Liquid purification or separation – Processes – Chemical treatment
Reexamination Certificate
1999-07-01
2001-08-21
Simmons, David A. (Department: 1724)
Liquid purification or separation
Processes
Chemical treatment
C210S908000
Reexamination Certificate
active
06277289
ABSTRACT:
FIELD OF THE INVENTION
This invention concerns a process for the treatment of wastewater streams containing aldehydes and/or ketones, in particular, alpha, beta-ethylenically unsaturated aldehydes comprising contacting said streams with organic diamines, organic triamines and organic tetramines, organic polyamines and/or inorganic ammonium compounds.
TECHNICAL BACKGROUND OF THE INVENTION
The toxicity of aldehydes and ketones, especially alpha, beta-ethylenically unsaturated aldehydes and ketones to biological waste treatment systems, even in low concentrations, has been recognized by those skilled in the art. A review article on this problem is presented by V. T. Stack, Jr. in Industrial and Engineering Chemistry, Volume 49 No. 5, page 913 (1957). Stack reports that of these compounds, acrolein has the most toxic effect on biological waste treatment processes. Wastewaters containing alpha, beta-ethylenically unsaturated aldehydes and ketones must be treated to reduce the concentration of these substances to very low levels before the waste water may be further treated by a biological system. Failure to adequately pretreat the wastewater streams results in the biomass being in danger of being killed or inhibited to a very low level of activity.
Treatment of waste streams containing alpha, beta-ethylenically unsaturated aldehydes and ketones are known in the art. U.S. Pat. No. 3,923,648 discloses a method for the disposal of such wastewaters comprising contacting them with sufficient base to render the pH of the wastewaters alkaline, maintaining the alkaline wastewaters at a temperature of about 25° C. to 100° C. for at least about 15 minutes and then degrading the wastewater in a biological system containing active biomass process rendering non-toxicity of alpha, beta-ethylenically unsaturated aldehydes and/or ketones to biological treatment systems by heating the wastewater with a slight excess of alkali at elevated temperatures. The preferred base is an alkali metal hydroxide, but the use of other bases is broadly disclosed including soluble organic amines such as methylamine, ethylamine, dimethylamine, triethylamine, and the like; and alkanolamines including monoalkanolamines, dialkanolamines, trialkanolamines, N-monoalkyl-monoalkanolamines, and N,N-dialkylalkanolamines and the like.
U.S. Pat. No. 5,459,229 discloses a process for the preparation of a 1,3-propanediol based polyester in which an aqueous acrolein-containing waste stream is treated with a sufficient quantity of base to increase the pH to above 7.5 for a time effective to lower the acrolein content, followed, optionally, by dilution and biotreatment. The base utilized is preferably an inorganic base, most preferably sodium hydroxide.
One objective of the present invention is to provide a more efficient and effective treatment to reduce the levels of alpha, beta-ethylenically unsaturated aldehydes and ketones in waste water streams.
SUMMARY OF THE INVENTION
The present invention provides a process for the reduction of the concentration of aldehydes and/or ketones, especially alpha, beta-unsaturated aldehydes and ketones, and most especially acrolein, in aqueous waste streams, particularily in aqueous waste streams resulting from the manufacture of 1,3-propanediol and polyesters and polyols derived therefrom in waste streams, said process comprising the steps of:
(a) contacting said aqueous waste stream with an effective amount of a nitrogen containing base selected from the group consisting of organic diamines, organic triamines and organic tetramines, organic polyamines, and inorganic ammonium compounds; and
(b) maintaining said contacted waste stream at essentially ambient temperatures for a sufficient length of time to afford at least a 50% reduction in the concentration of said aldehyde or ketone.
DETAILED DESCRIPTION OF THE INVENTION
This invention relates to a process for treating aqueous “waste water” streams containing aldehydes and ketones, particularly alpha, beta-ethylenically unsaturated aldehydes and ketones which are toxic to biological waste treatment systems using selected nitrogen containing base compounds to treat said waste waters.
