Field of the Invention
[0001] The present invention relates to a gasoline composition and its preparation method,
particularly to a gasoline composition with a high octane number and its preparation
method.
Background of the Invention
[0002] The conventional additive components which increase the octane number of a gasoline
are mainly lead-containing compounds, but due to their serious environmental pollution,
China has banned the production of lead-containing gasoline. At present, the octane
number of a gasoline may be raised by adding aromatic compounds, oxygen-containing
compounds or methylcyclopentadienyl manganese tricarbonyl (MMT).
[0003] The popular oxygen-containing compounds mainly include ether-based compounds and
alcohol-based compounds. The ether-based compounds include methyl
tert-butyl ether (MTBE), ethyl
tert-butyl ether (ETBE) and
tert-amyl methyl ether (TAME). Among the above ether-based compounds, MTBE is the most
popular, but MTBE has the following shortcomings. Firstly, the solubility of MTBE
in water is about 4.2wt%, and MTBE has a bad smell, so when the content of MTBE in
water exceeds 40-95pg/L, it will make the water give off a bad smell. Secondly, MTBE
is hardly biodegradable, so once the gasoline containing MTBE leaks, MTBE will stay
in the environment for a long time. Considering the serious pollution of MTBE to soil
and drinking water, the clean urban gasoline standard to be implemented in China in
the future limits the additive amount of MTBE and specifies the content of MTBE in
gasoline shall not exceed 15wt%. Alcohol-based compounds mainly include methanol,
ethanol and
tert-butanol, but alcohol-based compounds are highly soluble in water and liable to separate
from gasoline when contacting water, causing negative impact on engine performance,
so the use of alcohol-based compounds is limited to some extent. As aromatic compounds
are liable to negative environmental impact, the content of aromatic compounds added
to gasoline is strictly controlled, too.
[0004] Further, MMT is also a gasoline additive commonly used in China. MMT is an efficient
anti-knock additive of lead-free gasoline, which can raise the octane number of a
gasoline. The additive amount of MMT is small and its cost is low, so it is favored
by users. However, the combustion product of MMT will form deposit on the spark plug
of the motor, worsening the combustion condition. MMT is liable to decomposition when
exposed to light, resulting in decrease of octane number during the use of gasoline.
Meanwhile the generated manganese-containing waste gas will cause serious environmental
pollution. Today, the use of MMT is banned in most developed countries. Chinese national
stage-III motor vehicle emission standard currently adopted by China (i.e., China-III
Emission Standard) also explicitly specifies the manganese content of automatic gasoline
shall not be greater than 0.016g/L.
[0005] At present, people begin to focus on the application of ester-based compounds as
additive components to raise the octane number of gasoline.
[0006] CN1198466A discloses an additive composition of gasoline and its production method, which is
prepared by 0-5.0wt% cyclopentadiene, 0.4-1.6wt% alkenyl halide, 0-1.5wt% ethane halide,
0.3-4.0wt% ester-based compounds, 30.0-65.0wt% aromatic hydrocarbon, 0-5.0wt% enzyme,
1.0-5.0wt% organic anhydride, 0-10.0wt% castor oil, 30.00-60.0wt% solvent and 0.001-0.02wt%
dye. The ester-based compounds have a general formula o fC
xCOOC
y (wherein, x is an integer from 1 to 4, and y is an integer from 1 to 3), which may
be one or a mixture of two selected from the group consisting of ethyl acetate, propyl
acetate, butyl acetate, dimethyl malonate, diethyl malonate and so on, wherein the
mix ratio of the two ester-based compounds is genrally 1 : 1-1 : 3. Although the additive
composition may raise the octane number of gasoline, the content of aromatic hydrocarbon
therein is very high, so the increase of the octane number of gasoline benefits from
the addition of aromatic hydrocarbon. Moreover, as the content of aromatic hydrocarbon
is high, the additive composition is difficult to meet the increasingly strict environmental
protection standard. Furthermore, the additive composition of gasoline has a complex
composition and a complicated preparation process, which are disadvantage in cost
reduction.
[0007] CN1513954A discloses a multifunctional fuel and its production method. The raw materials of
the multifunctional fuel include main raw materials and auxiliary raw materials. The
main raw materials include light hydrocarbon, light oil, wood alcohol, sulfonated
oil, coal tar, gasoline and diesel oil. The auxiliary raw materials include ethyl
stearate, potassium permanganate, sodium hydroxide, water, ethanol, hydrogen peroxide,
ethyl naphthol, petroleum ether, ferrocene, acetone, toluene, phytic acid, sec-butyl
acetate, butyl valerate, isoamylene, ethyl acetate, calcium hypochlorite, sodium tetraborate
decahydrate, 2-phenethyl alcohol and cyclohexanone. The above auxiliary materials
constitute four formulae: A, B, C and D. By chemical reactions, they play the roles
of cosolvent, oxygenate, combustion improver, smoke suppressor, anti-knock agent,
antistatic agent, preservative and alkane number regulator. The proportion of each
formula is as follows:
Formula A: ethyl stearate 2-20wt%, potassium permanganate 3-15wt%, sodium hydroxide
2-15wt%, water 40-80wt% and ethanol 5-30wt%;
Formula B: ethyl naphthol 5-25wt%, petroleum ether 10-30wt%, hydrogen peroxide 5-20wt%,
ferrocene 5-30wt%, acetone 3-30wt% and toluene 5-30wt%;
Formula C: phytic acid 5-25wt%, sec-butyl acetate 3-30wt%, butyl valerate 5-30wt%, isoamylene 10-40wt%, ethyl acetate
5-20wt% and dicyandiamide 5-40wt%;
Formula D: dicyclohexylamine 2-20wt%, calcium hypochlorite 3-30wt%, sodium tetraborate
decahydrate 5-35wt%, 2-phenethyl alcohol 5-50wt%, cyclohexanone 5-30wt% and polyalkenyl
succinimide 5-35wt%.
[0008] By reactions, the above four formulae are made into an integrated additive E. Then
according to need, additive E is added to the main materials to obtain a multifunctional
fuel by reaction. Although the multifunctional fuel uses
sec-butyl acetate,
sec-butyl acetate is added to the multifunctional fuel as an adjuvant and its additive
amount is very low, which is lower than 0.5wt%. Further, although
CN1513954A also specifically discloses that during production of gasoline engine fuel, 50 parts
by weight of gasoline No.70, 30 parts by weight of wood alcohol and 20 parts by weight
of solvent oil No.120 may be mixed with 0.45 part of integrated additive E, it does
not disclose the detailed performance index of the gasoline engine fuel.
[0009] The main problems of the fuel additive disclosed in
CN1513954A lie in the following aspects. The fuel additive has many components, so the preparation
process is complex and the cost is too high. Futhermore, all of formulae A, B, C and
D contain olefins and the content of olefins is high, which is undesirable to the
reduction of olefin content in gasoline, so they are not environment friendly.
[0010] EP0905217A discloses a lead-free gasoline, which comprises C
2-C
15 oxygen-containing compounds, the content of the oxygen-containing compounds in gasoline
makes the content of oxygen atoms is in the range of 0.1-15wt% based on the total
amount of gasoline. The introduction of the oxygen-containing compounds may reduce
the amount of the smoke discharged from the engine, inhibit smouldering of the spark
plug and reduce carbon deposit of gasoline in the combustor. Although
EP0905217A specifically discloses that the oxygen-containing compounds may be esters, the examples
only disclose the gasoline respectively containing methyl
tert-butyl ether,
tert-amyl ethyl ether and methoxy propyl acetate, the octane numbers of which do not be
increased significantly.
[0011] GB2114596A discloses a fuel composition, which comprises 3-50% by volume
tert-butyl acetate.
GB2114596A specifically discloses a fuel composition comprising 90% gasoline and 10%
tert-butyl acetate by volume. The fuel composition has improved research octane number
and motor octane number compared with the gasoline as raw material, but
tert-butyl acetate is expensive as an upmarket chemical intermediate and is not economical
as an additive component of gasoline.
[0012] Therefore, it is becoming an increasingly important research topic to develop non-hazard
and cheap gasoline additives with a high octane number, a long induction period and
a low gum level, thereby improving the anti-knock property of gasoline.
Summary of the Invention
[0013] To overcome the defects of the prior art, the present invention provides a cheap,
pollution-free environment-friendly gasoline composition with good anti-knock property,
a long induction period and a low gum level, and its preparation method, which has
simple operation and low production cost.
[0014] The gasoline composition according to the present invention comprises raw gasoline
and
sec-butyl acetate, based on total amount of the gasoline composition, the
sec-butyl acetate has a content of 1-30wt%, the raw gasoline has a content of 70-99wt%.
[0015] The preparation method of the gasoline composition according to the present invention
comprises a step of adding
sec-butyl acetate into raw material gasoline, based on total amount of the gasoline composition,
the
sec-butyl acetate is added in an amount making content of the
sec-butyl acetate in the gasoline composition in a range of 1-30wt% and content of the
raw gasoline in a range of 70-99wt%.
[0016] The gasoline composition according to the present invention uses
sec-butyl acetate as an additive (i.e., a blending component). Compared with the existing
gasoline additives, particularly with the additives used to improve the anti-knock
property of a gasoline,
sec-butyl acetate has a high octane number, low toxicity, small solubility in water and
low cost, so
sec-butyl acetate is a more efficient, environment- friendly and economical gasoline
additive.
