JP3478825B2 - Lead-free MMT fuel composition - Google Patents

Description

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates generally to novel lead-free fuel compositions for spark ignition internal combustion engines. More particularly, the present invention relates to a combination of organomanganese and unleaded fuels and mechanical and / or chemical means capable of inhibiting the production of manganese dioxide (eg, Mn ₃ O ₄ ) during combustion, where the result is The resulting hydrocarbon emissions will meet minimum legal environmental standards.

Description of the Prior Art The incorporation of various organometallic compounds as antiknock agents into fuels for highly compressible spark ignition internal combustion engines has long been practiced. A common organometallic compound used for this purpose is tetraethyl lead (TEL). Generally, these organometallic compounds are useful as antiknock agents. However, some environmental hazards have been associated with these compounds alkyl lead compounds. This situation encourages the Environmental Protection Agency (EPA).
A series of orders were issued by and the leaded gasoline was gradually abolished.

Many compounds have been proposed and / or used in place of the tetraethyllead compound. For example, cycl
omatic) Manganese tricarbonyl (CMT), especially methylcyclopentadienyl manganese tricarbonyl (MMT)
Organomanganese compounds such as were previously accepted alternatives to TEL. However, these compounds have created a series of other environmental problems. That is, there was a steady increase in non-oxidized and / or partially oxidized hydrocarbon emissions from its use. Fuels containing this organomanganese compound produce levels of harmful hydrocarbon emissions that are above legally acceptable levels. Furthermore, according to experience in the industry, more than 1 / 16g (0.0165212g / liter) per gallon
It has been shown that the concentration of organomanganese containing Mn is a direct cause of plugging of the catalytic converter. Therefore, under US federal law, EPA Section 211 (f) (4)
The use of manganese (ie MMT) in all unleaded gasoline is prohibited in the absence of Waiver.
So far, all attempts to get this Weber have failed.

It is well known to those skilled in the art that many types of oxidizing components can be included with the lead-free base as a means of improving anti-knock properties and / or reducing carbon monoxide emissions of the fuel. These oxidizing components include low molecular weight alcohols, various ethers, esters, oxides, phenols, ketones and the like. Due to their properties, some of these components are used as pure engine fuel, ie methanol.

Some of these oxidizing components can be used in combination with one another. For example, in 1976, "Hydrocarbon Processing Magazine" (Hydrocarbo
n Processing) July issue, Csikos, Pallay, Laky et al., "Low-Lead Fuel with MTBE"
BE and C4 alcohols) and U.S. Pat. Nos. 4,207,077 and 4,207,976.

Much work has been done on the use of ethers, especially methyl t-butyl ether and t-amyl methyl ether in gasoline bases. See, for example, December 1977, "Hydrocarbon Treatment Magazine", Pecci and Floris, "Ether Ups Antiknock of Gasoline". The revised (42 USC7445) Clean Air Act (“CAA”) applies to the use and introduction of all additives in unleaded gasoline in the United States. 21st
The CAA in paragraph 1 (f) (4) allows EPA enforcers to refrain from applying the ban on new fuel additives in unleaded gasoline (“Weber”). Specifically, the CAA bans manganese (“Mn”) additives in unleaded fuel without Weber. However, before granting Weber, the applicant's application for Weber corresponds to the burden of demonstrating that the new fuel or fuel additive does not cause a failure of the emission control device or a failure to comply with specified emission standards. The enforcer must decide whether there is. Pursuant to this CAA paragraph, the enforcer has rejected and granted the deep Weber claim.

However, as noted in the case of organomanganese (ie MMT), EPA has rejected all four different Weber applications since 1978. This rejection is due to 1/8, 1/16, 1/32, 1 / 64g manganese per gallon (3.785 liters) manganese long-term hydrocarbon exhaust gas degradation or exhaust system failure (eg, It is based on the fact that it cannot be proved that it does not cause the catalyst plugging). 19
Published September 18, 1978, Federal Regist
er) Vol. 43, No. 181, "RE application to MMT Weber in Environmental Protection Bureau" and published on Tuesday, December 1, 1981, Federal Record Vol. 46, No. 230, "Ethyl Corporation (Ethyl Corporation
Corp.); Rejection of Fuel Weber Application; Summary of Judgment ”.

Manganese, or methylcyclopentadienyl manganese tricarbonyl (MMT), in unleaded gasoline was banned by federal law in the United States, despite the constant attempt to obtain Section 211 (f) Weber against MMT. Given the incompetence of the unobtainable industry and the great needs of the industry, there is an urgent need to find a way to use organomanganese compounds in unleaded gasoline in an environment-friendly manner, especially at significant concentrations.

SUMMARY OF THE INVENTION As presented herein, Applicants' discovery is based on the reason that organomanganese compounds exacerbate hydrocarbon emissions over time. Applicants have discovered that the production of manganese dioxide (eg, Mn ₃ O ₄ and Mn ₂ O ₃ ) during combustion is associated with increased engine deposits, catalyst plugging, and worse hydrocarbon emissions. . These are the characteristics that cause environmental manganese tricarbonyl compounds not to meet the emission standards of CAA regulations. The Applicant has found that controlling manganese dioxide during combustion provides a long-standing undiscovered solution to the problems of organomanganese compounds.

The Applicant's invention is distinguished from the prior art in that the Applicant has found the problem as well as the means for solving the problem.

