KR100356715B1 - Novel Clean Diesel Oil - Google Patents

Abstract

The present invention provides a clean diesel fuel in which vegetable oil and carbonate compounds are added to low sulfur diesel. The clean diesel fuel of the present invention uses a carbonate compound instead of the acylated compound used as a dispersant in the conventional diesel fuel, and after combustion, emissions of aromatic polymers, unburned fine dust, carbon monoxide, hydrocarbons, etc. are significantly reduced. In addition, the emissions of aldehydes and NOx were also reduced compared to conventional fuels containing vegetable fats and oils. Therefore, the clean diesel fuel of the present invention may be widely used as an environmentally friendly fuel.

Description

Clean Diesel Oil

The present invention relates to a novel clean diesel fuel. More specifically, the present invention relates to a clean diesel fuel in which vegetable oil and carbonate compounds are added to low sulfur diesel.

Diesel oil (diesel) is one of the petroleum products in wide use today. Diesel is used as a source of energy for heating and plant equipment and as a fuel for diesel engines. It is used as a very important resource because it is used in trucks, which are a means of transporting various materials, and buses, which are large personnel. However, air pollution from most diesel engines and boilers using diesel is very serious, and pollution caused by buses running in the city in particular is causing serious problems in two aspects: First, sulfur oxides are generated due to the excessive sulfur content in diesel oil, causing acidification of urban air; Second, aromatic compounds, carcinogens, are contained in the fumes (fine particles) generated during the non-combustion of diesel fuel due to the excessive amount of aromatic polymer in diesel fuel, which has a great negative effect on national health.

On the other hand, many international environmental reports warn that the soot from metropolitan cities is likely to cause lung cancer (see WHO ON8, 1991; Amis de la Terre, 1996; ORSIF, 1997). There are two ways to strengthen environmental regulations on diesel, which is a source of pollution:

1) minimization of sulfur content in diesel oil,

2) Minimization of the amount of aromatic polymer contained in the gas oil.

In Korea, sulfur content in diesel has been lowered from 2000ppm to 500ppm, but the sulfur content is still high in view of the domestic situation with high density of vehicles and population. In Europe, where pollution problems are less serious than in our country, sulfur content in diesel oil has been reduced to 360 ppm in 1996 and to 50 ppm in 2005. In addition, several European countries such as Sweden have developed diesel fuels for city with sulfur content of less than 10ppm and use them for heating fuel and city buses. In addition, the European regulatory standards for aromatic polymer content are limited to 11% or less, but there are no domestic regulatory standards, and in reality, there is a high population density, heavy traffic, high hills, etc. The use of environmentally toxic diesel fuels in metropolitan cities poses more serious health problems than any other country in the world.

There are two main ways to make clean diesel fuel known to date:

First is to lower the sulfur content of diesel. The domestic oil refining industry has a relatively good desulfurization facility, which makes it easy to lower the sulfur content. However, since sulfur in diesel fuels lubrication between metals in the engine, lowering the sulfur content causes the engine's fuel injectors to wear out, which greatly shortens the engine's lifespan and leads to incomplete combustion of fuel due to lack of lubrication. Promote the release of toxic particles due. In order to solve this problem, the development of lubricating additives has been made. Generally, additives used for the operation of diesel lubricating oil include lubricants, dispersants for complete dissolution thereof, antifoaming agents, and the like. Of these, ester hydrocarbons are most widely used as additives. In particular, methyl esters made from vegetable oils have been widely used in Europe since the early 1990s. Around 1993, the amount of consumption reached 500,000 tons in France and Italy thanks to tax benefits. Since the additive contains almost no sulfur-containing substance and has good lubricity, it is currently used by adding 2-5% to low sulfur (360 ppm or less) diesel oil.

