U.S. patent number 3,836,342 [Application Number 05/265,850] was granted by the patent office on 1974-09-17 for gasoline containing a methyl phenol and an ether.
This patent grant is currently assigned to Sun Research and Development Co.. Invention is credited to Barry A. Bisson, Jer-Yu Shang, Raymond Wynkoop.
United States Patent |
3,836,342 |
Shang , et al. |
September 17, 1974 |
GASOLINE CONTAINING A METHYL PHENOL AND AN ETHER
Abstract
A useful fuel for an internal combustion engine comprises a
hydrocarbon base stock of gasoline boiling range, a
methyl-substituted phenol and an ether containing a branched alkyl
group and boiling below 460.degree.F., said phenol and said ether
each being present in amount (e.g., 0.1-15 wt. %) sufficient to
increase the Research octane number (RON). The invention also
includes a gasoline blending system. For example, preferred
compositions can be made by blending 89 RON gasoline containing 5
vol. % p-cresol with 97 RON gasoline containing 5% methyl methoxy
propane. Beneficial synergism is noted in such blends for RON
blending values.
Inventors: |
Shang; Jer-Yu (Wilmington,
DE), Bisson; Barry A. (Wilmington, DE), Wynkoop;
Raymond (Gladwyne, PA) |
Assignee: |
Sun Research and Development
Co. (Philadelphia, PA)
|
Family
ID: |
23012115 |
Appl.
No.: |
05/265,850 |
Filed: |
June 23, 1972 |
Current U.S.
Class: |
44/448;
44/449 |
Current CPC
Class: |
C10L
1/023 (20130101); C10L 1/18 (20130101); C10L
1/1852 (20130101); C10L 1/1832 (20130101) |
Current International
Class: |
C10L
1/10 (20060101); C10L 1/02 (20060101); C10L
1/18 (20060101); C10L 1/00 (20060101); C10l
001/02 () |
Field of
Search: |
;252/386 ;44/56,69 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Unzelman et al., "Are there substitutes for lead antiknocks?" May
14, 1971, p. 888, API Division of Refining Proceedings. .
Van Winkle, Matthew, "Aviation Gasoline Manufacture," 1944, p. 199,
McGraw Hill Book Company..
|
Primary Examiner: Garvin; Patrick P.
Assistant Examiner: Metz; Andrew H.
Attorney, Agent or Firm: Church; Mr. George L. Hess; Mr. J.
Edward Bisson; Mr. Barry A.
Claims
The invention claimed is:
1. Gasoline comprising a hydrocarbon base stock of gasoline boiling
range, from 0.05 to 35% of a methyl substituted phenol and from
0.05 to 30 % of a hydrocarbyl ether having at least one branched
alkyl group and boiling below 460.degree.F., said phenol and said
ether each being present in amount sufficient to increase the
Research octane number.
2. Gasoline according to claim 1 and wherein the amounts of said
phenol and said ether are in the range of 0.1-15 wt. %.
3. Gasoline according to claim 2 and wherein the amount of said
phenol is in the range of 0.1-10 wt. % and the total of said
amounts is in the range of 1-15 wt. %.
4. Gasoline according to claim 1 and wherein said ether is methyl
methoxypropane.
5. Gasoline according to claim 1 and wherein said phenol is
selected from the group consisting of ortho, meta and paracresol
and mixtures of two or more said cresols.
6. Gasoline according to claim 5 and wherein said ether is methyl
methoxypropane.
7. Gasoline according to claim 6 and wherein said phenol consists
essentially of paracresol.
8. Gasoline according to claim 6 and wherein said amount of said
phenol is in the range of 0.5-15%, said amount of said ether is in
the range of 0.5-15% and the total of said amounts is in the range
of 1-16%.
9. Gasoline according to claim 8 and wherein the total of said
amounts is in the range of 2-10%.
10. Gasoline according to claim 1 wherein said ether is selected
from the group consisting of diisopropyl ether, diisobutyl ether,
methyl isopentyl ether, methyl isopropyl ether, and mixtures of two
or more said ethers.
11. The composition of claim 1 wherein said base stock contains in
the range of 40-75% paraffins, 0-10% naphthenes, 0-20% olefins, and
20-40% aromatics.
12. The composition of claim 1 wherein said base stock has an RON
in the range of 80-100 and an MON in the range of 75-95.
13. The composition of claim 12 wherein said base stock contains in
the range of 50-60% paraffins, 1-10% naphthenes, 2-10% olefins and
28-38% aromatics.
Description
SUMMARY OF THE INVENTION
The invention includes a novel gasoline blending system, the use of
this system to produce motor fuel of improved octane rating, and
novel gasoline compositions containing certain phenols and
ethers.