Degradation of harmful hydrocarbon (HC) emissions over time and other pollution problems associated with cyclic manganese tricarbonyl are primarily manganese dioxides, namely Mn ₃ O ₄ and M.
The Applicant has found that, secondarily, due to the formation of n ₂ O ₃ , the manganese dioxide is directly responsible for growing into particles of a size and mass of concern. . This particle growth and the progress of deposits in the engine occur instantaneously, simultaneously with the complex hydrocarbon combustion reactions that occur during and shortly after combustion. That is, these Mn oxides combine with each other and with other organic and inorganic materials found in gasoline and air during rapid combustion and exhaust processes.

Generally, those skilled in the art will appreciate that manganese dioxide (ie, Mn ₃ O ₄ and Mn
n As ₂ O ₃₎ for granted, and that is accepted as a primary and / or sole manganese (Mn) oxide product is produced during combustion.

The Applicant has found that it is the production of these manganese dioxides during the (suboptimal level) combustion process that ultimately causes spark plug and catalyst fouling, combustion chamber deposits and the like. This then evolves into a harmful hydrocarbon emissions issue, preventing organomanganese compounds from being qualified as EPA Section 211 (f) Webers and meeting proper environmental standards.

By promoting combustion to an optimum state and suppressing and / or eliminating the production of manganese dioxide during combustion, it is possible to suppress or even reduce harmful combustion exhaust substances (mainly hydrocarbon exhaust substances), catalyst plugging, etc. The applicant unexpectedly found out. Such restraints ensure that Applicants' fuel meets the required environmental standards and is eligible for EPA Section 211 Weber.

The present applicant has unexpectedly found that the suppression of these manganese oxides during combustion is mainly due to the effects of 1) increase in combustion speed (ignition speed) and 2) decrease in combustion temperature.

By increasing the combustion rate (ignition rate, fuel economy, etc.), i.e. by shortening the combustion interval, manganese dioxide, which gives rise to harmful exhaust emissions, is not readily produced. By increasing the burning rate, the combustion is efficient and clean when using organomanganese compounds. The Applicant has found that harmful HC and NO
x Unexpectedly found to reduce both emissions.

The Applicant has also found that it is possible to further suppress harmful combustion exhaust substances by lowering the combustion temperature. The lowering of the combustion temperature contributes to suppressing the production of manganese dioxide, which is a problem during combustion. The Applicant has unexpectedly found that reducing combustion temperature reduces both HC and NOx emissions.

In the practice of the present invention, compounds that lower the combustion temperature /
Ingredients and / or means are particularly preferred. The larger the temperature drop, the better.

Further, a fuel composition that lowers the temperature of the steam component as a result of vaporization to the combustion chamber before ignition is preferable.

Of course, compounds / components and / or means that increase the burning rate and decrease the burning temperature are particularly preferred.

By increasing the burning rate (eg, ignition rate, laminar or turbulent burning rate, fuel economy, burning efficiency, etc.) and simultaneously lowering the burning temperature, the production of manganese dioxide is sufficiently reduced and harmful exhaust gas is emitted. Can suppress substances.

The acceleration of burning rate and / or the phenomenon of lowering of burning temperature may be useful for manganese-free fuels. That is, a fuel that does not contain Mn, but contains harmful exhaust substances depending on the chemical properties, working conditions, etc., can be made cleaner by the invention of the applicant.

The use of specified concentrations of methylene dimethyl ether, carbonic acid dimethyl ester, and methyl t-butyl ether with specified concentrations of Mn in unleaded gasoline increases the burning rate of fuel burned in an engine specially designed for unleaded gasoline. , And the temperature drops, and harmful hydrocarbons and
It was unexpectedly discovered that NOx emissions were significantly reduced.

Therefore, the essential element of the scope of the claims of the present invention lies in the engine itself that exhibits excellent effects. This is unexpected. The reason for this is that the use of Mn in the fuel that burns in such conventional engines has increased harmful hydrocarbons and NOx emissions.

Accordingly, the practice of the present invention involves the use of engines and exhaust systems specifically designed to use unleaded fuel.

Upon discovery of the problem, it is expected that other studies will identify other compounds that enhance the burning rate.

Some of the mechanisms for increasing the burning rate are well known to those skilled in the art. Therefore, in the practice of the present invention, compounds / components and / or means that increase the burning rate are desirable. For example, it is desirable to increase the partial vapor pressure of the vaporized component before combustion, resulting in an increase in combustion rate. Compounds / components and / or means that act to increase the Reid Vapor Pressure (RVP) of the finished gasoline and then increase the burning rate are also desirable.

In carrying out the present invention, O ₂ which increases the fuel-air equivalent ratio
A compound / component and / or means, such as a sensor exhaust system,
It is desirable to increase the burning rate, whether it is chemical or mechanical.

In practicing the present invention, a combustion catalyst that acts to improve combustion, combustion efficiency and fuel economy, especially a combustion catalyst that further lowers the combustion temperature and / or increases the combustion rate is desirable.

Certain molecular properties have been determined by the Applicant that reduce the manganese dioxide produced during combustion. This includes H, H ₂ , CO and / or OCH ₃ (methoxy groups) and / or OH
(Hydroxyl group) H, H ₂ , at relatively high concentration,
Compounds / components in which CO, OCH ₃ and / or OH groups are present and / or are intermediate combustion products are preferred. The higher the relative weight percentage of these structural components in the component / compound and / or that occurs during combustion, the better. These characteristics can be single or collective. Again, it is an object of the present invention to reduce harmful exhaust emissions by increasing the burning rate and / or lowering the combustion temperature.

