EP3498807B1

EP3498807B1 - Composite additive for fuel

Info

Publication number: EP3498807B1
Application number: EP18186817.5A
Authority: EP
Inventors: Jae-Kon Kim; Shin Kim; Cheon Kyu Park; Jong Han Ha
Original assignee: Korea Petroleum Quality & Distribution Authority
Current assignee: Korea Petroleum Quality & Distribution Authority
Priority date: 2017-12-18
Filing date: 2018-08-01
Publication date: 2020-11-18
Anticipated expiration: 2038-08-01
Also published as: EP3498807A1; US20190185773A1; KR101869762B1; CN109929618A; JP6587721B2; JP2019108519A; CN109929618B

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. §119 to Korean Patent Application No. 10-2017-0173912, filed on December 18, 2017 , in the Korean Intellectual Property Office.

TECHNICAL FIELD

The following disclosure relates to a composite additive for fuel used in various kinds of fuel.

BACKGROUND

Due to a price increase, resource shortage, a risk of supply intervention, and environmental problems of fossil fuel or petroleum-based fuel, which provides the foundations for industrial development including the industrial revolution, recently, biofuel has been particularly spotlighted as an alternative of a petroleum-based product.
Generally, the biofuel means all fuels derived from biomass. The biomass is often prepared from vegetable sources such as corn, soy, flaxseed, sugarcane, and palm oil, but a raw material of the biomass may be generally expanded to all currently living organisms or metabolic byproducts thereof occupying one portion in a carbon cycle.
As a technology and research for producing bioenergy from the existing biomass, research for replacing gasoline and diesel corresponding to transportation oil has been mainly conducted. In order to replace gasoline, biobutanol prepared by fermenting sugarcane, corn, or the like, has been developed.
However, in a case of using existing biobutanol as the transportation fuel as it is, there is a limitation in that stability is deteriorated as compared to the petroleum based fuel due to a water incorporation problem, a phase separation problem caused by water incorporation, and the like. Particularly, at the time of using biobutanol as a fuel additive, there is a problem in that a phase separation phenomenon is significantly exhibited as compared to other fuel additives.
Since the fossil fuel or petroleum-based fuel also differs only in degree, but still involves the water incorporation problem, the phase separation problem, and the like, research into a composite additive for fuel capable of further improving physical/chemical stability of renewable fuel including bioalcohol and fossil fuel according to the related art such as gasoline, and the like, has been required.

[Related Art Document]

[Patent Document]

(Patent Document 1) Korean Patent Laid-Open Publication No. 10-2013-0029314 (March 22, 2013 ) US2015/0210948 deals with the phase separation of fuels comprising biobutanol by a adding xylene and toluene.

SUMMARY

The invention is defined by the appended claims.
An embodiment of the present invention is directed to providing a composite additive for fuel capable of significantly delaying a phase separation phenomenon even in poor environmental conditions such as high humidity, a low temperature, storage for a long period of time, and the like, preventing freezing in winter due to a lower freezing point, and having an excellent cleaning effect on impurities fixedly adhered in an engine.
Another embodiment of the present invention is directed to providing a composite additive for fuel capable of preventing fuel from being used, for example, as a drink so as to prevent the fuel from being used for other purposes except for fuel to cause fatal problems, while implementing the above-mentioned effects.
In one general aspect, a composite additive for fuel contains: biobutanol wherein the biobutanol is n-butanol which is prepared from biomass,; a ketone based compound selected from one or two or more of methylethylketone, methylisopropylketone, methylisobutylketone, and 5-methyl-3-heptanone; and an ether based compound selected from one or more of methyl tert-butylether and ethyl tert-butylether.
The composite additive for fuel contains 10 to 100 parts by weight of the ketone based compound and 0.1 to 20 parts by weight of the ether based compound, based on 100 parts by weight of biobutanol.
The composite additive for fuel may further contain tert-butanol.
The composite additive for fuel may contain 10 to 100 parts by weight of tert-butanol, based on 100 parts by weight of biobutanol.
The composite additive for fuel may further contain denatonium benzoate.
The composite additive for fuel may contain 10 to 100 parts by weight of tert-butanol and 0.001 to 1 part by weight of denatonium benzoate, based on 100 parts by weight of biobutanol.
The ketone based compound may contain one or two or more (C4-C6) ketone based compounds selected from methylethylketone, methylisopropylketone, and methylisobutylketone, and 5-methyl-3-heptanone.
The ketone based compound may contain 5 to 100 parts by weight of 5-methyl-3-heptanone, based on 100 parts by weight of the (C4-C6) ketone based compound.
The composite additive for fuel may be contained and used in fuel.
The fuel may be gasoline fuel or alcohol based fuel.