[0017] The
sec-butyl acetate in the gasoline composition according to the present invention can
raise the octane number and anti-knock index of the current gasoline, thus improving
the anti-knock property of gasoline. Meanwhile, the
sec-butyl acetate in the gasoline composition may also play a role in diluting the content
of aromatic hydrocarbons in the gasoline component, thereby alleviating environmental
pollution from aromatic hydrocarbon. Furthermore, the gasoline composition containing
sec-butyl acetate has a long induction period and a low gum level. In addition,
sec-butyl acetate is cheap and will not increase the cost of gasoline.
[0018] Specifically, compared with the catalyzed gasoline as raw gasoline, the research
octane number of the gasoline composition obtained by adding
sec-butyl acetate in an amount of 9.8wt% to a catalyzed gasoline is increased from 90.4
to 93.0, the motor octane number is increased from 81.4 to 83.6, and the anti-knock
index is increased from 85.9 to 88.3; and the induction period of the catalyzed gasoline
containing
sec-butyl acetate in an amount of 9.8wt% is greater than 600min, and the actual gum level
is only 2.77mg/100mL.
[0019] The preparation method of the gasoline composition according to the present invention
has no particular limitation to the purity of
sec-butyl acetate and is highly adaptable to raw materials. Furthermore, according to
the preparation method of the present gasoline composition, the
sec-butyl acetate can be used flexibly, which may not only substitute the existing gasoline
additives but also be used in combination with the existing gasoline additives. In
other words, the preparation method of the gasoline composition provided by the present
invention is flexible. The gasoline composition may be obtained by adding
sec-butyl acetate into the unblended gasoline from a refinery or a chemical plant (such
as a fraction of catalyzed gasoline, and a fraction of straight run gasoline), or
by adding
sec-butyl acetate into the existing finished gasoline. So, the preparation method of
the present invention has a good broad spectrum and can improve the performance of
both the finished gasoline on sale and the unblended gasoline.
[0020] In addition, the preparation method of the gasoline composition according to the
present invention has a simple operation of adding
sec-butyl acetate into the raw material oil and stirring evenly without complex process
such as heating and reaction.
Detailed Description of the Embodiments
[0021] The gasoline composition according to the present invention comprises raw gasoline
and
sec-butyl acetate, based on total amount of the gasoline composition, the
sec-butyl acetate has a content of 1-30wt%, the raw gasoline has a content of 70-99wt%.
[0022] Sec-butyl acetate is a colorless and transparent liquid, which is insoluble in water,
but soluble in most organic solvents. Through research, the inventor of the present
invention found
sec-butyl acetate has excellent overall performance and is a good gasoline additive.
Below, it is described in details in combination with relevant performance indices
1. Density
[0023] The density of automotive gasoline is 0.70-0.78kg/m
3 in general, and the density of
sec-butyl acetate is 0.862kg/m
3. If added in an amount not greater than 30wt%, the added
sec-butyl acetate has no impact on the density of automotive gasoline.
2. Octane number and anti-knock index
[0024] Octane number is an important index measuring the anti-knock property of automotive
gasoline and also an important index measuring gasoline additive.
[0025] The motor octane number and the research octane number (when the octane number is
100 or below) are both determined by comparing a test sample with the knock tendency
of the reference fuel with known octane number under standard conditions. The reference
fuel is a mixture of
iso-octane (the octane number is 100) and
n-heptane (the octane number is zero). The volume percentage of
iso-octane in the reference fuel with knocking intensity equivalent to that of the test
sample is the octane number of the test sample. The motor octane number is determined
in accordance with GB/T503, and the research octane number is determined in accordance
with GB/T5487.
[0026] The motor octane number and the research octane number adopt basically same measurement
methods and devices except the standard conditions upon measurement. The motor octane
number is characterized by the harsh conditions of high temperature of the mixed gas
(heated to 149°C in general) and high rotating speed of the engine (900r/min±10r/min)
and is typically used to determine the anti-knock property of gasoline when the engine
throttle is fully open and the engine runs at a high speed. In comparison, the research
octane number is characterized by the moderately harsh conditions of low temperature
of the mixed gas (not heated in general) and low rotating speed of the engine (600r/min±6r/min)
and is typically used to evaluate the anti-knock property of a gasoline during transition
of the engine from low speed to medium speed. As a general rule, the research octane
number of a same kind of gasoline is higher than the motor octane number. The values
of the research octane number and the motor octane number can be approximately converted
by the following relational expression:

[0027] The difference between the research octane number and the motor octane number is
called gasoline sensitivity.
[0028] Sec-butyl acetate has a high octane number, wherein the research octane number (RON)
reaches 119 and the motor octane number (MON) reaches 107, obviously higher than the
octane number of the components or additives commonly used to raise the octane number
of gasoline (Table 1).
Table 1
| Items |
Reformed gasoline |
Heavy aromatic hydrocarbon |
Butene alkylated oil |
Ethanol |
Methanol |
tert-butyl methyl ether |
ethyl tert-butyl ether |
methyl tert-butyl ether |
sec-butyl acetate |
| MON |
88.2 |
94.0 |
95.9 |
96 |
98 |
98 |
102 |
99 |
107 |
| RON |
100.0 |
107.0 |
97.3 |
111 |
114 |
111 |
118 |
117 |
119 |
[0029] The motor octane number and the research octane number are both determined on a special
single-cylinder engine under the standard test conditions and can hardly reflect the
anti-knock property of a fuel under the running condition of a vehicle. So an empirical
relationship for the anti-knock property of a fuel under the running condition of
a vehicle is put forth, i.e.:

[0030] Anti-knock index is used to reflect the average anti-knock property of a gasoline
under general conditions. As the above expression indicated, the higher the octane
number of gasoline is, the better its anti-knock property will be and the more obviously
the power and economy of the engine will be reflected. The anti-knock index of
sec-butyl acetate is 113, obviously higher than the anti-knock index of other gasoline
additives listed in Table 1.
3. Distillation range
[0031] Vaporability is one of the most important features of a gasoline. Before entering
the engine cylinder, the gasoline is firstly gasified quickly in the vaporizer and
forms a combustible gas with the air. Normally, gasoline stays in the intake tube
only 0.005-0.05s, and its evaporation time in the cylinder is only 0.02-0.03s. In
order to form a uniform and combustible mixed gas in such a short time, the more important
factor in addition to the structure and operating conditions of the gasoline engine
is the vaporability of gasoline. The indices reflecting the vaporability of a gasoline
are distillation range and saturated vapor pressure. In Chinese standard for the quality
of automotive gasoline, distillation range indices include 10vol% evaporating temperature,
50vol% evaporating temperature, 90vol% evaporating temperature and final boiling point
(i.e.: dry point).
(1) 10vol% evaporating temperature
[0032] 10vol% evaporating temperature reflects the amount of the fraction with a low boiling
point in a gasoline, which has a critical influence on the easiness of starting up
a gasoline engine and also has a close relation with the tendency of air lock. Lower
10vol% evaporating temperature means a larger amount of the fraction with a low boiling
point in gasoline with a higher vaporability, so easier starting up a gasoline engine
at low temperature. However, excessively low evaporating temperature may lead to air
lock. Chinese standard for the quality of automotive gasoline requires 10vol% evaporating
temperature shall not be higher than 70°C.
(2) 50vol% evaporating temperature
[0033] 50vol% evaporating temperature reflects the average vaporability of a gasoline, which
has a close relation with the time for rising temperature after starting up a gasoline
engine and the promptness of acceleration. The lower the 50vol% evaporating temperature
of a gasoline is, the larger the evaporation capacity will be at normal temperature,
thereby shortening the time for rising temperature of a gasoline engine, and making
the acceleration of the engine sensitive and make its running gentle. If 50vol% evaporating
temperature is too high, when the engine needs to be geared to high speed from low
speed and fuel supply increases sharply, most of the gasoline cannot be gasified,
resulting in incomplete combustion and even sudden flameout. Chinese standard for
the quality of automotive gasoline requires 50vol% evaporating temperature shall not
be higher than 120°C.
(3) 90vol% evaporating temperature and final boiling point
[0034] 90vol% evaporating temperature and final boiling point reflects the amount of heavy
fraction in a gasoline. If the temperature is too high, it means the gasoline contains
too much heavy fraction and it is difficult to ensure complete evaporation and complete
combustion of the gasoline under the use conditions. This will lead to increase of
carbon deposit in the cylinder and rise of specific fuel consumption. Moreover, the
heavy gasoline fraction incompletely evaporated will also flow into the crankcase
and dilute the lubricating oil, thereby increasing abrasion. Chinese standard for
the quality of automotive gasoline requires 90vol% evaporating temperature shall not
be higher than 190°C and final boiling point shall not be higher than 205°C.
[0035] Sec-butyl acetate has a boiling point of 112.3°C and has certain volatility. When added
to a gasoline, the 10vol% and 50vol% evaporating temperature of the gasoline will
rise slightly, while 90vol% evaporating temperature will decrease slightly. There
is no negative impact on the vaporability of the gasoline composition.