Compounds previously identified by the applicant to be effective in achieving this end include carbon monoxide, methylene dimethyl ether (also known as methylal, dimethoxymethane), carbonic acid dimethyl ester (also as dimethyl carbonate). (Known) methyl t-butyl ether (MTBE) and C1 to C6 (C1 to C6) low molecular weight alcohols, especially methanol and ethanol. Applicants believe that many other compounds exist.

Applicants note that the desired OCH ₃ (methoxy group) structure is common with methanol, methylene dimethyl ether (methylal) and carbonic acid dimethyl ester (dimethyl carbonate). The Applicant believes that these methanol, methylene methyl ether (methylal) and carbonic acid dimethyl ester (dimethyl carbonate) compounds are optimal for achieving the Applicant's objectives.

Therefore, oxygenates that use methanol and ethanol during manufacture are considered effective and are considered within the scope of the present invention. It is believed that the intermediate combustion and other characteristics of such compounds clearly fulfills Applicants' objectives.

Example of test fuel   This application has tested several fuels, as shown below.

A. Methanol fuel composition 0.033025g per liter of MMT
Manganese, 5% by volume methanol and 5% by volume ethanol and unleaded gasoline base.

B. ISO / HEX fuel 0.033025 g manganese per liter MMT, 10% by volume isopropanol and 10% by volume hexanol and unleaded gasoline base.

C. MTBE Fuel 0.033025 g manganese per liter MMT, 14.6 vol% MTBE and unleaded gasoline base.

D. DMC fuel 0.033025 g manganese per liter MMT,
4.6% by volume dimethyl carbonate (DMC) and unleaded gasoline base.

E. Methylal fuel 0.033025 g manganese per liter MMT, 7.2 vol% methylal and unleaded gasoline base.

F.THF fuel 0.033025g manganese per liter of MMT, 1.
6 Tetrahydrofuran volume% and unleaded gasoline base.

G. High Manganese (Mn) Fuel 0.5284 g manganese per liter MMT, 5 vol% methanol and unleaded gasoline base.

H. Manganese Fuel Based on 0.033025g manganese and unleaded gasoline per liter of MMT.

I. Base fuel Unleaded gasoline base (clean fuel).

Test Method The fuel in the above example has a throttle body fuel injector and an oxygen sensing system-a closed loop fuel controller, 350 C
Tested on a 1988 Chevrolet C1500 pickup truck equipped with an ID V-8 engine. By having this oxygen sensing system, means were provided to adjust the stoichiometry to compensate for variations in oxygen content in the various test fuels. Due to this feature, HC and
The bias of NOx is eliminated. That is, most of the test fuel, which has a high oxygen content and the property of diluting combustion, and oxygen,
Alternatively, it is hard to tell the superiority or inferiority of the exhaust characteristics with the fuel that does not contain at all.

Furthermore, this is an essential feature of unleaded fuel engines and exhaust systems, especially with regard to the regulated exhaust emission control system of the present invention.

The engine head and valves were cleaned prior to testing each fuel. A new oxygen sensing system and spark plug were also installed.

Each fuel mainly underwent two tests. In the first test ("Test 1"), at steady state at 1000 rpm for 40 hours,
HC and NOx emissions from the engine were measured without a duty cycle. The purpose of this unloaded, steady state test was to expose hydrocarbon (HC) emissions as they deteriorate over time. These test conditions promoted the degradation of HC exhaust emissions more than would be expected when performing a much longer durability test.

Prior to the introduction of each new test fuel, a clean engine was run-in with the base fuel ("clean fuel") until the emissions were stable. Generally, this required about 3-6 hours of steady state operation. Hydrocarbon and NOx emissions were measured periodically using a Beckman Exhaust Analyzer. See Table 1 for a summary of the data.

The second test (“Test 2”) was performed immediately after the first test, using the same fuel with the same engine, which is still warm. The second test was performed with the vehicle mounted on a stationary chassis dynamometer. The test is carried out under various load conditions, for example 15-24
50 mph (80.5 km / h "kp" under the displayed horsepower ("ihp")
h ”). In this test, combustion temperature, HC and N
Differences in Ox emissions and fuel economy were measured. See Figures 1-6 for a summary of the results.

The test results of Test 1 and Test 2 are shown as follows.

A. Methanol fuel 0.033025 grams of manganese, 5% by volume of methanol in MMT per liter of composition,
5% by volume ethanol and unleaded gasoline base.

B. ISO / HEX Fuel MMT 0.033025 grams manganese per liter, 10 volume% isopropanol, 10 volume% hexanol and unleaded gasoline base.

-Test 2-Not Performed C. MTBE Fuel 0.033025 grams of manganese per liter of MMT, 14.6% by volume MTBE, and unleaded gasoline base.

D. DMC fuel 0.033025 g manganese, 4.6 vol% dimethyl carbonate (DMC) per liter of MMT,
And unleaded gasoline base.

E. Methylal Fuel MMT 0.033025 grams manganese per liter, 7.2% by volume methylal and unleaded gasoline base.

F. THF fuel 0.033025 grams of manganese per liter of MMT, 1.6% by volume of tetrahydrofuran and unleaded gasoline base.

-Test 2 (not carried out) G. High MN fuel 0.5284 g manganese per liter MMT, 5 vol% methanol and unleaded gasoline base.

-Test 2- (Not Performed) H. Manganese Fuel 0.033025 grams of manganese per liter of MMT, and unleaded gasoline base.

I. Base fuel Unleaded gasoline base (clean fuel) Analysis of Table 1 Table 1 shows the results of HC emissions for Test 1. Table 1
Show that manganese, THF and high Mn fuels significantly increase HC emissions over time. Table 1 shows that this increase is due to ISO / HEX, methanol, MTBE, methylal and DMC.
It is shown to be much greater than for fuel.