Preferred nitrogen containing base compounds include organic polyamines, defined herein as organic amines comprising two or more amines, preferrably diamines such as hexamethylene diamine, 2-methyl pentamethylene-diamine, 2-methyl hexamethylene diamine, 3-methyl hexamethylene diamine, 2,5-dimethyl hexamethylene diamine, 2,2-dimethylpentamethylene diamine, 5-methylnonane diamine, dodecamethylene diamine, 2,2,4- and 2,4,4-trimethyl hexamethylene diamines, 2,2,7,7-tetramethyl octamethylene diamine, metaxylylidene diamine, paraxylylidene diamine, diaminodicyclohexyl methane, C
2
-C
16
aliphatic diamines which may be substituted with one or more alkyl groups, and N-alkyl, and N′N-dialky derivatives thereof. The most preferred diamine is hexamethylene diamine. Other nitrogen containing bases containing more than 2 amine groups are also useful in the present invention. These include triamines, for example bis hexamethylene triamine, tetramines and other polyamines.
Another preferred class of nitrogen-containing base compounds is inorganic ammonium salt, e.g., ammonium carbonate.
A specific advantage that accrues to the use of hexamethylene diamine with acrolein-containing waste streams is that an insoluble solid reaction product separates from the reaction system. This allows the bulk removal of acrolein and the reaction product and the resulting carbon load from the waste stream before said waste stream is fed to the optional subsequent biological treatment. This process also eliminates the toxicity associated with the acrolein reaction products in waste streams.
The temperature utilized for the treatment is not critical. The application of this process to an industrial waste stream takes place at the existing waste stream temperature, from about 0° C. to 65° C., defined herein as “essentially ambient conditions”.
Alpha, beta-unsaturated aldehydes and ketones treatable by the process of the present invention include acrolein, methacrolein (methacrylaldehyde), crotonaldehyde, 2,4-hexadienal, acetaldehyde and methyl vinyl ketone. Other aldehydes such as acetaldehyde can also be similarly treated.
The treatment process of the present invention is especially useful for the treatment of waste aqueous streams containing acrolein resulting from the manufacture of 1,3-propanediol and polyesters and polyols derived therefrom, e.g. poly(trimethylene naphthalate). Of these, a preferred application is to waste streams resulting from the manufacture of 1,3-propanediol based polyesters, most specifically to waste streams resulting from the manufacture of poly(trimethylene terephthalate) (3GT).
The preparation of 3GT polyester resins involves the reaction of excess 1,3-propanediol with terephthalic acid or a lower dialkyl ester of terephthalic acid at elevated temperature. The major toxic by-products of this reaction, acrolein and allyl alcohol, are contained in solution in the distillate. Although the amounts of these byproducts are low, it is desirable to further reduce the level of byproducts in the distillate, especially for preparing 3GT polyester from terephthalic acid and excess 1,3-propanediol.
REFERENCES:
patent: 3462477 (1966-04-01), Caporali et al.
patent: 3893895 (1975-07-01), Dehnert et al.
patent: 3923648 (1975-12-01), Lashley, Jr.
patent: 5459229 (1995-10-01), Kelsey et al.
patent: 5606094 (1997-02-01), Roof et al.
patent: 5798433 (1998-08-01), Schmidt et al.
patent: 1 431 511 (1976-04-01), None
patent: 110 861 (1986-07-01), None
patent: 547 553 A1 (1993-06-01), None
patent: 812 337 B1 (1997-12-01), None
patent: 01 094994 (1989-04-01), None
International Search Report dated Oct. 30, 2000.
Derwent Abstract XP002150095 of JP 01 094994 published Apr. 13, 1989.
Opposition of EP 812 337 B1 by E.I. DuPont de Nemours and Company, assignee of the subject application.
Encyclopedia of Polymer Science and Technology, John Wiley & Sons, Inc. 1964, vol. 1, p. 173.
Kirk-Othmer
Kurian Joseph Varapadavil
Liang Yuan Feng
E. I. Du Pont de Nemours and Company
Hoey Betsey Morrison
Simmons David A.
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