4. Residue amount
[0036] The residue amount of a gasoline is also an important factor directly reflecting
the quality of the gasoline, which reflects the content of the heavy components of
the gasoline most difficult to vapor and the content of the oxidized gelatinous material
generated in the process of storage. High residue amount will result in increment
of carbon deposit in the combustor and valve assembly and serious gumming in the air
intake system and the carburetor throat, thereby affecting the normal operation of
the engine. China-III Emission Standard specifies the residue amount shall not be
greater than 2%.
Sec-butyl acetate basically has no residue amount, thereby having no negative impact
on the residue amount of the gasoline composition.
5. Saturated vapor pressure
[0037] Under the specified conditions, when the gas phase and liquid phase of an oil product
in a test unit reaches a balance, the maximum pressure of the vapor on the liquid
surface is called saturated vapor pressure. Saturated vapor pressure is used to assess
the evaporation intensity of a gasoline, which is an index measuring whether the gasoline
can easily generate air lock in the fuel supply system of a gasoline engine, and meanwhile
may also measure the loss tendency of the gasoline during storage and transport. The
higher the saturated vapor pressure of a gasoline is, the higher the vaporability
will be and the more easily the engine can be started up, but the greater the tendency
of air lock is, the larger the evaporation loss will be. Therefore, the requirements
on the saturated vapor pressure of gasoline are dependent on the atmospheric pressure
and ambient temperature. China-III Emission Standard specifies gasoline vapor pressure
shall not be greater than 88kPa from November 1 to April 30 of next year and not greater
than 72kPa from May 1 to October 31.
[0038] When
sec-butyl acetate is added into a gasoline, the saturated vapor pressure of the gasoline
declines slightly, but the influence is small and the gasoline containing
sec-butyl acetate can still meet the requirement of Chinese national standard.
6. Induction period
[0039] Induction period refers to the time period of an oil product keeping in a stable
status under the specified conditions of accelerated oxidation, which can be determined
by the method specified in GB/T8018. The summary of the method is as follows. A test
sample is oxidized in an oxygen bomb, which is firstly filled oxygen to 68gkPa at
15°C-25°C then heated to 98°C-102°C. Pressure is read at a specified time interval
or continuously recorded till a turning point occures. The needed time when the test
sample reaches its turning point is the induction period measured at the test temperature.
From the measured induction period, the induction period at 100°C may be calculated.
The induction period of a gasoline is measured by minute. Apparently, if the induction
period of a gasoline is long, the tendency of oxidation and gumming is small. China-III
Emission Standard specifies the induction period of a gasoline shall not be smaller
than 480min. The induction period of
sec-butyl acetate is greater than 600min, so it meets the requirement of China-III Emission
Standard.
7. Water-soluble acids or alkalis
[0040] Water-soluble acids are inorganic acids and low-molecule organic acids. Water-soluble
alkalis refer to sodium hydroxide and
etc. They are the residues of oil refining in general, and have strong corrosion to metal,
thereby being forbidded to exist in gasoline. The content of water-soluble acids or
alkalis in a gasoline may be determined in accordance with GB/T259. Summary of the
method is as follows. Water-soluble acids or alkalis in a test sample are extracted
with distilled water or aqueous solution of ethanol. Then methyl orange or phenolphthalein
indicator is used respectively to check the color change of the extract, or the pH
value is determined by a pH meter to judge the existence of water-soluble acids or
alkalis.
Sec-butyl acetate product basically contains no water-soluble acids and water-soluble
alkalis, so it conforms to the relevant Chinese national standard.
8. Mechanical impurities and water
[0041] The finished gasoline refined by an oil refinery contains no mechanical impurities
and water, but gasoline is inevitably contaminated by external environment during
transport, storage and use, causing the entry of mechanical impurities and water into
gasoline. The mechanical impurities in gasoline may block the carburetor jet and the
gasoline filter, meanwhile intensify the abrasion of the carburetor jet and the cylinder
piston assembly. The water in gasoline may be frozen in winter, which may block the
filter or fuel way in serious cases, resulting in interruption of fuel supply. In
addition, water may also accelerate the corrosion of parts, dissolve antioxidant,
accelerating gasoline oxidation to generate gum, result in decomposition of lead tetraethyl
and make the additives such as export agent lose effect. The common method to check
the mechanical impurities and water in gasoline is performed by putting a test sample
into a 100mL glass measuring cylinder and keeping it stand 8-12h. The test sample
shall remain transparent and have no suspended and settled mechanical impurities and
water. When there is dissent, mechanical impurities may be determined by the method
specified in GB/T511 and water may be determined by the method specified in GB/T260.
It is determined by test that
sec-butyl acetate contains no suspended or settled mechanical impurities and water.
9. Content of aromatic hydrocarbon
[0042] During production of
sec-butyl acetate, no aromatic hydrocarbon is generated, so the content of aromatic hydrocarbon
in
sec-butyl acetate is zero.
10. Olefin content
[0043] The standard for the quality of automotive gasoline specifies olefin content shall
be smaller than or equal to 30vol%. Although a small amount of olefin is generated
during the production of
sec-butyl acetate, the olefin content is low and the influence on the increasing of olefin
content of the gasoline is non-significant.
11. Oxygen content
[0044] The limitation to oxygen content in automotive gasoline is mainly from the consideration
of calorific value. With the increasing of oxygen content in a gasoline, the effective
combustible components in the gasoline will decrease, thus reducing calorific value
and impairing the power of the engine. In addition, if the oxygen content in gasoline
is too high, the carbon deposit in the cylinder will decrease, which makes the exhaust
valve of the cylinder lose the protection of carbon deposit, leading to more seriouse
abrasion. In the prevailing automotive gasoline standard, the oxygen content in gasoline
shall be lower than 2.7wt%. Although the oxygen content of
sec-butyl acetate is 27.6wt%, the gasoline containing
sec-butyl acetate may meet the requirement of automotive gasoline standard by controlling
the additive amount of
sec-butyl acetate in gasoline.
12. Iron content
[0045] No iron devices are used during the production of
sec-butyl acetate, so
sec-butyl acetate product contains no iron.
13. Existent gum
[0046] Existent gum is typically used to indicate the tendency of deposit formation of gasoline
in the intake pipeline and intake valve, which is the gasoline evaporation residue
insoluble in
n-heptane determined under the specified conditions. It may be determined in accordance
with GB/T8019. The summary of the method is as follows. A known amount of fuel is
evaporated under the condition of controlled temperature and controlled air. The residues
before extracted by
n-heptane and after extracted by
n-heptane are weighed respectively. The obtained results are reported by mg/100mL.
In this way, the existent gum of the gasoline is determined. China-III Emission Standard
specifies the existent gum of a gasoline shall not be greater than 5mg/100mL at the
time of leaving the factory. The existent gum of
sec-butyl acetate is only 0.5-1.2mg/100mL, so it conforms to the requirement of China-III
Emission Standard.
14. Doctor test
[0047] Doctor test refers to a test in which sodium plumbite reacts with light oil products
under the existence of sublimed sulfur to check mercaptan or hydrogen sulfide in oil,
which may be determined by the method specified in SH/T0174. The methodological principle
of the doctor test is as follows. 10mL of a test sample and 5mL of a sodium plumbite
solution are put into a 50mL measuring cylinder with ground stopper and shaken violently.
If the test sample contains hydrogen sulfide, black lead sulfide will be produed.
If there is no the above reaction, then a little amount of pure and dry sublimed sulfur
powder is added and the mixture is shaken again. If the test sample contains mercaptan,
the color of the oil layer and sulfur membrane will be changed after a series of reactions.
Sec-butyl acetate has passed the doctor test.
15. Copper strip corrosion (50°C, 3h)
[0048] Under specified conditions, the copper corrosion tendency of the oil product is tested
and whether gasoline contains free sulfur and activated sulfide is checked. It is
determined by the method specified in GB/T5096. The summary of the method is as follows.
A polished copper strip is immersed into a certain amount of a test sample and heated
to the designated temperature according to the product standard, and is kept for a
specific time at the temperature. When the test cycle ends, the copper strip is taken
out and is compared with the standard color palettes of corrosion to determine corrosion
level after washed. There are four levels of standard color palettes: level 1 means
slight color change; level 2 means moderate color change; level 3 means serious color
change; and level 4 means corrosion. The copper strip corrosion (50°C, 3h) of a gasoline
specified in China-III Emission Standard shall not be greater than level 1. The copper
strip corrosion of
sec-butyl acetate is 1a, so it conforms to the requirement of China-III Emission Standard.
16. Sulfur content
[0049] Sulfur content refers to the content of sulfur and its derivatives in a gasoline
(such as: hydrogen sulfide, mercaptan and bisulfide), which is expressed by mass percentage.
When the sulfur and its deratives in a gasoline meet water or vapor, sulfurous acid
and sulfuric acid will be produced. Under the condition of gasoline combustion, this
tendency is even stronger. Sulfurous acid and sulfuric acid are highly corrosive to
metals. In addition, sulfur can also reduce the octane number of gasoline and the
perceptibility of gasoline to lead tetraethyl (i.e.: weaken the increment amplitude
of octane number of gasoline by the addition of lead tetraethyl). Therefore, China-III
Emission Standard specifies sulfur content shall not be greater than 150ppm. Sulfur
content may be determined by the method specified in GB/T380.