One embodiment is gasoline comprising a hydrocarbon base stock of
gasoline boiling range, a methyl substituted phenol and an ether
having at least one branched alkyl group and boiling below
460.degree.F., said phenol and said ether each being present in
amount sufficient to increase the Research octane number.
Another embodiment is a gasoline blending system comprising a
supply of a relatively high Research octane number gasoline
containing an octane improving amount of an ether boiling below
460.degree.F., and a supply of a relatively low Research octane
number gasoline containing an octane improving amount of a methyl
substituted phenol boiling below about 460.degree.F., and means for
blending said two supplies to produce gasolines having octane
numbers intermediate to those of said high and low octane number
gasolines.
The preferred methyl substituted phenols include the cresols (e.g.,
p-cresol), the xylenols (e.g., 2,3 dimethyl phenol) and the
trimethyl-substituted phenols (e.g., hydroxy pseudocumene, hydroxy
mesetylene, and hemimelitol) and mixtures of such phenols, with the
cresols being the preferred additives to a low RON hydrocarbon base
stock in our blending system where the high RON hydrocarbon base
contains an ether additive.
The preferred ethers comprise the dialkyl ethers wherein at least
one alkyl group is branched, and include diisopropyl ether,
diisobutyl ether, methyl isopentyl ether, methyl isopropyl ether,
and mixtures of two or more said ethers. Phenyl alkyl ethers can
also be used (e.g., isopropyl phenyl ether). One non-branched alkyl
phenyl ether, methyl phenyl ether (methoxy benzene) can be used in
a gasoline containing a methyl phenol or as the ether in the
blending system described herein.
The ethers and phenols which can be used in our invention include
those described by G. H. Unzdman, E. J. Forster and A. M. Burns, in
API Preprint (Div. of Refining) No. 47-71, titled "Are There
Substitutes for Lead Antiknocks?," presented at the API Meeting in
San Francisco, May 14, 1971.
Generally, the amount of the ether can be in the range of 0.05-30%
and the amount of the phenol in the range of 0.05-35% (the limit
being determined by solubility); however, the preferred amounts are
in the range of 0.1-15%. More preferred, the phenol is in the range
of 0.5-10 wt. % and the total of said amounts is in the range of
1-15 wt. %.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying FIGS. 1 and 2 illustrate the beneficial
synergistic effect on research octane blending and motor octane
blending values which can be obtained by practice of the blending
system of the present invention wherein the low RON gasoline
contains p-cresol and the high RON gasoline contains methyl methoxy
propane.
As is described in more detail hereinafter, the data for FIGS. 1
and 2 were obtained with gasoline base stocks of slightly different
composition and are presented for purposes of illustration. If
desired, the data in Table 2 herein can be plotted, in a manner
similar to FIG. 1, to provide a comparison of RON and MON blending
values for the same gasoline bases.
FURTHER DESCRIPTION
In a preferred blending system the low RON gasoline contains a
cresol (or mixture of cresols) and preferably contains p-cresol
(typically, 1-15 wt. %, more preferred 2-10 wt. %) and the high RON
gasoline contains methyl tertiary butyl ether, methyl methoxy
propane (MMOP), typically 1-20 wt. %, more preferred 2-15 wt. %
(e.g., 7%).
The gasolines can also contain a lead antiknock (e.g., 0.1-4 cc.
TEL/gal), a lead scavenger (e.g., organo bromides, ethylene
dichloride), deposit modifiers (e.g., boron and phosphorous
compounds), lower acyclic alcohols (e.g., methanol, ethanol,
isopropanol, butanol, etc.), a lead appreciator (e.g.,
t-butylacetate), oxidation inhibitors (e.g., aromatic amines and/or
alkyl phenols, such as 2,6-di-t-butyl-p-cresol), metal deactivators
(e.g., NN'-disalicylidene-1,2-propylene diamine), corrosion
inhibitors (e.g., high molecular weight phosphoric, carboxylic or
sulfonic acids or their reaction products with nitrogen bases, such
as amines, and include "Ethyl MPA"), antistatic additives (e.g.,
"Shell ASA-3") and anti-icing additives (e.g, methylcellosolve and
glycerol). Some of these gasoline additives are described, for
example, by J. P. Heuston, "Chemical Additives in Petroleum Fuels,"
S. African Ind. Chemist, 20:65-70, 74 (1966).
In our gasoline blending system, one or both of the gasolines can
contain an acyclic alcohol containing in the range of 1-4 carbon
atoms preferably the supply which contains the ether contains in
the range of 1-15 wt. % of the alcohol. Such alcohols increase the
RON of the gasolines.