Applicants note that changes in HC emissions during the last 20 hours of the test (Column B) demonstrate long-term degradation of HC emissions. During this time even the base fuel (without Mn) underwent a significant degradation of HC emissions. Base fuel shows 38% increase, HC emissions increase 41% each
It shows that the increase amount is slightly smaller than that of the manganese fuel and the THF fuel (column B).

In contrast, ISO / HEX, methanol, MTBE, methylal and DMC fuels did not show similar significant increases in HC emissions. The increase in HC emissions for these fuels was significantly higher than for manganese fuels, ranging from a 15% increase in methanol to a 25% decrease in DMC. The reduction in HC emissions was significant in 9% of methylal fuel and 25% of DMC fuel (column B). Incredibly, ISO / HEX, methanol, MTBE, methylal and DMC fuels (all containing Mn) showed much lower HC emission increases than the base fuel (without Mn).

Manganese, high Mn and THF fuels are all base fuels (306
7 (ppm), which is much higher than that of the latter (column D) HC emissions (3390, 6554, 4130 ppmc, respectively).

In contrast, ISO / HEX, methanol, MTBE, methylal and DMC fuels have high HC emission levels (3
390 ppmc) (Column D). HC emissions levels for these fuels range from 2953 ppmc for methanol to 2 for ISO / HEX.
It was low in the range up to 024 ppmc (Column D).
Surprisingly, the hydrocarbon emissions of ISO / HEX, methanol, MTBE, methylal and DMC (column D) were also all below the base (clean) fuel (3076 ppmc).
This result was the most unexpected.

In short, the manganese, THF, and high manganese test fuels show very high increases in HC emissions over time. In contrast, ISO / HEX, methanol, MTBE, methylal and DMC fuels. These are better than manganese fuels as well as base fuels (without Mn) to control HC emissions.

Explanatory drawing of FIGS. 1 to 6 of the second test 1 Difference in combustion temperature. In this figure, as a function of engine load,
Manganese, base, methanol, MTBE, methylal and
The engine exhaust gas temperature (“EGT”) of DMC fuel is compared. The second test was loaded with the engine at 50 mph to derive the difference in fuel combustion temperature as measured by engine exhaust gas temperature (“EGT”). At 15ihp, the EGTs of all tested fuels (except MTBE) are relatively close to each other. Base and manganese fuels are identical at 707 ° F (375 ° C), but DMC, methanol and methylal fuels are 717 ° F (381 ° C), 722 ° F (383 ° C) to 724 ° F, respectively.
It is distributed close to (384 ℃). MTBE fuel temperature was tested at 16 ihp and measured as 749 ° F (398 ° C).

As load increases, manganese and base fuel EG
T rose rapidly. The increase in manganese fuel was the largest. For example, at 20ihp, the base fuel temperature is 828 °
F (442 ℃), and manganese temperature is 860 ℃ at the same ihp.
It was F (460 ° C).

In contrast, methanol, MTBE, methylal and
The EGT rise rate of DMC fuel was low. For example, at 24ihp,
785 ° F for methanol, methylal and DMC fuels
(418 ° C), 795 ° F (424 ° C) and 798 ° F (426 ° C) were grouped in close proximity. Similarly, MTBE is 778 at 22ihp.
It showed a lower rise rate of ° F (414 ° C).

The most important point in Figure 1 is that it demonstrates that methanol, MTBE, methylal and DMC fuels enjoy significantly lower combustion temperatures than base or manganese fuels at the same load. For example, in Figure 1, E of manganese fuel at 20 ihp
It shows that GT is 104 ° F (40 ° C) higher than methanol fuel. In addition, FIG. 1 shows fuels containing both Mn and oxygenates (ie, methanol, MTBE, methylal and
It also shows that the DMC fuel) has a much lower combustion temperature than the base fuel. For example, methanol fuel is 72 ° F (22 ° C) lower than the base fuel.

Figure 1 shows EGT between two types of fuel as the load increases.
It shows that the difference is large.

Figure 2 Combustion temperature and hydrocarbon emissions This figure shows the hydrocarbon emissions for the second test as a function of engine gas temperature ("EGT"). This figure shows that there is a direct relationship between HC emissions and engine gas temperature. This relationship is most pronounced for methanol, MTBE, methylal and DMC fuels. Figure 2 shows HC for various oxygen additives
/ EGT change rate is higher than HC / EGT change rate for oxygen-free fuel. FIG. 2 shows that the lower the combustion temperature of any oxygen additive, the lower the HC emissions.

Figure 3 Combustion temperature and NOx emissions This figure is a function of EGT
The result of NOx emission is shown. Fig. 3 shows NOx as in Fig. 2.
Emissions and E of methanol, MTBE, methylal and DMC fuels
It shows a direct and significant relationship with GT. This figure clearly shows that at low EGT, NOx emissions are much lower, especially for methanol, MTBE, methylal and DMC fuels compared to base and manganese fuels.