DETAILED DESCRIPTION OF EMBODIMENTS

Hereinafter, a composite additive for fuel according to the present invention will be described in detail.
Here, technical terms and scientific terms used in the present specification have the general meaning understood by those skilled in the art to which the present invention pertains unless otherwise defined, and a description for the known function and configuration unnecessarily obscuring the present invention will be omitted in the following description.
Unless the context clearly indicates otherwise, it should be understood that a term in singular form used in the present invention includes the term in plural form.
Unless particularly described, the term "%" unclearly used herein refers to "wt%".
A composite additive for fuel according to the present invention contains biobutanol; a ketone based compound selected form one or two or more of methylethylketone, methylisopropylketone, methylisobutylketone, and 5-methyl-3-heptanone; and an ether based compound selected from one or more of methyl tert-butylether and ethyl tert-butylether. As used herein, the term "biobutanol" means general biobutanol to be used as fuel known in the art. More specifically, the biobutanol, which is butanol prepared from biomass in order to be used as fuel, is substantially normal butanol.
In the composite additive for fuel, the ketone based compound and the ether based compound are essential constitution ingredients for improving a phase separation delay property and an engine cleaning property, and are more effective in delaying a phase separation phenomenon that fuel is phase-separated into an oil layer and a water layer by infiltration or incorporation of water. More specifically, in a case of using one of the ketone based compound and the ether based compound alone in the composite additive for fuel according to the present invention, the phase separation delay property may be slightly decreased, but in the case of using both of the ketone based compound and the ether based compound as in the present invention, the phase separation delay property is significantly improved, and the engine cleaning property in addition to the phase separation delay property may be improved. In addition, as respective ingredients are mixed, a freezing point may be significantly decreased, such that there is an effect of minimizing freezing even in an environment of a significantly low temperature such as winter, and this effect may be further improved by further adding other ingredients to be described below.
The composite additive for fuel contains 10 to 100 parts by weight of the ketone based compound and 0.1 to 20 parts by weight of the ether based compound, and more preferably, 20 to 80 parts by weight of the ketone based compound and 1 to 7 parts by weight of the ether based compound, based on 100 parts by weight of biobutanol.
More preferably, the ketone based compound contains one or two or more (C4-C6) ketone based compounds selected from methylethylketone, methylisopropylketone, and methylisobutylketone, and 5-methyl-3-heptanone. In detail, the (C4-C6) ketone based compound and 5-methyl-3-heptanone are used together in the ketone based compound, which is more effective in suppressing the phase separation phenomenon. That is, as a ketone based compound having a relative low carbon number and a ketone based compound having a relatively high carbon number are used together, free energy of an entire system may be minimized, and dissolved water may stably exist in a form such as micelles, such that the phase separation phenomenon may be significantly decreased even in poor environmental conditions such as high humidity in the fuel, a low temperature, and storage for a long period of time, and the like.
When the composite additive for fuel according to the exemplary embodiment of the present invention contains the (C4-C6) ketone based compound and 5-methyl-3-heptanone, a composition ratio of them is not particularly limited, but in order to effectively implement the above-mentioned effect, the ketone based compound may contain 5 to 100 parts by weight and preferably 10 to 60 parts by weight of 5-methyl-3-heptanone, based on 100 parts by weight of the (C4-C6) ketone based compound. However, this is only a preferable example, but the present invention is not limited thereto.
The composite additive for fuel according to the exemplary embodiment of the present invention may further contain tert-butanol and/or denatonium benzoate, and preferably, the composite additive for fuel contains both tert-butanol and/or denatonium benzoate. More specifically, in the case in which the composite additive for fuel contains both tert-butanol and denatonium benzoate, the phase separation delay property and the engine cleaning property may be significantly improved as compared to the case in which one of tert-butanol and denatonium benzoate is contained alone. As tert-butanol having steric hindrance is mixed together with denatonium benzoate present in a form of salt, both of the phase separation delay property and the engine cleaning property may be significantly improved.
Further, when the composite additive for fuel according to the exemplary embodiment contains denatonium benzoate, the composite additive for fuel has a specific flavor and taste, such that the composite additive for fuel has an effect of preventing the fuel from being used for other purposes except for fuel.
When the composite additive for fuel according to the exemplary embodiment of the present invention contains tert-butanol, a composition ratio thereof is not particularly limited. For example, the composite additive for fuel may contain 10 to 100 parts by weight, preferably, 15 to 60 parts by weight of tert-butanol, based on 100 parts by weight of the biobutanol. However, this is only a preferable example, but the present invention is not limited thereto.
When the composite additive for fuel according to the exemplary embodiment of the present invention contains denatonium benzoate, a composition ratio thereof is not particularly limited. For example, the composite additive for fuel may contain 0.001 to 1 part by weight, preferably, 0.001 to 0.5 parts by weight of denatonium benzoate, based on 100 parts by weight of the biobutanol. However, this is only a preferable example, but the present invention is not limited thereto.
When the composite additive for fuel according to the exemplary embodiment of the present invention contains tert-butanol and denatonium benzoate, a composition ratio thereof is not particularly limited. For example, in order to effective implement the above-mentioned effects, the composite additive for fuel may contain 10 to 100 parts by weight of tert-butanol and 0.001 to 1 part by weight of denatonium benzoate, preferably, 15 to 60 parts by weight of tert-butanol and 0.001 to 0.5 parts by weight of denatonium benzoate, based on 100 parts by weight of the biobutanol. However, this is only a preferable example, but the present invention is not limited thereto.
The composite additive for fuel according to the present invention may be contained and used in various kinds of fuel such as biofuel, fossil fuel, and the like, but preferably, the composite additive for fuel may be added to and used in alcohol based fuel or gasoline fuel.
Hereinafter, the present invention will be described in more detail through Examples, but they are provided only for clearly understanding the present invention, and the scope of the present invention is not limited thereby.