In the blending system, on a lead free basis the high RON gasoline
will typically have an RON in the range of 90-105 and the low RON
gasoline will be at least 5 RON lower. However, where one or both
gasolines contain a lead antiknock compound (such as mixed methyl
and ethyl leads, e.g., dimethyl diethyl lead, etc.), the high RON
gasoline can have an RON as high as 120 (the low RON gasoline
being, typically, in the range of 75-90 RON).
In our blending system, typically, the hydrocarbon base of the high
RON gasoline can contain in the range of 20-40% aromatics, 0-20%
olefins, 0-10% naphthenes, with the balance being paraffins (the
minimum paraffin content being 45%, more preferred 55%). The low
RON gasoline can contain in the range of 15-40% aromatics, 0-25%
olefins, 2-20% naphthenes, with the balance being paraffins, the
minimum paraffin content being 35% (more preferred 45%).
In our preferred gasoline compositions, containing both the ether
and phenol (such as the blends from our system), the preferred
hydrocarbon base stock contains in the range of 40-75% paraffins,
0-10% naphthenes, 0-20% olefins and 20-40% aromatics. More
preferred, the base stock will have an RON in the range of 80-100,
and an MON in the range of 75-95. For the synergistic effect
disclosed herein with p-cresol and MMOP, the preferred base stock
contains in the range of 50-60% paraffins, 1-10% naphthenes, 2-10%
olefins and 28-38% aromatics.
ILLUSTRATIVE EXAMPLES
EXAMPLE 1
Typical low Research octane rating and high Research octane rating
hydrocarbon base stocks, in the gasoline boiling range, were
obtained by blending selected refinery streams, including
catalytically cracked gasoline, straight run gasoline, reformate,
"aviation" alkylate, etc.
Table III reports the percentages by volume of paraffins,
naphthenes, olefins and aromatics in these base stocks. Table IV
reports in more detail on the composition of a "stabilized" sample
of each blend stock.
Methyl methoxy propane (MMOP) was added, 5 wt. %, to a sample of
the high RON base stock and p-cresol, 5 wt. %, was added to a
sample of the low RON base stock.
A series of blends was made of various proportions of the high RON
base with the low RON base and of the high RON base plus 5% MMOP
with the low RON base plus 5% p-cresol.
Research octane ratings were obtained for each of the base stocks
and blends. The significance of the blending value octane number
and its method of calculation are described in U.S. Pat. No.
3,030,195, issued 4-17-62 to Evan B. Ewan. The blending value RON
was then calculated for selected blends. The results of these tests
and calculations are reported in Table I and are summarized by the
curves in FIG. 1. A beneficial synergistic effect was noted for the
RON blending values of the blends containing both p-cresol and
MMOP.
There was an insufficient amount of the two hydrocarbon bases to
permit testing for motor octane number (MON).
EXAMPLE 2
High and low RON hydrocarbon base stocks, in the gasoline boiling
range, were obtained by blending the same types of selected
refinery streams and in about the same proportions as in Example 1.
Since the refinery streams were not identical to those used in the
Example 1 bases, the chemical compositions and octane ratings were
not the same as in Example 1, but represent the usual variation
which is encountered in refining practice. 5 wt. % p-cresol was
added to a sample of the low RON base and 5 wt. % MMOP was added to
the high RON base. The two gasolines were blended as in Example 1
and both research (RON) and motor (MON) octane numbers were
obtained. Research and motor blending values were calculated. Table
II reports the results of these tests and calculations. Slight
synergism (in comparison with Example 1) was noted in the RON
blending values for some blends and greater synergism (but less
than in Example 1) was noted for most blends in the MON blending
values. FIG. 2 presents curves summarizing the results of the motor
octane number testing of this example.
Table V attached hereto presents analyses of typical refinery
streams which can be used to make hydrocarbon base stocks which can
be used in the present invention. Table V also shows proportions
for blending these streams to make a high RON and a low RON base
which are particularly desirable in our blending system. The low
RON base analyzes (in volume %), 40% paraffins, 7% naphthenes, 15%
olefins and 38% aromatics. The high RON base contains 63%
paraffins, 0% naphthenes, 3% olefins and 34% aromatics.
In gasoline for automobiles using conventional piston engines, it
has been found that knocking under actual road conditions (or road
octane) can be better correllated with a function such as R+M/2 or
R+2M,/2, which combines RON (i.e., R) and MON (i.e., M), than with
either RON or MON. Therefore, it is apparent that both of the
previous examples indicate that the present blending system and
gasolines can provide improved performance in an automobile under
actual road conditions.