Fig. 4 Display burn rate This figure measures burn rate indirectly as a function of load via fuel economy measurements. It is well known to the person skilled in the art that an improvement in fuel economy indicates an increase in the ignition rate or burning rate without an increase in BTU (calorific value). Figure 4 shows miles per gallon ("mpg") as a function of load (ihp) (ie 0.42566 kilometers per liter ("kp"
l ”)). FIG. 4 illustrates the substantial difference in fuel economy (“FE”) between base fuel and oxygenated fuel that begins at about the same time as loading. 20
At ihp, the fuel economy of base fuel is 13.2 mpg (5.619 kp
l), in contrast, methylal, methanol, DMC and MTBE each have 15.7 mpg (6.683 kp
l), 15.9mpg (6.768kpl), 16.5mpg (7.0234kpl), 1
Note that it is 7.2mpg (7.321kpl).
The difference between these raw materials shows that the fuel economy is improved by 19 to 30% with respect to the base fuel. These FE
The improvement of the value indicates that the burning rates of methylal, methanol, DMC and MTBE fuels were sufficiently increased.

Figure 5 Burn rate and HC emissions This figure shows HC emissions as a function of fuel economy, ie the indicated burn rate. Figure 4
Shows a close correlation between increased burning rate and improved HC emissions. Figure 5 demonstrates that an increase in the burning rate of methylal, methanol, DMC and MTBE results in improved HC emissions. This correlation is most pronounced with methanol fuel.

Figure 6 Burning rate and NOx emissions This figure shows NOx emissions as a function of fuel economy. The figure shows a close correlation between the increase in the indicated burn rate and the improvement in NOx emissions. This correlation is seen in the case of oxygenated fuel, but it is not remarkable in the case of base fuel.

Preferred Embodiments In order to serve the purpose of promoting the burning rate and / or to lower the combustion temperature, although not a requirement, in the range in which the oxygenating compound is used, the oxygen content as a total weight% of the compositional additive compound. The amount is preferably 15% or more of the total weight of the oxygen additive. A low oxygen concentration is acceptable, but a relatively high oxygen content as a percentage by weight of total oxygenated compound / component is preferred. It is certain that the simpler the molecular structure of a compound / component, the better.
More complex molecular structures are acceptable, especially if the intermediate combustion products increase the burning rate and / or lower the burning temperature.

It is preferred that the finished fuel containing the components / compounds have improved thermal efficiency (eg, fuel economy) over the base fuel alone.

Applicants understand that, upon discovery of the source of the problem, many means can be used to achieve the expected effect.

In addition, the discovery of the source of the problem has led to the addition of oxygenates and non-oxygenates, many other ingredients, compounds, combinations thereof and / or mechanical / chemical means to the formation of manganese dioxide during combustion. Applicant also understands that routine research recognizes to suppress and / or eliminate.

By practicing this invention, the fuel utilizing Applicants' discovery of the source of the problem meets the minimum environmental standards and has previously denied the combination of organic manganese and unleaded gasoline EPA.
(US Environmental Protection Agency) Considered to be eligible for Section 211 Weber.

By carrying out the present invention, it is considered that a lead-free fuel containing no problematic Mn (containing no organic manganese compound) can be more effective by the discovery of the problem by the applicant. It is believed that organomanganese compounds may be needed to control harmful emissions from these fuels.

It is believed that research can identify certain ethers, phenols, esters, oxides, ketones, alcohols and / or other chemical agents that solve Applicants' discovery of the source of the problem.

The production of ethers is also well known to those skilled in the art. For example, U.S. Pat.Nos. 4,262,145, 4,175,210, 4,25
2,541, 4,270,929, 3,482,952, 2,384,866
No. 1,488,605, 4,256,465, 4,267,393,
No. 4,330,679, No. 4,299,999, No. 4,302,298, No. 4,3
No. 10,710, No. 4,324,924, No. 4,329,516, No. 4,336,40
No. 7, No. 4,320,233, No. 2,874,033, No. 3,912,463,
See Nos. 4,297,172 and 4,334,890.

C2-C6 ethers that may be used in the practice of the present invention include branched and straight chain ethers, diethers having two oxygen atoms and two ether linkages and three oxygen atoms and multiple ether linkages. There are triethers that have. Non-limiting examples of C2-C6 ethers that can be used are dimethyl ether, methyl ethyl ether,
Diethyl ether, ethyl propyl ether, methyl normal propyl ether, ethyl isopropyl ether, methyl isopropyl ether, ethyl normal propyl ether, propyl propyl ether, propyl isopropyl ether, isopropyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl t-butyl ether, ethyl There are s-butyl ether, methyl normal butyl ether, methyl isobutyl ether, methyl t-butyl ether, methyl s-butyl ether, methyl normal amyl ether, methyl s-amyl ether, methyl t-amyl ether and methyl isoamyl ether. A non-limiting list of further examples of acceptable diethers (having two oxygen atoms and two ether linkages) are methylene dimethyl ether, methylene diethyl ether, methylene dipropyl ether, methylene dibutyl ether and methylene diisopropyl ether.

Substantial amounts of H, H _2, CO, ethers free radical OCH ₃ and / or OH is intermediate combustion products is thought to be optimal.

Preferably the ether used is anhydrous. Within the preferred concentration range, most C2-C6 ethers are miscible with petroleum hydrocarbons. Such ethers are preferably used in an amount within the soluble range. But,
If desired, an excess of ether can be incorporated into the fuel by using means such as mutual solvents.

Acceptable ketones include ketones having 3 to about 12 carbon atoms. However, low alkenyl ketones appear somewhat preferred. Representative low alkenyl ketones include diethyl ketone, methyl ethyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, ethyl butyl ketone, butyl isobutyl ketone, ethyl propyl ketone, and the like. Other ketones include acetone, diacetone alcohol, diisobutyl ketone, isophorone, methyl amyl ketone, methyl isamyl ketone, methyl propyl ketone, and the like. A representative cyclic ketone is ethyl phenyl ketone. H, H _2, CO, ketone free radical OCH ₃ and / or OH is intermediate combustion products is thought to be optimal.

