Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
1998-12-11
2001-05-08
Wood, Elizabeth D. (Department: 1764)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
C502S224000, C502S232000, C502S233000, C502S234000
Reexamination Certificate
active
06228797
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to catalyst systems useful in hydrocarbon upgrading processes and to methods for their production and use.
In another aspect, this invention relates to catalyst systems and processes for oligomerizing hydrocarbons employing the novel catalyst systems of this invention.
Perfluoroalkylsulfonic acids are useful for oligomerization of olefins having in the range of from 3 to 8 carbon atoms per molecule to diesel fuel range hydrocarbons having in the range of from 8 to 24 carbon atoms per molecule. However, many of these compounds are waxy, low surface area solids. The perfluoroalkyl groups of the perfluroalkylsulfonic acids tend to inhibit the dissolution of hydrocarbons into the perfluoroalkylsulfonic acids, and mass transfer limitations occur resulting in low catalyst activity.
Therefore, it is desirable to develop catalyst systems comprising perfluoroalkylsulfonic acid wherein the perfluoroalkylsulfonic acid is supported on a high-surface-area support so as to significantly increase the activity of the perfluoroalkylsulfonic acid in oligomerizing at least one olefin to diesel fuel range hydrocarbons.
SUMMARY OF THE INVENTION
It is an object of this invention to provide a novel catalyst system which is useful for at least partially oligomerizing at least one olefin to diesel fuel range hydrocarbons.
A further object of this invention is to provide a method of preparing a novel catalyst system effective for at least partially oligomerizing at least one olefin to diesel fuel range hydrocarbons.
It is a further object of this invention to employ this novel catalyst system as a catalyst in the at least partial oligomerization of at least one olefin to diesel fuel range hydrocarbons.
It is still a flirter object of the present invention to increase the efficiency of the oligomerization of at least one olefin to diesel fuel range hydrocarbons.
Yet another object of the present invention is to provide an improved oligomerization process of increased efficiency.
According to a first embodiment of the present invention, a method which can be used for producing a catalyst system is provided. The method comprises the steps of:
dissolving at least a portion of at least one perfluoroalkylsulfonic acid salt of the formula C
n
F
2n+1
SO
3
X in a basic solution comprising a base to thereby form a first liquid material, wherein n ranges from 2 to 20 and X is an element selected from the group consisting of sodium and potassium;
dissolving at least a portion of at least one hydrolyzable silane compound in a first acidic solution comprising a first acid to thereby form a to second liquid material comprising at least one silanol comprising hydroxy groups and silicon;
mixing the first liquid material and the second liquid material to thereby form a gel comprising silica and the at least one perfluoroalkylsulfonic acid salt;
contacting the gel with a second acidic solution comprising a second acid to thereby form an acid-treated gel and to thereby convert at least a portion of the at least one perfluoroalkylsulfonic acid salt to at least one perfluoroalkylsulfonic acid of the formula C
n
F
2n+1
SO
3
H and to thereby convert at least a portion of the second acid to an acid salt;
removing at least a portion of the acid salt from the acid-treated gel to thereby form a purified gel; and
drying the purified gel to thereby form the catalyst system.
According to a second embodiment of the present invention, an alternative method which can be used for producing a catalyst system is provided. The method comprises the steps of:
mixing at least one perfluoroalkylsulfonic acid salt of the formula C
n
F
2n+1
SO
3
X with silica gel and water to thereby form a gel comprising silica and at least one perfluoroalkylsulfonic acid salt, wherein n ranges from 2 to 20 and X is an element selected from the group consisting of sodium and potassium;
contacting the gel with an acidic solution comprising an acid to thereby form an acid-treated gel and to thereby convert at least a portion of the at least one perfluoroalkylsulfonic acid salt to at least one perfluoroalkylsulfonic acid of the formula C
n
F
2n+1
SO
3
H and to thereby convert at least a portion of the acid to an acid salt;
removing at least a portion of the acid salt from the acid-treated gel to form a purified gel; and
drying the purified gel to thereby form the catalyst system.
According to a third embodiment of the present invention, a process is provided for oligomerizing at least a portion of a hydrocarbon feedstock comprising at least one olefin having in the range of from 3 to 8 carbon atoms per molecule. The process comprises contacting the hydrocarbon feedstock with a catalyst system prepared by the method of the first embodiment or, alternatively, the method of the second embodiment.
Other objects and advantages will become apparent from the detailed description and the appended claims.
DETAILED DESCRIPTION OF THE INVENTION
According to the first embodiment of the present invention, the catalyst system can be prepared by the following method.
At least a portion of at least one perfluoroalkylsulfonic acid of the formula C
n
F
2n+1
SO
3
H, wherein n ranges from 2 to 20, can be converted to at least one perfluoroalkylsulfonic acid salt of the formula C
n
F
2n+1
SO
3
X, wherein X comprises an element selected from the group consisting of sodium and potassium, by contacting the perfluoroalkylsulfonic acid with a first basic solution comprising water and a compound of the formula XOH. The at least one perfluoroalkylsulfonic acid can be contacted in any suitable manner known to effect the contact of the at least one perfluoroalkylsulfonic acid with the compound. It is preferred for the at least one perfluoroalkylsulfonic acid to be dissolved in an aqueous solution comprising XOH to thereby form the at least one perfluoroalkylsulfonic acid salt.
Alternatively, at least a portion of at least one perfluoroalkylsulfonyl halide of the formula C
n
F
2n+1
SO
2
Y, wherein n ranges from 2 to 20 and Y is a halide selected from the group consisting of chlorine, fluorine, bromine, iodine, astatine and mixtures of any two or more thereof, preferably fluorine and chlorine, can be converted to at least one perfluoroalkylsulfonic acid salt of the formula C
n
F
2n+1
SO
3
X wherein X comprises an element selected from the group consisting of sodium and potassium, by contacting the perfluoroalkylsulfonyl halide with a first basic solution comprising water and a compound of the formula XOH. The at least one perfluoroalkylsulfonyl halide can be contacted in any suitable manner known to effect the contact of the at least one perfluoroalkylsulfonyl halide with the compound. It is preferred for the at least one perfluoroalkylsulfonyl halide to be dissolved in an aqueous solution comprising XOH to thereby form the at least one perfluoroalkylsulfonic acid salt.
Perfluoroalkylsulfonic acids are not easily purified. Thus, producing a sufficient quantity of purified perfluoroalkylsulfonic acid using typical separation techniques, such as distillation, to produce an effective oligomerization catalyst is extremely expensive and inefficient. However, the perfluoroalkylsulfonic acid salt (as produced above) of the perfluoroalkylsulfonic acid can be easily separated from the aqueous solution, by washing, settling and filtration techniques, resulting in a purified perfluoroalkylsulfonic acid salt.
The purified at least one perfluoroalkylsulfonic acid salt can be dissolved in a basic solution comprising a base comprising hydroxy groups to form a first liquid material.
At least one hydrolyzable silane compound can be dissolved in a first acidic solution comprising a first acid and water to thereby form a second liquid material comprising at least one silanol comprising hydroxy groups and silicon.
Suitable hydrolyzable silane compounds include, but are not limited to, alkoxysilane compounds, preferably, tetramethoxysilane and tetraethoxysilane.
Any suitable acid effective in hydrolyzing the hydrolyzab
Greenwood G. J.
Randolph Bruce B.
Anderson Jeffrey R.
Phillips Petroleum Company
Wood Elizabeth D.
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