[0050] The sulfur content of
sec-butyl acetate is very low. When the sulfur content is below 3ppm, it is very suitable
to produce clean gasoline fuel containing little or no sulfur.
17. Methanol content
[0051] No methanol is produced during the production of
sec-butyl acetate and the raw materials contain no methanol, either. So, the content
of methanol in
sec-butyl acetate product is 0.
18. Benzene content
[0052] Benzene is a highly hazardous chemical product. The automotive gasoline standard
specifies the content of benzene shall not be greater than 1.0vol%. Benzene content
may be determined by the method specified in SH/T0693. When there is objection to
the determination of benzene content, the result determined by the method specified
in SH/T0713 shall prevail. According to the determination result,
sec-butyl acetate product contains no benzene.
19. Manganese content
[0053] Manganese content refers to the total content of manganese existing in form of methylcyclopentadienyl
manganese tricarbonyl (MMT) in gasoline. No other types of manganese-containing additives
shall be added. China-III Emission Standard specifies manganese content shall not
be greater than 0.016g/L, which is determined by the method specified in SH/T0711.
Beijing Gasoline Emission Standard C specifies manganese content shall not be greater
than 0.006g/L. According to the determination result,
sec-butyl acetate product contains no manganese.
[0054] The foregoing analysis results indicate
sec-butyl acetate has superior performance indices and is a good gasoline additive.
[0055] The gasoline composition according to the present application, based on the total
amount of the gasoline composition, the
sec-butyl acetate may have a content of 1-30wt%. When the content of
sec-butyl acetate in the gasoline composition is lower than 1wt%, it is difficult to
achieve a desirable effect of raising octane number and anti-knock index of a gasoline.
When the content of
sec-butyl acetate in the gasoline composition is higher than 30wt%, the gasoline composition
will become more corrosive to the rubber washers in the fuel filling pipes and fuel
guns of gasoline stations and the rubber oil conduits of gasoline engines. From the
perspective of further lowering the corrosion to the rubber products contacting the
gasoline composition and controlling the oxygen content of the gasoline composition,
based on the total amount of the gasoline composition, the
sec-butyl acetate preferably has a content of 2-10wt%.
[0056] The raw gasoline in the gasoline composition according to the present invention may
be various kinds of raw gasoline popular in the art, without particular limitation.
Specifically, the raw gasoline may be commercial finished gasoline containing various
kinds of additives, such as gasoline No. 90, gasoline No. 93 or gasoline No. 97; or
the gasoline fraction from an oil refinery or a chemical plant, such as catalytically
cracked gasoline, alkylated gasoline, reformed gasoline, reformed raffinate oil, hydrotreated
coker gasoline, straight run gasoline or light hydrocarbon C5. The light hydrocarbon
C5 refers to various kinds of hydrocarbons containing five carbon atoms as well as
their mixtures.
[0057] The raw gasoline in the gasoline composition according to the present invention may
also contain one or more selected from the group consisting of ether-based compounds,
alcohol-based compounds and aromatic hydrocarbons. Based on the total amount of the
gasoline composition, total amount of the ether-based compounds, the alcohol-based
compounds and the aromatic hydrocarbons is 0.02-33wt%.
[0058] The aromatic hydrocarbons may be various kinds of aromatic hydrocarbons popular in
the art, without particular limitation. Preferably, the aromatic hydrocarbons are
one or more selected from the group consisting of benzene, toluene, ethylbenzene,
xylene (including
o-xylene, m-xylene and
p-xylene), trimethylbenzene (including all the isomers of trimethylbenzene) and C10
aromatic hydrocarbons. The C10 aromatic hydrocarbons refer to the aromatic hydrocarbons
with 10 carbon atoms as well as their mixture. Based on the total amount of the gasoline
composition, the aromatic hydrocarbons preferably have a content of 0.02-33wt%. From
the perspective of environmental protection, based on the total amount of the gasoline
composition, the benzene preferably has a content of 0.01-0.88wt%.
[0059] The ether-based ompounds may be various kinds of ethers well known to those skilled
in the art. Preferably, the ether-based compounds are one or more selected from the
group consisting of methyl
tert-butyl ether, ethyl
tert-butyl ether,
tert-amyl methyl ether and dibutyl ether. Preferably, based on the total amount of the
gasoline composition, the ether-based compounds have a content of 0.1-15wt%.
[0060] The alcohol-based compounds may be various kinds of alcohol compounds popular in
the art. Preferably, the alcohol-based compounds are one or more selected from the
group consisting of methanol, ethanol,
n-butanol,
sec-butanol and
tert-butanol. Based on the total amount of the gasoline composition, the alcohol-based
compounds preferably have a content of 0.02-10wt%.
[0061] The performance indices of the gasoline composition according to the present invention
conform to national automotive gasoline standard III (
GB17930-2006 (III) (Table 2). The gasoline composition not only has a high octane number but also
is pollution free and environmental friendly.
Table 2
| Items |
Quality indices |
| No. 90 |
No. 93 |
No. 97 |
| Research octane number (RON) |
≥90 |
≥93 |
≥97 |
| Anti-knock index (RON+MON)/2 |
≥85 |
≥88 |
/ |
| Lead content (g/L) |
≤0.005 |
| 10vol% evaporating temperature (°C) |
≤70 |
| 50vol% evaporating temperature (°C) |
≤120 |
| 90vol% evaporating temperature (°C) |
≤190 |
| Final boiling point (°C) |
≤205 |
| Residue amount (vol%) |
≤2 |
| Vapor pressure (from November 1 to April 30) (kPa) |
≤88 |
| Vapor pressure (from May 1 to October 31) (kPa) |
≤72 |
| Induction period (min) |
≥480 |
| Water-soluble acid or alkali |
not detected |
| Mechanical impurities and water |
not detected |
| Aromatic hydrocarbon content (vol%) |
≤40 |
| Olefin content (vol%) |
≤30 |
| Oxygen content (wt%) |
≤2.7 |
| Iron content (g/L) |
≤0.01 |
| Existent gum (mg/100mL) |
≤5 |
| Doctor test |
Pass |
| Copper strip corrosion (50°C, 3h) (level) |
≤1 |
| Sulfur content (wt%) |
≤0.015 |
| Methanol content (wt%) |
≤0.3 |
| Benzene content (vol%) |
≤1.0 |
| Manganese content (g/L) |
≤0.016 |
[0062] The present invention further provides a preparation method of the gasoline composition,
which comprises a step of adding
sec-butyl acetate into raw material gasoline, based on the total amount of the gasoline
composition, the
sec-butyl acetate is added in an amount making cotent of the
sec-butyl acetate in the gasoline composition in a range of 1-30wt% and making content
of the raw gasoline in a range of 70-99wt%.
[0063] The present invention has no particular limitation to the method for adding
sec-butyl acetate into raw material gasoline. It may be any one of the methods well known
to those skilled in the art as long as it may ensure the raw gasoline and
sec-butyl acetate are mixed evenly and the content of
sec-butyl acetate is within the specified range. For example, a predetermined amount
of
sec-butyl acetate may be added into raw gasoline in a mixer under stirring; or
sec-butyl acetate and raw gasoline may be simultaneously added to a mixer and stirred
them evenly.
[0064] According to the preparation method of the gasoline composition of the present invention,
based on the total amount of the gasoline composition, the
sec-butyl acetate is added in an amount making content of the
sec-butyl acetate in the gasoline composition in a range of 1-30wt%. Preferably, based
on the total amount of the gasoline composition, the
sec-butyl acetate is added in an amount making content of the
sec-butyl acetate in the gasoline composition in a range of 2-10wt%.
[0065] As
sec-butyl acetate can obviously enhance the overall performance of a gasoline, in particular
octane number, and has no strict requirement on the purity of
sec-butyl acetate per se, the present invention has no particular limitation to the source
of
sec-butyl acetate. It may be any commercial
sec-butyl acetate. From the perspective of further lowering the content of olefin in
the gasoline composition and raising the octane number of the gasoline composition,
the purity of
sec-butyl acetate may be 80wt% or above, preferably 90wt% or above, more preferably 97.5wt%
or above and still more preferably 99wt% or above. When the purity of
sec-butyl acetate is within the foregoing range, it can not only ensure that the content
of olefin in the gasoline composition conforms to China-III Emission Standard but
also make the octane number of the gasoline composition meet use requirements and
lower the cost of the gasoline composition.
[0066] The preparation method of the gasoline composition according to the present invention
may further comprise a step of adding one or more selected from the group consisting
of ether-based compounds, alcohol-based compounds and aromatic hydrocarbons into raw
material gasoline. Based on the total amount of the gasoline composition, total amount
of the ether-based compounds, the alcohol-based compounds and the aromatic hydrocarbons
in the gasoline composition is 0.02-33wt%.
[0067] The present invention has no particular limitation to the addition sequence of
sec-butyl acetate, ether-based compounds, alcohol-based compounds and aromatic hydrocarbons.
The step of adding one or more selected from the group consisting of ether-based compounds,
alcohol-based compounds and aromatic hydrocarbons into raw gasoline and the step of
adding
sec-butyl acetate into raw gasoline can realize the objective of the present invention
when various sequences are used.