Acceptable esters include anisole (methyl ester of benzene), isopropyl acetate and ethyl acrylate.

The preferred chemical means for achieving these results are:
The addition of compounds or combinations of compounds and / or components that individually or jointly act to increase the ignition rate / burn rate and / or reduce the combustion temperature.

Examples of desired fuel compositions containing oxygenates have an oxygen weight percent of the composition of about 0.1 to 2 with or without cosolvent.
About 0.000 per liter of 0.0 oxygen additive and unleaded fuel
It has 264 to 0.264200 g of manganese. In more desirable compositions, the weight percent oxygen of the composition, with or without cosolvent
Has an oxygen content of about 0.5-10.0 and an organomanganese concentration of about 0.004128-0.099075 g per liter of fuel composition. Although not a requirement, anhydrous fuel is preferred.

In another desirable composition, the oxygen weight percent of the composition with or without cosolvent is about 1.0 to 5.0 and the organomanganese concentration is about 0.004128 to 0.066050 g per liter of fuel composition.

Controlling hydrocarbon emissions Unacceptable off-engine hydrocarbons (engine out hydrocarb
on, EOHC) Cyclomatic Manganese Tricarbonyls (CM), which have been thought to be too much for reasons related to exhaust gas and catalyst plugging.
The T) concentration, when configured to solve Applicants' discovery of the source of the problem, is capable of preventing unacceptable long-term degradation of hydrocarbon exhaust emissions and catalyst plugging. Applicant found. In other words, for example, manganese concentrations of 1/64, 1/32, and even 1/16 g or more per 3.785 liters are sufficient. Looking at the prior art literature on this subject, this result is totally unpredictable. Labels with 1 / 8th, or even 3 / 8g manganese per 3.785 liters appear to be ideal.

Since the manganese oxide of cyclic manganese tricarbonyl plays a leading role in the deposition of hydrocarbons, it is desirable to balance the amount of cyclic manganese tricarbonyl used and the effectiveness of the manganese dioxide reducing means. This is necessary to maximize the effect of the invention. In carrying out the applicant's invention, from about 0.000264 per liter
A manganese concentration of 0.2642 g can be used. However, a manganese concentration level of 0.00825 g per liter, more preferably 0.016505 g or more and 0.1321 g or less, is more preferable.

From the point of emission effect, about 0.00825-0.0 per liter
A concentration of cyclic manganese tricarbonyl of 99075g is acceptable. Manganese concentrations in the range of about 0.033025 to 0.06605 g per liter are preferred.

In terms of octane effect, the desired range is about 0.000264 to 0.06605 g manganese per liter of composition. A more desirable range is about 0.004128 to 0 per liter of composition.
033025 g of manganese. A preferred range is 1 of the composition
It is about 0.004128 to 0.016512 g of manganese per liter.

The preferred cyclic manganese tricarbonyl used in the composition is cyclopentadienyl manganese tricarbonyl. More preferred cyclic manganese tricarbonyl is methylcyclopentadienyl manganese tricarbonyl (MM
T). As discussed in the present invention, the composition may also include homologues or other cyclic manganese tricarbonyl substitutes. Non-limiting listings of these other acceptable alternatives include alkenyl, aralkyl,
There are aralkenyl, cycloalkyl, cycloalkenyl, aryl and alkenyl groups.
Other non-limiting examples of acceptable cyclic manganese tricarbonyl antiknock compound include, but are not limited to, benzylcyclopentadienyl manganese tricarbonyl, 1,2-dipropyl 3-cyclohexylcyclopentadienyl manganese tricarbonyl, 1,2-diphenyl. Cyclopentadienyl manganese tricarbonyl, 3-propenyldienyl manganese tricarbonyl, 2-tolylindenyl manganese tricarbonyl, fluorenyl manganese tricarbonyl, 2,3,4,7-propyl fluorenyl manganese tricarbonyl, 3, -Naphthylfluorenyl manganese tricarbonyl, 4,5,6,7-tetrahydroindenyl manganese tricarbonyl, 3-3 ethenyl-4,7-dihydroindenyl manganese tricarbonyl, 2-ethyl 3
(A-Phenylethenyl) 4,5,6,7-tetrahydroindenyl manganese tricarbonyl, 3- (a-cyclohexylethenyl) -4,7-dihydroindenyl manganese tricarbonyl, 1,2,3,4 , 5,6,7,8-octahydrofluorenyl manganese tricarbonyl and the like. Mixtures of such compounds can also be used. Generally, the above compounds can be prepared by methods well known to those skilled in the art. Representative preparation methods are described, for example, in US Pat. Nos. 2,819,416 and 2,818,417.

To further reduce hydrocarbon emissions, Applicants are considering the use of other additives as well as the components used by Applicants. It is a gum and corrosion inhibitor, detergent, multipurpose additive, lead scavenger that is necessary or desirable to maintain cleanliness of fuel systems and control exhaust emissions.

Applicant's invention considers a method of suppressing harmful combustion exhaust emissions generated in an internal combustion engine. The process comprises an unleaded gasoline base consisting of hydrocarbons and a cyclopentadienyl manganese tricarbonyl anti-knock agent compound having a manganese concentration of about 0.000264 to 0.2642 g per liter of fuel composition, during exhaust combustion of the fuel. Mixing with chemical and / or mechanical means to counteract the formation of manganese heavy oxides and / or harmful oxides. Next, Applicants' method considers combustion of a fuel composition in an internal combustion engine. The resulting engine exhaust material is exhausted through an exhaust system that includes a catalytic exhaust system so that the exhaust and / or exhaust emission control system meets the requirements of Section 211 (f) Weber.