Second, the method of increasing the amount of methyl ester added. In this case, the major pollutants emitted from diesel fuel, CO ₂ and CO, dust and SOx, were significantly reduced. However, there is a drawback that the amount of methane and aldehydes which are relatively irritating, which is considered as another pollutant, is maintained at a higher level than that of general diesel. On the other hand, methyl ester may cause precipitation of saturated fatty acid ester components contained in fatty acids under cold conditions such as in winter weather in Korea, resulting in deterioration of microtubules and filters of the fuel supply system. The use of dispersants has emerged as a material that can solve the precipitation problem of such additives. As dispersants, for example, nitrogen-containing acylated nitrogen compounds have been introduced (see, eg, PCT / EP 96/0045, US Pat. 3,272,746, US Pat. 3,444,170, EP 0,336,664, etc.). It is described that nitrogen compounds can prevent precipitation of esters to maintain the lubricating properties of ester compounds. However, these nitrogen compounds may improve the lubrication performance, but may be another pollutant to be discharged, it has been pointed out that the problem of reducing the emission of aldehydes.

Therefore, the addition of environmentally-friendly bio-materials and non-nitrogen-containing dispersants, which act as a wear protection to low-sulphur diesel fuels, improves the lubrication performance of the diesel oil, while also reducing sulfur oxide emissions. There is a constant need to develop clean diesel fuel that can improve the oxidation performance of aldehydes and aromatic polymers, thereby reducing emissions of carcinogenic polymer dust and particles.

Accordingly, the present inventors have made diligent efforts to develop diesel fuels with minimal pollution while maintaining the lubricity of diesel fuel in which vegetable oil is added to diesel oil. Therefore, when the carbonate compound is used as a dispersant instead of the nitrogen compound used as a conventional dispersant, In addition, the emission of various pollutants including aromatic polymers, as well as the emission of nitrogen oxides, was found to be significantly reduced compared to conventional diesel fuels, and the present invention was completed.

After all, it is an object of the present invention to provide a new clean diesel fuel in which the amount of pollution is significantly reduced compared to conventional diesel fuel.

The clean diesel fuel of the present invention is 0.004 to 35.0 parts by weight of vegetable fats and oils and low carbon diesel having a sulfur content of less than 500 ppm with respect to 100 parts by weight of the electric low sulfur light oil, and the carbonate compound 0.004 to 5.0 represented by the following general formula (I): Contains parts by weight:

(Ⅰ)

Where

R ₁ and R ₂ are each saturated or unsaturated aliphatic hydrocarbons, aromatic hydrocarbons or alcohols having 1 to 22 carbon atoms; Or a compound having a carbon length of 1 to 22 carbon atoms and including an ester and an ether functional group therein.

Wherein the vegetable oil is fatty acid methyl ester; Or it is preferable that the content of fatty acid monoglyceride is 40 weight% or more, and the mixture containing fatty acid ethyl ester, fatty acid monoglyceride, fatty acid diglyceride, and fatty acid triglyceride is used. If the content of fatty acid monoglycerides in the mixture does not reach 40% by weight, it is not preferable because the viscosity of the mixture is excessive and incomplete combustion occurs. On the other hand, the content of vegetable fats and oils is preferably 0.004 to 35.0 parts by weight based on 100 parts by weight in the case of low sulfur, when the content of vegetable oils does not reach 0.004 parts by weight, the lubrication action is sharply lowered, exceeding 35.0 parts by weight In this case, the content of aldehyde in the exhaust gas is increased.

In addition, the compound represented by the general formula (I) is used in the present invention as a dispersant to allow the electric vegetable oil to be effectively dispersed in diesel oil, and these carbonate compounds have a hydrophilic group and a hydrophobic group in one molecule, thus making it a fatty acid ester. Not only helps to disperse, but also contains 3 or more oxygen in the molecule, thereby reducing the amount of aldehyde generated during combustion, and also helps to burn aromatic polymers, thereby reducing the emission of carcinogenic dust. In addition, these molecules are almost non-toxic and, unlike dispersants in nitrogen compounds, they do not contain nitrogen in the molecule, thereby reducing the amount of NOx relatively. The amount of the electric carbonate compound is preferably 0.004 to 5.0 parts by weight relative to the weight 100 in the case of low sulfur, when the content of the carbonate compound does not reach 0.004 parts by weight, the amount used is too small to function as a dispersant. When the amount exceeds 5.0 parts by weight, the micelle phenomenon occurs in the mixture, and the dispersing effect no longer increases.