[0068] The present invention has no particular limitation to the additive amount of the
ether-based compounds, alcohol-based compounds and aromatic hydrocarbons, and the
additive amount may be a conventional amount in the art as long as the total amount
of ether-based compounds, alcohol-based compounds and aromatic hydrocarbons in the
gasoline composition is 0.02-33wt% based on the total amount of the gasoline composition.
Anyway, from the perspectives of environmental protection and cost reduction, the
ether-based compounds are added in an amount making total content of the ether-based
compounds in the gasoline composition in a range of 0.1-15wt%, the alcohol-based compounds
are added in an amount making total content of the alcohol-based compounds in the
gasoline composition in a range of 0.02-10wt%, and the aromatic hydrocarbons are added
in an amount making total content of the aromatic hydrocarbons in the gasoline composition
in a range of 0.02-33wt%. From the perspective of environmental protection, based
on the total amount of the gasoline composition, the benzene in the aromatic hydrocarbons
are added in an amount making total content of the benzene in the gasoline composition
in a range of 0.01-0.88wt%.
[0069] The types of the ether-based compounds, alcohol-based compounds and aromatic hydrocarbons
added to the gasoline composition have been described hereinbefore, so it is omitted
herein.
[0070] Below the present invention will be described in more details in connection with
examples.
[0071] In the following embodiments, tests are done by the method specified in Chinese national
standard
GB17930-2006 (III).
Example 1
[0072] This example is intended to describe the gasoline composition and its preparation
method provided by the present invention.
[0073] Sec-butyl acetate used in this example is purchased from Hunan Zhongchuang Chemical Co.,
Ltd and has a purity of 97.8wt%, the physical and chemical parameters of which are
listed in Table 3.
[0074] 2 parts by weight of
sec-butyl acetate are added into 98 parts by weight of raw gasoline (hydrogenated gasoline
from catalytic cracking provided by Sinopec Changling Branch) and mixed evenly, so
as to obtain a gasoline composition of the present invention. In the obtained gasoline
composition, the content of
sec-butyl acetate is 2wt%. The technical indices of the obtained gasoline composition
containing
sec-butyl acetate are listed in Table 3.
Example 2
[0075] This example is intended to describe the gasoline composition and its preparation
method provided by the present invention.
[0076] The raw gasoline and
sec-butyl acetate used in this example is same as those in Example 1.
[0077] 5.1 parts by weight of
sec-butyl acetate are added into 94.9 parts by weight of raw gasoline and mixed evenly,
so as to obtain a gasoline composition of the present invention. In the obtained gasoline
composition, the content of
sec-butyl acetate is 5wt%. The technical indices of the obtained gasoline composition
containing
sec-butyl acetate are listed in Table 3.
Example 3
[0078] This example is intended to describe the gasoline composition and its preparation
method provided by the present invention.
[0079] The raw gasoline and
sec-butyl acetate used in this example is same as those in Example 1.
[0080] 10 parts by weight of
sec-butyl acetate are added into 90 parts by weight of raw gasoline and mixed evenly,
so as to obain a gasoline composition of the present invention. In the obtained gasoline
composition, the content of
sec-butyl acetate is 9.8wt%. The technical indices of the obtained gasoline composition
containing
sec-butyl acetate are listed in Table 3.
Example 4
[0081] This example is intended to describe the gasoline composition and its preparation
method provided by the present invention.
[0082] The raw gasoline and
sec-butyl acetate used in this example is same as those in Example 1.
[0083] 30.7 parts by weight of
sec-butyl acetate are added into 69.3 parts by weight of raw gasoline and mixed evenly,
so as to obtain a gasoline composition of the present invention. In the obtained gasoline
composition, the content of
sec-butyl acetate is 30wt%. The technical indices of the obtained gasoline composition
containing
sec-butyl acetate are listed in Table 3.
Comparative Example 1
[0084] The raw gasoline and
sec-butyl acetate used is same as those in Example 1.
[0085] 0.5 part by weight of
sec-butyl acetate is added into 99.5 parts by weight of raw gasoline and mixed evenly,
so as to obtain a gasoline composition. In the obtained gasoline composition, the
content of
sec-butyl acetate is 0.5wt%. The technical indices of the obtained gasoline composition
containing
sec-butyl acetate are listed in Table 3.
Comparative Example 2
[0086] The raw gasoline and
sec-butyl acetate used is same as those in Example 1.
[0087] 35.8 parts by weight of
sec-butyl acetate are added into 64.2 parts by weight of raw gasoline and mixed well,
so as to obtain a gasoline composition. In the obtained gasoline composition, the
content of
sec-butyl acetate is 35wt%. The technical indices of the obtained gasoline composition
containing
sec-butyl acetate are listed in Table 3.
Table 3
| Analytical items |
Test results |
| Catalyzed gasoline |
sec-butyl acetate |
Example 1 |
Example 2 |
Example 3 |
Example 4 |
Comparative Example 1 |
Comparaive Example 2 |
| Density (kg/m3) |
722.0 |
860.0 |
724.7 |
728.8 |
735.5 |
762.5 |
722.2 |
770.3 |
| 10vol% evaporating temperature (°C) |
40.5 |
- |
40.9 |
42.5 |
44.5 |
52.5 |
40.6 |
55.0 |
| 50vol% evaporating temperature (°C) |
86.7 |
- |
87.0 |
90.5 |
93.5 |
97.5 |
86.8 |
99.8 |
| 90vol% evaporating temperature (°C) |
154.3 |
- |
153.6 |
152.0 |
150.0 |
146.8 |
154.2 |
144.5 |
| Final boiling point (°C) |
191.0 |
- |
189.6 |
187.5 |
185.0 |
181.2 |
190.8 |
178.6 |
| Residue amount (vol%) |
1.5 |
- |
1.5 |
1.5 |
1.5 |
1.5 |
1.5 |
1.5 |
| Full efllux (vol%) |
97.5 |
- |
97.5 |
97.5 |
97.5 |
97.5 |
97.5 |
97.5 |
| Aromatic hydrocarbon (vol%) |
26.5 |
0 |
26.0 |
25.2 |
23.9 |
18.6 |
26.4 |
17.2 |
| Olefin (vol%) |
31.9 |
2.0 |
30.7 |
30.4 |
28.9 |
22.9 |
31.7 |
21.4 |
| Doctor test |
pass |
pass |
pass |
pass |
pass |
pass |
pass |
pass |
| Total sulfur (wt%) |
0.016 |
0 |
0.016 |
0.015 |
0.014 |
0.011 |
0.016 |
0.010 |
| MON |
81.4 |
104 |
81.8 |
82.4 |
83.6 |
87.0 |
81.5 |
87.5 |
| RON |
90.4 |
117 |
91.0 |
91.6 |
93.0 |
97.5 |
90.5 |
98.0 |
| Anti-knock index |
85.9 |
110.5 |
86.4 |
87.0 |
88.3 |
92.3 |
86.0 |
92.8 |
| Water-soluble acid or alkali |
not detected |
not detected |
not detected |
not detected |
not detected |
not detected |
not detected |
not detected |
| Vapor pressure (kPa) |
68.5 |
4.2 |
67.0 |
65.0 |
63.0 |
50.5 |
68.2 |
49.0 |
| Oxygen content (wt%) |
0.1 |
27.0 |
0.6 |
1.4 |
2.7 |
8.2 |
0.2 |
9.5 |
| Methanol content (wt%) |
0.01 |
0 |
0.01 |
0.01 |
0.01 |
0.01 |
0.01 |
0.01 |
| Benzene content (vol%) |
0.68 |
0 |
0.67 |
0.65 |
0.61 |
0.48 |
0.68 |
0.44 |
| Existent gum (mg/100mL) |
3.0 |
0.7 |
2.95 |
2.89 |
2.77 |
2.31 |
2.99 |
2.2 |
| Copper strip corrosion |
1a |
1a |
1a |
1a |
1a |
1a |
1a |
1a |
| Induction period (min) |
560 |
>600 |
>600 |
>600 |
>600 |
>600 |
>600 |
>600 |
[0088] The result in Table 3 indicates that the gasoline composition containing
sec-butyl acetate in a content of 2-30wt% has a higher octane number and anti-knock index.
Example 5
[0089] This example is intended to describe the gasoline composition and its preparation
method provided by the present invention.
[0090] The raw gasoline used in this example is same as that in Example 1.
[0091] Sec-butyl acetate used in this example is purchased from Hunan Zhongchuang Chemical Co.,
Ltd. and has a purity of 98.5wt%, the performance indices of which are listed in Table
4.
[0092] 8.1 parts by weight of
sec-butyl acetate are added into 91.9 parts by weight of raw gasoline and mixed evenly,
so as to obtain a gasoline composition of the present invention. In the obtained gasoline
composition, the content of
sec-butyl acetate is 8wt%. The technical indices of the obtained gasoline composition
containing
sec-butyl acetate are listed in Table 4.
Comparative Example 3
[0093] The raw gasoline used in this comparative example is same as that in Example 1. The
methyl
tert-butyl ether used in this comparative example is purchased from Shanghai Yuanjing
Chemicals Co., Ltd. and has a purity of 98.5wt%.