Applicants' invention further contemplates a method of suppressing harmful combustion exhaust emissions from internal combustion engines. An unleaded gasoline base consisting of a hydrocarbon and a cyclopentadienyl manganese tricarbonyl anti-knock agent compound having a manganese concentration of about 0.000264 to 0.2642 g per liter of fuel composition are used to accelerate the burning rate of the fuel and / or Combine with chemical and / or mechanical means to reduce the combustion temperature. The fuel composition is then combusted in a spark ignited internal combustion engine, and the resulting exhaust material is exhausted through an exhaust system that includes a catalytic exhaust system, the exhaust material of Section 211 (f) Weber. I am trying to meet the requirements.

Use of Cosolvents It has been considered that cosolvents can be used for several reasons, including technical dilution, vapor pressure suppression and phase stability correction. Cosolvents are C2-C12 fatty alcohols, C
3-C12 ketone, C2-C12 ether, ester, oxide,
It can be selected from the group consisting of phenol and the like. Use one or more co-solvents of a particular co-solvent, and / or
Alternatively, it is within the scope of the invention to use any one or more co-solvents simultaneously.

It is also within the scope of this invention to mix different co-solvents such as mixed alcohols, ethers, esters, oxides, phenols and / or ketones. For example, mixed cosolvent alcohols, especially mixed cosolvent alcohols in the range of C2 to C8, have been found to have the effect of particularly improving both the RVP value and the octane mix number.

Acceptable concentrations of cosolvent will vary depending on the concentrations of the other ingredients and the composition thereof, but are typically in the range of about 0.1 to 20.0% by volume of the composition. Generally, a more desirable concentration will be about
It is in the range of 0.1 to 15.0% by volume. The preferred concentration is about 0.1-
It is in the range of 10% by volume and the most preferred concentration is about 0.1-5.0.
It is in the range of volume%.

It is also within the scope of the invention to use co-solvent mixtures of unique and / or different molecular weight. For example, RV
P, evaporative gases, volatility and use of high molecular weight alcohol mixtures (particularly C4 to C12 in various combinations and concentrations) as a means to control the loss of distillation capacity in the early and middle stages,
It is also within the scope of this invention to lower the final boiling point and to further include hydrocarbons boiling above the gasoline temperature in the composition.

Technical dilution is associated with early and mid-stage descending distillation curves. It is contemplated that cosolvents may be used alone or in combination with hydrocarbons boiling above the mid-boiling point to improve the reduction in distillation temperature to mitigate technical dilution. By using one of the higher boiling hydrocarbons, this temperature drop can be corrected independently of the cosolvent. This hydrocarbon, when added to the composition, compensates for the reduction in distillation temperature.

It has also been found within the scope of the invention to use high molecular weight cosolvents in combination with the other necessary elements of the invention to reduce harmful emissions. For example, azeotropic co-solvents in combination with heavy hydrocarbons that produce toxic emissions are one such means, resulting in heavy hydrocarbons with accelerated combustion and / or reduced combustion temperatures. And co-solvent oxygen burns together.

Unleaded Base Gasoline Composition The gasoline to which the present invention is applied is unleaded gasoline.
The gasoline base in Applicants' fuel composition is a conventional engine fuel that normally boils in the range of about 70-440 ° F. However, the boiling range outside the range of gasoline is considered,
It is available. Almost all grades of unleaded gasoline used in spark ignition internal combustion engines are considered. The use of other non-internal combustion engine fuels is also being considered.

Generally, the fuel base contains both straight run components and cracked feedstock components, with or without alkylated hydrocarbons, reformed hydrocarbons and the like. This fuel is, for example, pure stock oil (stra
ight stocks), saturated hydrocarbons such as alkylated products (with or without detergent), antioxidants, dispersants,
Metal deactivator, lead scavenger, rust inhibitor, multifunctional additive,
Emulsifier, demulsifier, fluidized oil, deicer, combustion catalyst,
It can be prepared from corrosion and gum inhibitors, surfactants, catalysts and / or other similar or well known additives. It is contemplated that, under certain conditions, these additives may be included at concentrations above the normal levels required to control the components of Applicants' invention.

Base gasoline is usually a mixture of feedstocks obtained from several refining processes. The final mixture is produced by hydrocarbons produced by other treatments, such as alkylate produced by the C4 olefins reaction, butane with acid catalysts such as sulfuric acid or hydrofluoric acid, and reformers. Aromatic compounds may also be included.

Olefins are usually produced by taking measures such as pyrolysis and catalytic cracking. Dehydrogenation of paraffins to olefins can replenish the gaseous olefins produced in the refinery to produce feedstock for either polymerization or alkylation steps. The saturated gasoline component consists of paraffin and naphthenate.
These saturated compounds are (1) pure gasoline by distillation (straight-run gasoline), (2) alkylation process (alkylate), and (3) isomerization treatment (conversion of standard paraffins to branched octaffins of fine octane). Is obtained by Saturated gasoline components also occur in so-called natural gas.
In addition to the above, the pyrolysis feedstock, catalytic cracking feedstock and catalyst reformate contain saturated components. The preferred gasoline base is
It has an octane number (R + M) / 2 in the range 70-95. A preferred gasoline base contains olefins in the range of 1-30% by volume and saturated hydrocarbons in the range of about 40-80% by volume.

