Mineral oils: processes and products – Chemical conversion of hydrocarbons – With prevention or removal of deleterious carbon...
Reexamination Certificate
1998-11-05
2001-03-13
Griffin, Walter D. (Department: 1764)
Mineral oils: processes and products
Chemical conversion of hydrocarbons
With prevention or removal of deleterious carbon...
C208S04800Q, C585S950000, C203S008000, C203S009000
Reexamination Certificate
active
06200461
ABSTRACT:
FIELD OF THE INVENTION
The present invention provides for methods and compositions for inhibiting the polymerization of ethylenically unsaturated hydrocarbons, such as olefins and diolefins.
BACKGROUND OF THE INVENTION
Common industrial methods for producing ethylenically unsaturated monomers include a variety of purification processes such as distillation to remove impurities. Purification operations are often carried out at elevated temperatures and this can increase the rate of undesired polymerization. Polymerization, such as thermal polymerization, during the monomer purification process, results not only in loss of desired monomer end-product, but also in production efficiency caused by polymer formation and agglomeration on process equipment. In heat requiring operations, such agglomeration adversely affects heat transfer efficiency.
Typically the monomers are stabilized with the addition of substances which will act as inhibitors or retarders of polymerization.
Certain ethylenically unsaturated monomers such as the diolefins butadiene and isoprene will polymerize when left in storage tanks and during transportation at temperatures as low as room temperature. This polymerization is initiated by reaction of the diolefin monomer with oxygen present in the monomer containing system. This reaction will form peroxides and free radical species which will perpetuate the reaction with the diolefin monomer.
Various approaches have been attempted with regard to this problem of polymerization. U.S. Pat. No. 3,148,225 teaches that N,N-dialkylhydroxylamines will inhibit the polymerization of popcorn polymer formation in olefin monomer recovery systems. In comparative studies, p-aminophenol was less effective than the hydroxylamines at inhibiting popcorn polymer formation. U.S. Pat. No. 3,342,723 tests p- and o-aminophenols for inhibiting fouling of hydrocarbon liquids. These compounds proved effective at inhibiting the formation and adhesion of coke-like deposits during refinery operations. o-phenylenediamine was also demonstrated to be effective in the oil refining apparatus.
U.S. Pat. No. 5,510,547 teaches that a combination of a phenylenediamine compound and a hydroxylamine compound is effective as inhibiting the polymerization of vinyl aromatic monomers during processing conditions. U.S. Pat. No. 4,720,566 teaches that a combination of a hydroxylamine and a phenylenediamine compound is effective at inhibiting the polymerization of acrylonitrile during its production.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides for methods and compositions for inhibiting the polymerization of ethylenically unsaturated hydrocarbons comprising adding an effective inhibiting amount of a composition comprising an aminophenol compound and at least one of a phenylenediamine compound and a hydroxylamine compound “(Aminophenol compositions”).
The ethylenically unsaturated monomers are characterized as polymerizable ethylenically unsaturated hydrocarbons and include olefins and diolefins. The olefins contain about 2 to about 20 carbon atoms, preferably 2 to 8 carbon atoms and the diolefins are conjugated and contain about 2 to about 20 carbon atoms with 4 to 6 carbon atoms preferred. Examples of these compounds include ethylene dichloride, ethylene glycol, aromatics from ethylene plants and pyrolysis gasoline.
The aminophenol compounds generally have the formula:
where the amino group can be ortho, meta or para to the hydroxyl group. Preferably, the o-aminophenol is preferred.
The phenylenediamine compounds useful in the present invention generally have the formula:
wherein R
1
, R
2
, R
3
and R
4
are the same or different and are hydrogen, alkyl, aryl, alkaryl or aralkyl groups having about 1 to about 20 carbon atoms. Preferably the phenylenediamine compound is selected from the group consisting of N,N′-bis-di-sec-butyl-p-phenylenediamine and N-phenyl-N′-(1,4-dimethylpentyl)-p-phenylenediamine.
The hydroxylamine compounds useful in the present invention generally have the formula:
wherein R
5
and R
6
are the same or different and are hydrogen, alkyl, aryl, alkaryl, aralkyl or hydroxyalkyl groups and have about three to about twenty carbon atoms. The preferred hydroxylamine compounds are selected from the group consisting of N, N′-diethylhydroxylamine (DEHA) and bis-N, N′-(hydroxypropyl-hydroxylamine) (HPHA).
The aminophenol compositions of the present invention are effective at inhibiting the polymerization of ethylenically unsaturated monomers during both storage and processing conditions. Storage conditions also include transportation of the monomers. These conditions will usually have oxygen present and can be at elevated temperatures of up to 100° C. The processing conditions are usually distillation and purification processes and are run at elevated temperatures of 95° and 125° C. where oxygen can be present or absent.
For purposes of the present invention, the term “effective amount for the purpose” is that amount of aminophenol compositions necessary to inhibit polymerization of the ethylenically unsaturated monomers. This amount will vary according to the conditions under which the monomers are subjected during the storage and/or handling thereof. During processing, for example, high temperatures and higher monomers contamination will require larger amounts of the aminophenol compositions.
Preferably, the total amount of the aminophenol compositions added to the ethylenically unsaturated monomer will range from about 1 part to about 10,000 parts per million parts of monomer. More preferably, the aminophenol compositions are added at a range of about 1 part to about 100 parts per million parts monomer.
The weight ratios of aminophenol compound to the other compounds present in the aminophenol compositions is presented in Table A below.
TABLE A
Aminophenol Compound
Phenylenediamine Compound
1:9 to 9:1
Hydroxylamine Compound
1:9 to 9:1
Accordingly, it is possible to produce a more effective vinyl aromatic monomer polymerization inhibition treatment than is obtainable by the use of one ingredient alone when measured at comparable treatment levels. This enhanced activity will allow for the concentration of each of these ingredients to be lowered and the total quantity of polymerization inhibitor particularly at higher processing temperatures may be reduced.
The aminophenol compositions of the present invention may be added to the ethylenically unsaturated hydrocarbon as either a dispersion or as a solution using a suitable liquid carrier or solvent. Any solvent that is compatible with the individual ingredients and with the monomer may be employed.
The aminophenol compositions may be added to the ethylenically unsaturated hydrocarbon vinyl aromatic by any conventional method, either as individual components or as a combination of components. It is preferred that the ingredients be added to the monomer as a single treatment.
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BetzDearborn Inc.
Greenblum & Bernstein P.L.C.
Griffin Walter D.
Preisch Nadine
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