[0094] 8.1 parts by weight of methyl
tert-butyl ether are added into 91.9 parts by weight of raw gasoline and mixed evenly,
so as to obtain a gasoline composition containing methyl
tert-butyl ether. In the obtained gasoline composition, the content of methyl
tert-butyl ether is 8wt%. The technical indices of the obtained gasoline composition containing
methyl
tert-butyl ether are listed in Table 4.
Comparative Example 4
[0095] The raw gasoline used in this comparative example is same as that in Example 1. The
n-butyl acetate used in this comparative example is purchased from Wuxi Baichuan Chemical
Industry Co., Ltd. and has a purity of 98.5wt%.
[0096] 8.1 parts by weight of
n-butyl acetate are added into 91.9 parts by weight of raw material gasoline and mixed
evenly, so as to obtain a gasoline composition containing
n-butyl acetate. In the obtained gasoline composition, the content of
n-butyl acetate is 8wt%. The technical indices of the obtained gasoline composition
containing
n-butyl acetate are listed in Table 4.
Comparative Example 5
[0097] The raw gasoline used in this comparative example is same as that in Example 1. The
tert-butyl acetate used in this comparative example is purchased from Shanghai Cyclobase
Fine-Chemical Co., Ltd. and has a purity of 98.5wt%.
[0098] 8.1 parts by weight of
tert-butyl acetate are added into 91.9 parts by weight of raw gasoline and mixed evenly,
so as to obtain a gasoline composition containing
tert-butyl acetate. In the obtained gasoline composition, the content of
tert-butyl acetate is 8wt%. The technical indices of the obtained gasoline composition
containing
tert-butyl acetate are listed in Table 4.
Table 4
| Analytical items |
Test results |
| Catalyzed gasoline |
sec-butyl acetate |
methyl tert-butyl ether |
Example 5 |
Comparative Example 3 |
Comparative Example 4 |
Comparative Example 5 |
| Density (kg/m3) |
722.0 |
862.0 |
739.5 |
733.0 |
723.4 |
734.4 |
736.2 |
| 10vol% evaporating temperature (°C) |
40.5 |
- |
- |
44.2 |
41.5 |
44.5 |
43.6 |
| 50vol% evaporating temperature (°C) |
86.7 |
- |
- |
91.0 |
83.8 |
91.5 |
88.5 |
| 90vol% evaporating temperature (°C) |
154.3 |
- |
- |
150.4 |
146.2 |
150.9 |
149.2 |
| Final boiling point (°C) |
191.0 |
- |
- |
185.4 |
180.2 |
186.0 |
183.2 |
| Residue amount (vol%) |
1.5 |
- |
1.5 |
1.5 |
1.5 |
1.5 |
1.5 |
| Full efflux (vol%) |
97.5 |
- |
97.5 |
97.5 |
97.5 |
97.5 |
97.5 |
| Aromatic hydrocarbon (vol%) |
26.5 |
0 |
0 |
24.4 |
24.4 |
24.4 |
24.4 |
| Olefin (vol%) |
31.9 |
1.2 |
0.5 |
29.4 |
29.4 |
29.3 |
29.3 |
| Doctor test |
pass |
pass |
pass |
pass |
pass |
pass |
pass |
| Total sulfur (wt%) |
0.016 |
0 |
0.013 |
0.015 |
0.016 |
0.015 |
0.015 |
| MON |
81.4 |
106 |
99 |
83.4 |
83.0 |
82.5 |
84.0 |
| RON |
90.4 |
119 |
117 |
93.0 |
92.8 |
92.0 |
94.0 |
| Anti-knock index |
85.9 |
112 |
109 |
88.2 |
87.9 |
87.3 |
89.0 |
| Water-soluble acid or alkali |
not detected |
not detected |
not detected |
not detected |
not detected |
not detected |
not detected |
| Vapor pressure (kPa) |
68.5 |
4.6 |
55 |
64.8 |
67.8 |
63.5 |
- |
| Oxygen content (wt%) |
0.1 |
27.2 |
18.2 |
2.3 |
1.5 |
2.3 |
2.3 |
| Methanol content (wt%) |
0.01 |
0 |
0.08 |
0.01 |
0.02 |
0.01 |
0.01 |
| Benzene content (vol%) |
0.68 |
0 |
0 |
0.63 |
0.63 |
0.63 |
0.63 |
| Existent gum (mg/100mL) |
3.0 |
0.6 |
1.0 |
2.8 |
2.8 |
2.8 |
3.0 |
| Copper strip corrosion |
1a |
1a |
1a |
1a |
1a |
1a |
1a |
| Induction period (min) |
560 |
>600 |
>600 |
>600 |
>600 |
>600 |
>560 but <600 |
[0099] The result in Table 4 indicates that compared with the gasoline composition containing
methyl
tert-butyl ether and the gasoline composition containing
n-butyl acetate, the gasoline composition containing
sec-butyl acetate has higher octane number and anti-knock index. Compared with the gasoline
composition containing
tert-butyl acetate, the gasoline composition containing
sec-butyl acetate has less existent gum and a longer induction period. Further, the density
of the gasoline composition containing
sec-butyl acetate is lower than the gasoline composition containing
tert-butyl acetate, therefore,
sec-butyl acetate is more suitable for blending with gasoline.
Example 6
[0100] This example is intended to describe the gasoline composition and its preparation
method provided by the present invention.
[0101] The
sec-butyl acetate used in this example is purchased from Hunan Zhongchuang Chemical Co.,
Ltd. and has a purity of 80wt%.
[0102] 6.3 parts by weight of
sec-butyl acetate are added into 93.7 parts by weight of raw gasoline (commercial gasoline
No. 90) and mixed evenly, so as to obtain a gasoline composition of the present invention.
In the obtained gasoline composition, the content of
sec-butyl acetate is 5wt%. The technical indices of the obtained gasoline composition
containing
sec-butyl acetate are listed in Table 5.
Example 7
[0103] This example is intended to describe the gasoline composition and its preparation
method provided by the present invention.
[0104] The raw gasoline used in this example is same as that in Example 6. The
sec-butyl acetate used in this example is purchased from Hunan Zhongchuang Chemical Co.,
Ltd. and has a purity of 90wt%.
[0105] 5.6 parts by weight of
sec-butyl acetate are added into 94.4 parts by weight of raw gasoline and mixed evenly,
so as to obtain a gasoline composition of the present invention. In the obtained gasoline
composition, the content of
sec-butyl acetate is 5wt%. The technical indices of the obtained gasoline composition
containing
sec-butyl acetate are listed in Table 5.
Example 8
[0106] This example is intended to describe the gasoline composition and its preparation
method provided by the present invention.
[0107] The raw gasoline used in this example is same as that in Example 6. The
sec-butyl acetate used in this example is purchased from Hunan Zhongchuang Chemical Co.,
Ltd. and has a purity of 97.5wt%.
[0108] 5.1 parts by weight of
sec-butyl acetate are added into 94.9 parts by weight of raw gasoline and mixed well,
so as to obtain a gasoline composition of the present invention. In the obtained gasoline
composition, the content of
sec-butyl acetate is 5wt%. The technical indices of the obtained gasoline composition
containing
sec-butyl acetate are listed in Table 5.
Example 9
[0109] This example is intended to describe the gasoline composition and its preparation
method provided by the present invention.
[0110] The raw gasoline used in this example is same as that in Example 6. The
sec-butyl acetate used in this example is purchased from Hunan Zhongchuang Chemical Co.,
Ltd. and has a purity of 99wt%.
[0111] 5.1 parts by weight of
sec-butyl acetate are added into 94.9 parts by weight of raw gasoline and mixed evenly,
so as to obtain a gasoline composition of the present invention. In the obtained gasoline
composition, the content of
sec-butyl acetate is 5wt%. The technical indices of the obtained gasoline composition
containing
sec-butyl acetate are listed in Table 5.
Table 5
| Analytical items |
Test results |
| gasoline No. 90 |
Example 6 |
Example 7 |
Example 8 |
Example 9 |
| Density (kg/m3) |
702.3 |
709.1 |
709.8 |
710.4 |
710.5 |
| 10vol% evaporating temperature (°C) |
39.5 |
41.0 |
42.5 |
43.8 |
44.2 |
| 50vol% evaporating temperature (°C) |
79.5 |
80.3 |
82.0 |
83.5 |
83.8 |
| 90vol% evaporating temperature (°C) |
136.5 |
135.9 |
135.0 |
134.5 |
134.1 |
| Final boiling point (°C) |
175.6 |
171.2 |
169.5 |
168.8 |
168.4 |
| Residue amount (vol%) |
1.5 |
1.5 |
1.5 |
1.5 |
1.5 |
| Full efflux (vol%) |
97.5 |
97.5 |
97.5 |
97.5 |
97.5 |
| Aromatic hydrocarbon (vol%) |
32.1 |
30.5 |
30.5 |
30.5 |
30.5 |
| Olefin (vol%) |
15.4 |
15.6 |
15.1 |
14.7 |
14.7 |
| Doctor test |
pass |
pass |
pass |
pass |
pass |
| Total sulfur (wt%) |
0.016 |
0.015 |
0.015 |
0.015 |
0.015 |
| MON |
81.0 |
81.4 |
82.0 |
82.3 |
82.5 |
| RON |
90.2 |
90.7 |
91.2 |
91.5 |
91.7 |
| Anti-knock index |
85.6 |
86.1 |
86.6 |
86.9 |
87.1 |
| Water-soluble acid or alkali |
not detected |
not detected |
not detected |
not detected |
not detected |
| Vapor pressure (kPa) |
72.5 |
69.0 |
69.2 |
69.4 |
69.5 |
| Oxygen content (wt%) |
0.5 |
1.6 |
1.7 |
1.8 |
1.9 |
| Methanol content (wt%) |
0.01 |
0.01 |
0.01 |
0.01 |
0.01 |
| Benzene content (vol%) |
0.52 |
0.49 |
0.49 |
0.49 |
0.49 |
| Existent gum (mg/100mL) |
2.5 |
2.4 |
2.4 |
2.4 |
2.4 |
| Copper strip corrosion |
1a |
1a |
1a |
1a |
1a |
| Induction period (min) |
>600 |
>600 |
>600 |
>600 |
>600 |
[0112] The result in Table 5 indicates that the preparation method of the gasoline composition
according to the present invention have no particular limitation to the purity level
of
sec-butyl acetate and the
sec-butyl acetate with a purity level not lower than 80wt% is acceptable. So the preparation
method of the gasoline composition according to the present invention is highly adaptable
to raw materials.