[Example 1]

A composite additive for fuel was prepared by sufficiently stirring respective ingredients so as to satisfy ingredients and contents illustrated in the following Table 1.

[Example 2]

[Example 3]

[Example 4]

[Example 5]

[Example 6]

[Comparative Example 1]

[Comparative Example 2]

[Table 1]

Ingredient (kg)	B-1	B-2	K-1	K-2	K-3	K-4	E-1	E-2	D
Example 1	6.8	-	1.0	1.0	1.0	-		0.2	-
Example 2	9.5	-	-	-	-		0.4	0.1	-
Example 3	6.2	-	1.0	1.0	1.0	0.5	0.2	0.1	-
Example 4	6.2	2.0	0.5	1.0	1.0	1.0	0.2	0.1	-
Example 5	6.8	-	1.0	0.5	0.5	0.5	0.2	0.1	0.0004
Example 6	6.6	2.0	1.0	0.5	0.5	0.5	0.2	0.2	0.0005
Comparative Example 1	9.5	-	-	-	-	-	0.3	0.2	-
Comparative Example 2	8	-	0.5	0.5	0.5	0.5	-	-	-
B-1: biobutanol (normal butanol)
B-2: tert-butanol
K-1: methylethylketone
K-2: methylisopropylketone
K-3: methylisobutylketone
K-4: 5-methyl-3-heptanone
E-1: methyl-tert-butylether
E-2: ethyl-tert-butylether
D: denatonium benzoate

Evaluation of Phase Separation Delay Property

An experiment was performed on each of the composite additives for fuel in Examples 1 to 6 and Comparative Examples 1 and 2 by the following method, thereby evaluating a degree of phase separation delay.

In detail, each of the composite additives for fuel was injected into each test tube (100 ml), water (0.05%, 0.1%, 0.15%, 0.20%, 0.25%, 0.30%, 0.35%, 0.40%, 0.45%, and 0.50%) was further injected thereinto, respectively, and forcedly incorporated into the composite additive for fuel by violently shaking the test tube. Then, the test tube was allowed to stand for 10 minutes, and a changed layer was confirmed. Further, in order to finally confirm clear layer separation, centrifugation was performed at 20°C and 1,500 rpm for 10 minutes, and a scale of the layer generated in the test tube was measured.

[Table 2]

Phase Separation Suppression Property (ml)
Example 1	0.31
Example 2	0.25
Example 3	0.16
Example 4	0.15
Example 5	0.13
Example 6	0.09
Comparative Example 1	0.40
Comparative Example 2	0.38

As illustrated in Table 2, in Comparative Examples 1 and 2 in which one of the ketone based compound and the ether based compound was used alone, the phase separation delay property was the worst, but in Examples 1 to 6 in which the ketone based compound and the ether based compound were used together, the phase separation delay property was significantly improved.
In Examples 3 to 6 in which a (C4-C6) ketone based compound and a C8 ketone based compound (5-methyl-3-heptanone) were used together, the phase separation delay property was better than those in Examples 1 and 2 in which one of the (C4-C6) ketone based compound and the C8 ketone based compound (5-methyl-3-heptanone) were used alone.
From results in Examples 3 and 4 of Table 2, it may be appreciated that tert-butanol singly did not have a large influence on the phase separation delay property. Further, from results in Examples 5 and 6 of Table 2, it may be appreciated that only when denatonium benzoate was used together with tert-butanol, the phase separation delay property was significantly improved. From this result, it is thought that steric properties of tert-butanol and salt properties of denatonium benzoate act in combination to significantly suppress phase separation of a composition.

