounds and away from delinearization.
The majority of commercial processes for making alkylbenzenes rely on HF or aluminum chloride catalyzed alkylation of benzene. Quite recently, it has been discovered that certain zeolite catalysts can be used for alkylation of benzene with olefins. Such a process step has been described in the context of otherwise conventional processes for manufacture of linear alkylbenzenesulfonates. For example, the DETAL® process of UOP uses a zeolite alkylation catalyst. The DETAL® process and all other current commercial processes for alkylbenzenesulfonate manufacture are believed to fail to meet the internal isomer selectivity requirements of the inventive process and alkylation catalyst defined hereinafter. Moreover, the DETAL® process catalyst or catalysts are believed to lack the moderate acidity and intermediate pore size of alkylation catalysts used in the processes of the present invention. Other recent literature describes the use of mordenite as an alkylation catalyst, but no such disclosure makes the combination of specific process steps required by the instant invention. Moreover, in view of the linearity desired in alkylbenzenesulfonate products of conventionally known processes, they also generally include steps directed to the provision or making of a substantially linear hydrocarbon, not a delinearized one, prior to the alkylation. A possible exception is in U.S. Pat. No. 5,026,933 which includes, for example, oligomerization of lower olefin such as propylene under narrowly defined conditions using collidine-deactivated ZSM-23 to form a composition comprising a tetramer assertedly having 1.3 methyl branches per chain, followed by fractionation and an alkylation using mordenite catalyst. See Example XVII. See also U.S. Pat. No. 4,990,718 in which an alkylbenzene is made via a process that produces a vinylidene olefin by dimerization in presence of chromium catalyst but in which the vinylidene yield is adversely affected by oligomerization and in which distillation is required prior to alkylation. However, the processes of '933 and '718 have numerous shortcomings from the standpoint of the detergent industry in terms of cost, catalyst limitations in the propylene oligomerization or olefin dimerization stage, presence of large volumes of distillation fractions that would need to be discarded or find nondetergent customers, and limited range of product compositions, including mixtures of chainlengths attainable. Such developments by the petroleum industry are, in short, not optimal from the standpoint of the expert formnulator of detergent products.
BACKGROUND ART
U.S. Pat. No. 5,026,933; U.S. Pat. No. 4,990,718; U.S. Pat. No. 4,301,316; U.S. Pat. No. 4,301,317; U.S. Pat. No. 4,855,527; U.S. Pat. No. 4,870,038; U.S. Pat. No. 2,477,382; EP 466,558, Jan. 15, 1992; EP 469,940, Feb. 5, 1992; FR 2,697,246, Apr. 29, 1994; SU 793,972, Jan. 7, 1981; U.S. Pat. No. 2,564,072; U.S. Pat. No. 3,196,174; U.S. Pat. No. 3,238,249; U.S. Pat. No. 3,355,484; U.S. Pat. No. 3,442,964; U.S. Pat. No. 3,492,364; U.S. Pat. No. 4,959,491; WO 88/07030, Sep. 25, 1990; U.S. Pat. No. 4,962,256, U.S. Pat. No. 5,196,624; U.S. Pat. No. 5,196,625; EP 364,012 B, Feb. 15, 1990; U.S. Pat. No. 3,312,745; U.S. Pat. No. 3,341,614; U.S. Pat. No. 3,442,965; U.S. Pat. No. 3,674,885; U.S. Pat. No. 4,447,664; U.S. Pat. No. 4,533,651; U.S. Pat. No. 4,587,374; U.S. Pat. No. 4,996,386; U.S. Pat. No. 5,210,060; WO 95/17961, Jul. 6, 1995; WO 95/18084; U.S. Pat. No. 5,510,306; U.S. Pat. No. 5,087,788; U.S. Pat. No. 5,625,105 and U.S. Pat. No. 4,973,788 are useful by way of background to the invention. The manufacture of alkylbenzenesulfonate surfactants has recently been reviewed. See Vol. 56 in “Surfactant Science” series, Marcel Dekker, New York, 1996, including in particular Chapter 2 entitled “Alkylarylsulfonates: History, Manufacture, Analysis and Environmental Properties”, pages 39-108 which includes 297 literature references. Documents referenced herein are incorporated in their entirety.
SUMMARY OF THE INVENTION
The present invention is predicated on an unexpected discovery that combining a specifically defined delinearization step or steps of a non-lower olefin or paraffin (“non-lower” meaning having 10 or more carbon atoms) with a particularly defined selective alkylation step results in an unexpectedly superior alkylbenzenesulfonate surfactant product.
Accordingly, in one aspect, the present invention relates to a process for preparing modified alkylbenzenesulfonate surfactant suitable for use in cleaning products such as laundry detergents, hard surface cleaners, dishwashing detergents and the like, said process comprising (a) reducing the linearity of an olefin, preferably one having molecular weight of at least about 126 and no more than about 280, preferably no more than about 224, by a step of skeletally isomerizing, in the presence of a constrained skeletal isomerization catalyst, a substantially linear olefin preformed to have at least said molecular weight; and (b) a monoalkylation step having low internal isomer selectivity (from 0 to no more than 40 preferably from 0 to no more than 20, more preferably from 0 to no more than 10 using measures further defined hereinafter), of reacting the product of step (a) with an aromatic hydrocarbon selected from benzene, toluene and mixtures

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