Example 10
[0113] This example is intended to describe the gasoline composition and its preparation
method provided by the present invention.
[0114] The
sec-butyl acetate used in this example is purchased from Hunan Zhongchuang Chemical Co.,
Ltd. and has a purity of 99.5wt%, the octane number and anti-knock index of which
are listed in Table 6.
[0115] 8 parts by weight of
sec-butyl acetate are added to 92 parts by weight of raw gasoline (light hydrocarbon
C5 provided by CNOOC and Shell Petrochemicals Company Limited) and mixed evenly, so
as to obtain a gasoline composition of the present invention. In the obtained gasoline
composition, the content of
sec-butyl acetate is 8wt%. The octane number and anti-knock index of the obtained gasoline
composition containing
sec-butyl acetate are listed in Table 6.
Example 11
[0116] This example is intended to describe the gasoline composition and its preparation
method provided by the present invention.
[0117] The
sec-butyl acetate used in this example is purchased from Hunan Zhongchuang Chemical Co.,
Ltd. and has a purity of 80wt%, the octane number and anti-knock index of which are
listed in Table 6.
[0118] 37.5 parts by weight of
sec-butyl acetate are added into 62.5 parts by weight of raw gasoline (straight run gasoline
provided by Sinopec Changling Branch) and mixed evenly, so as to obtain a gasoline
composition of the present invention. In the obtained gasoline composition, the content
of
sec-butyl acetate is 30wt%. The octane number and anti-knock index of the obtained gasoline
composition containing
sec-butyl acetate are listed in Table 6.
Example 12
[0119] This example is intended to describe the gasoline composition and its preparation
method provided by the present invention.
[0120] The
sec-butyl acetate used in the example is purchased from Hunan Zhongchuang Chemical Co.,
Ltd. and has a purity of 90wt%, the octane number and anti-knock index of which are
listed in Table 6.
[0121] 16.7 parts by weight of
sec-butyl acetate are added into 83.3 parts by weight of raw gasoline (reformed raffinate
oil provided by Sinopec Shanghai Branch) and mixed evenly, so as to obtain a gasoline
composition of the present invention. In the obtained gasoline composition, the content
of
sec-butyl acetate is 15wt%. The octane number and anti-knock index of the obtained gasoline
composition containing
sec-butyl acetate are listed in Table 6.
Example 13
[0122] This example is intended to describe the gasoline composition and its preparation
method provided by the present invention.
[0123] The
sec-butyl acetate used in this example is purchased from Hunan Zhongchuang Chemical Co.,
Ltd. and has a purity of 95wt%, the octane number and anti-knock index of which are
listed in Table 6.
[0124] 2.1 parts by weight of
sec-butyl acetate are added into 97.9 parts by weight of raw gasoline (reformed gasoline
provided by Sinopec Changling Branch) and mixed evenly, so as to obtain a gasoline
composition of the present invention. In the obtained gasoline composition, the content
of
sec-butyl acetate is 2wt%. The octane number and anti-knock index of the obtained gasoline
composition containing
sec-butyl acetate are listed in Table 6.
Table 6
| Analytical items |
Test results |
| sec-butyl acetate 99.5% |
Light hydrocarbon C5 |
Example 10 |
sec-butyl acetate 80% |
straight run gasoline |
Example 11 |
sec-butyl acetate 90% |
Reformed raffinate oil |
Example 12 |
sec-butyl acetate 95% |
Reformed gasoline |
Example 13 |
| MON |
107 |
72 |
76.6 |
90 |
55 |
69.5 |
98 |
68 |
74.5 |
103 |
98 |
98.2 |
| RON |
119 |
83 |
87.7 |
101 |
56 |
74 |
110 |
70 |
77.5 |
115 |
105 |
105.2 |
| Anti-knock index |
113 |
77.5 |
82.2 |
95.5 |
55.5 |
71.8 |
104 |
69 |
76 |
109 |
101.5 |
101.7 |
[0125] The result in Table 6 indicates that the preparation method of the gasoline composition
according to the present invention may be used to raise the octane number of the raw
gasoline from various sources and has a good broad spectrum.
Example 14
[0126] This example is intended to describe the gasoline composition and its preparation
method provided by the present invention.
[0127] The
sec-butyl acetate used in this example is purchased from Hunan Zhongchuang Chemical Co.,
Ltd. and has a purity 95wt%, the physical and chemical parameters of which are listed
in Table 7.
[0128] 10.5 parts by weight of
sec-butyl acetate and 10 parts by weight of toluene (purchased from Sinopec Changling
Refinery, purity 98.5wt%) are added into 79.5 parts by weight of raw gasoline (hydrogenated
gasoline from catalytic cracking purchased from Sinopec Changling Branch) respectively,
and mixed evenly, so as to obtain a gasoline composition of the present invention.
In the obtained gasoline composition, the content of
sec-butyl acetate is 10wt% and the content of toluene is 10wt%. The technical indices
of the obtained gasoline composition are listed in Table 7.
Comparative Example 6
[0129] A gasoline composition is obtained by the method same as Example 14, except that
no
sec-butyl acetate is added and 20.5 parts by weight of toluene is added into 79.5 parts
by weight of raw gasoline and mixed evenly, so as to obtain a gasoline composition.
The technical indices of the obtained gasoline composition are listed in Table 7.
Example 15
[0130] This example is intended to describe the gasoline composition and its preparation
method provided by the present invention.
[0131] The
sec-butyl acetate and raw material gasoline used in this example is same as those in
Example 14.
[0132] 2.1 parts by weight of
sec-butyl acetate and 2 parts by weight of methyl
tert-butyl ether (purchased from Shanghai Yuanjing Chemicals Co., Ltd., purity 98.5wt%)
are added to 95.9 parts by weight of raw material gasoline and mixed evenly, so as
to obtain a gasoline composition of the present invention. In the obained gasoline
composition, the content of
sec-butyl acetate is 2wt% and the content of methyl
tert-butyl ether is 2wt%. The technical indices of the obtained gasoline composition are
listed in Table 7.
Comparative Example 7
[0133] A gasoline composition is obtained by the method same as Example 15, except that
no
sec-butyl acetate is added, and 4.1 parts by weight of methyl
tert-butyl ether is added to 95.9 parts by weight of raw gasoline and mixed evenly, so
as to obtain a gasoline composition. The technical indices of the obtained gasoline
composition are listed in Table 7.
Example 16
[0134] This example is intended to describe the gasoline composition and its preparation
method provided by the present invention.
[0135] The
sec-butyl acetate and raw gasoline used in this example is same as those in Example 14.
[0136] 5.3 parts by weight of
sec-butyl acetate and 3 parts by weight of ethanol (purchased from Henan Tianguan Fuel
Ethanol Co., Ltd., purity 98.5wt%) are added into 91.7 parts by weight of raw gasoline
and mixed evenly, so as to obtain a gasoline composition of the present invention.
In the obtained gasoline composition, the content of
sec-butyl acetate is 5wt% and the content of ethanol is 3wt%. The technical indices of
the obtained gasoline composition are listed in Table 7.
Comparative Example 8
[0137] A gasoline composition is obtained by the method same as Example 16, except that
no
sec-butyl acetate is added, and 8.3 parts by weight of ethanol is added into 91.7 parts
by weight of raw gasoline and mixed evenly, so as to obatin the gasoline composition.
The technical indices of the obtained gasoline composition are listed in Table 7.