Typically, engine gasoline bases used in formulating the fuel mixtures of the present invention are within the parameters of ASTM D-439 and are standard ASTM distillation procedures (ASTM D-86).
Has an initial boiling point in the range of about 70-115 ° F and a final boiling point in the range of about 380-437 ° F. The intermediate gasoline fraction boils and evaporates at temperatures within this range.

In terms of phase stability and water resistance, the preferred base gasoline composition is C8, especially when low molecular weight alcohols are used.
Or, it contains as many aromatic compounds as possible in the environment having a carbon number of less than this. The preferred order of this aromatic compound is benzene, toluene, m-xylene, methylbenzene, o-xylene, isopropylbenzene, N-propylbenzene and the like. The second most preferred gasoline component after the aromatic compound is an olefin from the viewpoint of phase stability. The preferred order of this olefin is 2-methyl-2-
Butene, 2-methyl-1-butene, 1-pentene and the like. However, attention must be paid to the olefin content from the viewpoint of minimizing the high reactivity of the olefin and the smog factor. The last preferred gasoline component, after olefins, is paraffin in terms of phase stability, for example when using alcohols. The preferred rank of this paraffin is cyclopentane, N-pentane, 2,3-dimethylbutane, isohexane, 3-methylpentane and the like.

Generally, from the viewpoint of phase stability, aromatic compounds are preferable to olefins, and olefins are preferable to paraffins.
Within each particular class, low molecular weight components are preferred over high molecular weight components.

It is also desirable to use base gasoline with a low sulfur content, as sulfur oxides contribute to irritating and asphyxiating smog and other environmental pollution. To be economically viable, the base gasoline contains at most 0.1% by weight of sulfur in the form of conventional sulfur-containing impurities.
Fuels having a sulfur content of only 0.02% by weight are particularly preferred for use in the present invention.

The gasoline base of the present invention may also contain other high octane organic components, including phenols (eg p
-Cresol, 2,4-xylenol, 3-methoxyphenol), ester (e.g. isopropyl acetate, ethyl acrylate), oxide (e.g. 2-methylfuran), ketone (e.g. acetone, cyclopentanone), alcohol (Furon, full frill),
There are ethers (eg MTBE, TAME, dimethyl, diisopropyl), aldehydes and the like. May 14, 1971 San Francisco, California, American Petroleum Institute (American P
etroleum Institute), 36th Refining Mid-Year Meeting, 36th Refining Mid-Year Meeting, Anselman, G. H. (Unzelman, GH), Forster, E. J. (Forster, EJ) and Barnes,
A. M. (Burns, AM) "Are there alternatives to lead anti-knock agents?" (Are There Substitutions for
lead Anti-Knocks?).

The gasoline may further contain other antiknock agents such as cyclopentadienyl nickel nitrosyl, N-methylaniline. Antiknock accelerators such as 2,4-pentanedione can also be included. Gasoline may also contain a protective agent for the make-up valve and the valve seal recess. A non-limiting list of examples of these additives includes boron oxide, bismuth oxide, ceramic bond CaF2, iron phosphate, tricresyl phosphate, phosphorus and sodium based additives. The fuel is an antioxidant such as 2,6-di-t-butylphenol or 2,6-di-t-butyl-p-cresol, N-N-di-s.
A phenylenediamine such as -butyl-p-phenylenediamine and N-isopropylphenylenediamine can also be contained.

The gasoline base can contain hydrocarbons that boil beyond the range of normal gasoline. It is contemplated that in some cases these high boiling hydrocarbons can be incorporated into the finished normal boiling gasoline by exploiting the azeotropic effect of certain co-solvents / additives. Applicants have found that high molecular weight C4-C12 alcohols are particularly useful for lowering the final boiling point.

Those skilled in the art will appreciate that many variations and modifications of the invention disclosed herein are possible without departing from the spirit and scope of the invention.

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Claims (10)

(57) [Claims] 1. A fuel composition for a spark ignition internal combustion engine, the composition comprising: an unleaded gasoline base containing a hydrocarbon; and approximately 0.000264 grams to approximately 0.2642 grams of manganese per liter of the fuel composition. A cyclopentadienyl manganese tricarbonyl antiknock composition having a concentration, and an oxygen additive for performing at least one of increasing the burning rate and decreasing the burning temperature, the oxygen additive being dimethyl carbonate A fuel composition that is an ester. 2. The composition of claim 1, further comprising a cosolvent. 3. The fuel composition according to claim 1, wherein the final boiling point of the composition is lowered by a cosolvent. 4. The fuel composition according to claim 1, wherein the manganese concentration is greater than 0.008256 grams / liter. 5. The fuel comprises a dispersant, a detergent, an antioxidant, a metal deactivator, a rust inhibitor, a demulsifier, an emulsifier,
A fluidized oil, a combustion catalyst, an anti-icing agent, a surfactant, a gum inhibitor, a corrosion inhibitor, a multifunctional additive, an anti-knock accelerator, a lead scavenger and a combination thereof. The composition according to. 6. The composition of claim 1, wherein the fuel comprises an oxygen additive such that the fuel has a weight percent oxygen of about 0.5-10.0. 7. The composition of claim 1, wherein the composition has a final boiling point not exceeding 193 ° C (380 ° F). 8. A fuel composition comprising a hydrocarbon-based liquid fuel, a cyclopentadienyl manganese tricarbonyl antiknock composition, and carbonic acid dimethyl ester. 9. The composition of claim 8 further comprising a cosolvent. 10. The cosolvent is a C1-C12 alcohol, C2-C
The composition of claim 9 selected from the group consisting of 12 ethers, C3 to C12 ketones, esters, oxides, phenols and mixtures thereof.