Evaluation of Engine Cleaning Property

An experiment was performed by adding 1 wt% of each of the composite additives for fuel in Examples 1 to 6 and Comparative Examples 1 and 2 to gasoline using the following method, thereby evaluating a degree of the engine cleaning property.

More specifically, the experiment was performed according to a gasoline engine test method as described in the literature published by Society for Automotive Engineers (SAE) under the reference SAE # 922184 in 1992. Here, each experiment was performed for 5 hours under conditions of an engine speed of 3,000 rpm and a load of 2/3 of maximum load. At the beginning of each experiment, an engine was mounted with a new injector, before mounting the new injector, a flow rate of each injector was measured at each needle lift. At the end of each experiment, the injector was separated, and a flow rate at the same needle lift was measured. Efficiency of each of the tested composite additives for fuel was compared as a residual flow percentage, and the residual flow percentage was calculated by the following Equation 1. The results are illustrated in the following Table 2, and the larger the flow rate, the more excellent the engine cleaning effect.

Residual flow rate (%) = (average flow rate of injector at the end of the test / average flow rate of a new injector) \times 100

[Table 3]

Residual Flow Rate (%)
Needle Lift (mm)	0.1	0.2	0.3	0.4	0.5
Gasoline alone	13	23	29	39	51
Example 1	52	56	61	69	75
Example 2	48	53	58	65	73
Example 3	49	54	59	67	76
Example 4	52	57	62	70	78
Example 5	58	64	72	79	85
Example 6	71	76	85	91	96
Comparative Example 1	42	45	49	55	64
Comparative Example 2	44	47	51	58	67

As illustrated in Table 3, in Comparative Examples 1 and 2 in which one of the ketone based compound and the ether based compound was used alone, the engine cleaning property was the worst, but in Examples 1 to 6 in which the ketone based compound and the ether based compound were used together, the engine cleaning property was significantly improved.
In the case in which tert-butanol was added alone as in Example 4, there was no large influence on the engine cleaning property, but in the case in which denatonium benzoate was added alone, the engine cleaning property was improved. Particularly, it may be confirmed in Table 3 that in the case in which denatonium benzoate and tert-butanol were used together, the engine cleaning property was significantly improved as compared in the case in which denatonium benzoate was added alone.
The composite additive for fuel according to the present invention may significantly delay the phase separation phenomenon even in poor environmental conditions such as high humidity, a low temperature, storage for a long period of time, and the like, prevent freezing in winter due to a lower freezing point, and have an excellent cleaning effect on impurities fixedly adhered in an engine.
Further, the composite additive for fuel according to the present invention may prevent fuel from being used, for example, as a drink so as to prevent the fuel from being used for other purposes except for fuel to cause fatal problems, while implementing the above-mentioned effects.

Claims

A composite additive for fuel comprising:
biobutanol;

a ketone based compound selected from one or two or more of methylethylketone, methylisopropylketone, methylisobutylketone, and 5-methyl-3-heptanone; and

an ether based compound selected from one or more of methyl tert-butylether and ethyl tert-butylether,

wherein the biobutanol is n-butanol which is prepared from biomass, and

wherein the composite additive for fuel contains 10 to 100 parts by weight of the ketone based compound and 0.1 to 20 parts by weight of the ether based compound, based on 100 parts by weight of biobutanol.
The composite additive for fuel of claim 1, further comprising tert-butanol.
The composite additive for fuel of claim 2, wherein it contains 10 to 100 parts by weight of tert-butanol, based on 100 parts by weight of biobutanol.
The composite additive for fuel of claim 2, further comprising denatonium benzoate.
The composite additive for fuel of claim 4, wherein it contains 10 to 100 parts by weight of tert-butanol and 0.001 to 1 part by weight of denatonium benzoate, based on 100 parts by weight of biobutanol.
The composite additive for fuel of claim 1, wherein the ketone based compound contains one or two or more (C4-C6) ketone based compounds selected from methylethylketone, methylisopropylketone, and methylisobutylketone, and 5-methyl-3-heptanone.
The composite additive for fuel of claim 6, wherein the ketone based compound contains 5 to 100 parts by weight of 5-methyl-3-heptanone, based on 100 parts by weight of the (C4-C6) ketone based compound.
A fuel comprising the composite additive for fuel of claims 1.
The fuel of claim 8, wherein the fuel is gasoline fuel or alcohol based fuel.