Table 7
| Analytical items |
Test results |
| Catalyzed gasoline |
sec-butyl acetate |
Example 14 |
Example 15 |
Example 16 |
Comparative Example 6 |
Comparative Example 7 |
Comparative Example 8 |
| Density (kg/m3) |
722.0 |
855.5 |
750.5 |
725.2 |
731.1 |
751.7 |
722.7 |
727.6 |
| 10vol% evaporating temperature (°C) |
40.5 |
- |
45.0 |
40.0 |
43.2 |
44.8 |
39.5 |
41.3 |
| 50vol% evaporating temperature (°C) |
86.7 |
- |
95.0 |
88.0 |
88.5 |
94.5 |
87.2 |
86.5 |
| 90vol% evaporating temperature (°C) |
154.3 |
- |
152.0 |
153.0 |
150.2 |
151.0 |
151.5 |
147.6 |
| Final boiling point (°C) |
191.0 |
- |
187.0 |
189.0 |
182.3 |
185.5 |
187.0 |
178.8 |
| Residue amount (vol%) |
1.5 |
- |
1.5 |
1.5 |
1.5 |
1.5 |
1.5 |
1.5 |
| Full efflux (vol%) |
97.5 |
- |
97.5 |
97.5 |
97.5 |
97.5 |
97.5 |
97.5 |
| Aromatic hydrocarbon (vol%) |
26.5 |
0 |
31.1 |
25.4 |
24.3 |
41.6 |
25.4 |
24.3 |
| Olefin (vol%) |
31.9 |
4.6 |
26.4 |
30.8 |
29.5 |
30.6 |
25.4 |
29.5 |
| Doctor test |
pass |
pass |
pass |
pass |
pass |
pass |
pass |
pass |
| Total sulfur (wt%) |
0.016 |
0 |
0.013 |
0.015 |
0.015 |
0.013 |
0.016 |
0.015 |
| MON |
81.4 |
102 |
85.0 |
82.9 |
83.2 |
85.5 |
82.0 |
82.5 |
| RON |
90.4 |
115 |
94.5 |
91.2 |
92.3 |
95.0 |
91.0 |
92.0 |
| Anti-knock index |
85.9 |
108.5 |
89.8 |
87.1 |
87.8 |
90.3 |
86.5 |
87.3 |
| Water-soluble acid or alkali |
not detected |
not detected |
not detected |
not detected |
not detected |
not detected |
not detected |
not detected |
| Vapor pressure (kPa) |
68.5 |
4.2 |
60.0 |
66.0 |
63.4 |
55.2 |
66.5 |
64.0 |
| Oxygen content (wt%) |
0.1 |
26.2 |
2.5 |
0.86 |
2.3 |
0.1 |
0.84 |
3.0 |
| Methanol content (wt%) |
0.01 |
0 |
0.01 |
0.01 |
0.01 |
0.009 |
0.013 |
0.008 |
| Benzene content (vol%) |
0.68 |
0 |
0.54 |
0.68 |
0.63 |
0.54 |
0.68 |
0.63 |
| Existent gum (mg/100mL) |
3.0 |
1.2 |
2.5 |
2.9 |
2.8 |
2.4 |
2.9 |
2.8 |
| Copper strip corrosion |
1a |
1a |
1a |
1a |
1a |
1a |
1a |
1a |
| Induction period (min) |
560 |
>600 |
>600 |
>600 |
>600 |
>600 |
>600 |
>600 |
[0138] The result in Table 7 indicates that
sec-butyl acetate may be used in combination with other gasoline additives. By comparing
Example 14 with Comparative Example 6, it can be seen that
sec-butyl acetate not only may be used to raise the octane number and anti-knock index
of gasoline, but also may be used to dilute the aromatic hydrocarbon in gasoline.
By comparing Example 15 with Comparative Example 7 and comparing Example 16 with Comparative
Example 8, it can be seen that under the condition of a same additive amount, the
gasoline composition containing
sec-butyl acetate has a higher octane number and anti-knock index.
Example 17
[0139] This example is intended to describe the gasoline composition and its preparation
method provided by the present invention.
[0140] The
sec-butyl acetate and raw gasoline used in this example is same as those in Example 5.
[0141] 5 parts by weight of
sec-butyl acetate, 5 parts by weight of ethyl
tert-butyl ether (purchased from Guangzhou Weibo Chemical Co., Ltd., purity 98.5wt%),
20 parts by weight of xylene (purchased from Sinopec Changling Refinery, purity 98.5wt%)
and 2 parts by weight of
tert-butanol (purchased from Shanghai Xingao Chemical Reagent Co., Ltd., purity 98.5wt%)
are added into 68 parts by weight of raw gasoline respectively and mixed evenly, so
as to obain a gasoline composition of the present invention. In the obtained gasoline
composition, the content of
sec-butyl acetate is 5wt%, the content of ethyl
tert-butyl ether is 5wt%, the content of xylene is 20wt% and the content of
tert-butanol is 2wt%. The technical indices of the obtained gasoline composition are listed
in Table 8.
Comparative Example 9
[0142] A gasoline composition is obtained by the method same as Example 17, except that
no
sec-butyl acetate is added, while 10 parts by weight of ethyl
tert-butyl ether, 20 parts by weight of xylene and 2 parts by weight of tert-butanol are
added to 68 parts by weight of raw gasoline respectively and mixed evenly, so as to
obtain a gasoline composition. In the obtained gasoline composition, the content of
ethyl
tert-butyl ether is 10wt%, the content of xylene is 20wt% and the content of tert-butanol
is 2wt%. The technical indices of the obtained gasoline composition are listed in
Table 8.
Example 18
[0143] This example is intended to describe the gasoline composition and its preparation
method provided by the present invention.
[0144] The
sec-butyl acetate and raw gasoline used in this example are same as those in Example
5.
[0145] 5 parts by weight of
sec-butyl acetate, 1 part by weight of methyl
tert-butyl ether (purchased from Shanghai Yuanjing Chemicals Co., Ltd., purity 98.5wt%)
and 10 parts by weight of xylene (purchased from Sinopec Changling Refinery, purity
98.5wt%) are added into 84 parts by weight of raw gasoline respectively and mixed
evenly, so as to obtain a gasoline composition of the present invention. In the obtained
gasoline composition, the content of
sec-butyl acetate is 5wt%, the content of methyl
tert-butyl ether is 1wt% and the content of xylene is 10wt%. The technical indices of
the obtained gasoline composition are listed in Table 8.
Comparative Example 10
[0146] A gasoline composition is obtained by the method same as Example 18, except that
no
sec-butyl acetate is added, while 6 parts by weight of methyl
tert-butyl ether and 10 parts by weight of xylene are added into 84 parts by weight of
raw gasoline respectively and mixed evenly, so as to obtain a gasoline composition.
In the obtained gasoline composition, the content of methyl
tert-butyl ether is 6wt% and the content of xylene is 10wt%. The technical indicds of
the obtained gasoline composition are listed in Table 8.
Table 8
| Analytical items |
Test result |
| Catalyzed gasoline |
sec-butyl acetate |
Example 17 |
Example 18 |
Comparative Example 9 |
Comparative Example 10 |
| Density (kg/m3) |
722.0 |
862.0 |
759.4 |
742.5 |
753.8 |
736.9 |
| 10vol% evaporating temperature (°C) |
40.5 |
- |
55.0 |
52.5 |
53.0 |
50.5 |
| 50vol% evaporating temperature (°C) |
86.7 |
- |
94.8 |
92.0 |
92.8 |
90.5 |
| 90vol% evaporating temperature (°C) |
154.3 |
- |
143.0 |
149.5 |
141.0 |
147.0 |
| Final boiling point (°C) |
191.0 |
- |
172.3 |
180.5 |
169.8 |
177.5 |
| Residue amount (vol%) |
1.5 |
- |
1.5 |
1.5 |
1.5 |
1.5 |
| Full efflux (vol%) |
97.5 |
- |
97.5 |
97.5 |
97.5 |
97.5 |
| Aromatic hydrocarbon (vol%) |
26.5 |
0 |
38.0 |
32.3 |
38.0 |
32.3 |
| Olefin (vol%) |
31.9 |
1.2 |
21.8 |
27.0 |
21.8 |
26.8 |
| Doctor test |
pass |
pass |
pass |
pass |
pass |
pass |
| Total sulfur (wt%) |
0.016 |
0 |
- |
- |
- |
- |
| MON |
81.4 |
106 |
87.5 |
84.5 |
86.5 |
84.0 |
| RON |
90.4 |
118.5 |
98.0 |
94.0 |
97.0 |
93.5 |
| Anti-knock index |
85.9 |
112.3 |
92.8 |
89.3 |
91.8 |
88.8 |
| Water-soluble acid or alkali |
not detected |
- |
not detected |
not detected |
not detected |
not detected |
| Vapor pressure (kPa) |
68.5 |
4.6 |
48.6 |
60.8 |
49.7 |
62.5 |
| Oxygen content (wt%) |
0.1 |
27.2 |
2.6 |
1.6 |
2.1 |
1.2 |
| Methanol content (wt%) |
0.01 |
0 |
0.01 |
0.01 |
0.01 |
0.013 |
| Benzene content (vol%) |
0.68 |
0 |
0.46 |
0.6 |
0.46 |
0.6 |
| Existent gum (mg/100mL) |
3.0 |
0.6 |
2.3 |
2.8 |
2.3 |
3.0 |
| Copper strip corrosion |
1a |
1a |
1a |
1a |
1a |
1a |
| Induction period (min) |
560 |
>600 |
>600 |
>600 |
>600 |
>600 |
[0147] The result in Table 8 indicates that
sec-butyl acetate may be used in combination with other additives and the gasoline composition
containing
sec-butyl acetate has a higher octane number and anti-knock index.