Among the cresols, the ortho and meta isomers are less preferred in
gasoline than p-cresol. That is, paracresol has higher research and
motor octane blending values (and lower sensitivity) than the other
isomers. Each of these isomers can absorb (or dissolve) in the
order of 2 wt. % water and, with about 15 wt. % cresols in gasoline
the water solubility is about 0.5 wt %. If this amount of water is
added to the gasoline, it reduces flame temperature and, thus, the
NOx (nitrogen oxides) emission and increases the power output of
the engine.
TABLE I
__________________________________________________________________________
p-CRESOL AND METHYL t-BUTYL ETHER IN GASOLINE BLENDS
__________________________________________________________________________
Base Composition (Volume %) RUN A B C D E F G H Low RON Base Stock
+ 5% Wt. p-Cresol 100 -- 85.7 71.4 57.1 42.9 28.6 14.3 High RON
Base Stock + 5% Wt. MMOP -- 100 14.3 28.6 42.9 57.1 71.4 85.7
Research, F-1 Clear Duplicates 89.0 97.8 90.4 91.6 93.0 94.6 95.6
97.0 89.1 97.8 90.6 91.8 93.0 94.6 95.6 96.8 Average 89.05 97.8
90.5 91.7 93.0 94.6 95.6 96.9 A' B' C' D' E' F' G' H' Low RON Base
Stock 100 -- 85.7 71.4 57.1 42.9 28.6 14.3 High RON -Base Stock --
100 14.3 28.6 42.9 57.1 71.4 85.7 Research, F-1 Clear Duplicates
83.6 96.3 85.2 87.0 88.9 90.3 92.0 93.6 83.8 92.2 85.4 87.0 88.8
90.4 92.0 93.6 Average 83.7 96.25 85.3 87.0 88.85 90.35 92.0 93.6
Increased RON 5.35 1.55 5.20 4.70 4.15 4.25 3.60 3.30 Blending
Value RON 191 127 189 181 172 175 164 160
__________________________________________________________________________
##SPC1##
TABLE III ______________________________________ GASOLINE
COMPOSITION (VOLUME PERCENT) Blends (Base Stocks) Low RON High RON
______________________________________ Paraffins 55 58 Naphthenes 9
6 Olefins 10 4 Aromatics 26 32 TOTAL 100 100 Research Octane No.
(RON) 85 95 Motor Octane No. (MON) 78 85
______________________________________
TABLE IV ______________________________________ STABILIZED*
GASOLINE COMPOSITION (VOLUME PERCENT) Base Stock Low RON High RON
______________________________________ Paraffins 50.9 59.7
Paraffins 50.9 59.7 Naphthenes 9.5 2.0 Monocyclic paraffins 8.8 1.9
di-cyclic paraffins 0.6 0.1 tri-cyclic paraffins 0.1 0 Olefins 9.6
3.7 Aliphatic monoolefins 7.6 3.2 Cyclic monoolefins 2.0 0.5
Aromatics 30.2 34.6 (Alkyl Benzenes) (29.2) (34.4) Benzene 1.1 0.5
Toluene 5.5 15.8 C.sub.8 's 10.0 10.0 C.sub.9 's 8.0 5.6 C.sub.10
's 3.6 2.1 C.sub.11 's 1.0 0.4 (Alkyl Naphthalene) (1.0) (0.2)
Naphthalene 0.5 0.2 Methyl naphthalene 0.5 0.0 TOTAL 100.2 100.0
______________________________________ * Stabilized by distillation
to remove components boiling below 100.degree.F.
TABLE V
__________________________________________________________________________
Base Stock Vol.% Component Refinery Analysis (Vol. % of Component)
Low High Component Paraffins Naphthenes Olefins Aromatics RON RON
__________________________________________________________________________
Alkyl benzenes* 100 11.0 Reformate 35.2 0.6 0.1 64.1 10.6 25.8
Catalytic Gasoline 11.9 8.0 20.3 59.8 63.4 Straight Run Gaso. 55.8
33.2 1.2 9.8 2.5 Isopentane 100 12.1 7.4 Isomerizate** 89.8 10.2
0.8 Alkylate 98.0 2.0 1.8 40.6 Poly Gasoline 100 0.3 2.1 Udex
Raffinate 86.8 6.4 3.6 3.2 1.0 Butanes*** 7.5 13.1
__________________________________________________________________________
* Typically bottoms from toluene manufacture, containing mostly
xylenes (typically 50-80%) and toluene (typically 5-30%), remainder
(e.g., 5-15%) being other alkyl benzenes (up to C.sub.11). **
Product of hydroisomerization of refinery streams which contain
normal paraffins (e.g., Udex raffinate). ***The proportion of the
butane component can be varied to obtain the desired Reid Vapor
Pressure (typically in the range of 9-15 psi). Propane can also be
present in winter gasoline.
* * * * *