Preferably, the carbonate compound represented by the general formula (I) is dimethyl carbonate (dimethyl carbonate, DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), diphenyl carbonate (diphenyl carbonate, DPnC) Or one or more compounds selected from the group consisting of carbonate compounds represented by the general formula (II):

(Ⅱ)

Where

R ₃ and R ₄ are each hydrogen, saturated or unsaturated aliphatic hydrocarbons, aromatic hydrocarbons or alcohols having 1 to 21 carbon atoms; or, esters, ethers, having from 1 to 21 carbon atoms It is a compound containing a functional group.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention in more detail, it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited by these examples in accordance with the gist of the present invention. will be.

Example 1 Preparation of Clean Diesel Fuel and Analysis of Pollutants (I)

First, 6.7 kg of commercially available light oil (500 ppm sulfur), 3.0 kg of oleic acid methyl ester (more than 98% purity) made from sunflower oil and 0.3 kg of dimethyl carbonate were injected into a mixer equipped with a 30 L stirring device. After stirring sufficiently, a clean diesel fuel was produced.

Next, for the clean diesel fuel produced in the electricity, the amount of pollutant generation was measured. The measurement of pollutant emissions was carried out using a diesel engine (exhaust rate 2,637cc) mounted on the company's 12-seater minibus, preheated for 30 minutes after starting, and then the fuel used at 2000 rpm. The amount of aromatic polymer, unburned fine dust, carbon monoxide, hydrocarbon, aldehyde and NOx generated per unit weight was measured. Carbon monoxide, hydrocarbons and NOx emissions were measured using Prolabo's model Testo 360. The concentration of aromatic polymers was measured by Merck's tube indicator, Gastec tube No. It was measured using 121, and the concentration of aldehyde was measured by Gastec tube No. of the company. 92 was used. On the other hand, the measurement of the amount of unburned fine dust was performed by a method of measuring the difference in filter weight before and after the passage of exhaust air, using a Prolabo micro filter (diameter 110mm, pore size 0.3mm).

Example 2 Preparation of Clean Diesel Fuel and Analysis of Pollutants (II)

First, 0.4 kg of vegetable oil mixture (52% oleic acid monoglyceride, 36% oleic acid diglyceride, 12% oleic acid triglyceride) prepared from 6.7 kg of commercially available light oil (500 ppm sulfur) and soybean oil, and 0.1 kg of glycerin carbonate oleate Was injected into a mixer equipped with a 30-liter stirring device, and then sufficiently stirred to prepare a clean diesel fuel. Next, with respect to the clean diesel fuel produced in the electricity, the amount of pollutant generation was measured in the same manner as in Example 1.

Comparative Example 1 :

Except that dimethyl carbonate was not added, the fuel of the same composition as the diesel fuel prepared in Example 1 was prepared, and then the amount of pollutant generation was measured in the same manner as in Example 1.

Comparative Example 2 :

The amount of generation of various pollutants was measured in the same manner as in Example 1 with respect to the diesel oil in which dimethyl carbonate and vegetable oil were not added at all.

The above experimental results are summarized in Table 1 below. For reference, the pollutant items included emissions of aromatic polymers, unburned fine dust, carbon monoxide, hydrocarbons, aldehydes and NOx.

Metric unit Example 1 Example 2 Comparative Example 1 Comparative Example 2 Aromatic polymer Μg / km 1.4 2.1 2.2 7.1 Unburned fine dust g / kg 0.06 0.07 0.08 0.15 carbon monoxide g / km 0.2 0.2 0.3 0.6 hydrocarbon g / km 0.04 0.05 0.06 0.10 Aldehyde Mg / km 26 29 49 40 NOx g / km 0.61 0.63 0.70 0.65

In Table 1, when only vegetable oil was added to the conventional diesel fuel, the emissions of aromatic polymers, unburned fine dust, carbon monoxide, and hydrocarbons were decreased, but emissions of aldehydes and NOx were increased. However, in the case of using the clean diesel fuel of the present invention, it can be seen that not only the emissions of these pollutants are significantly reduced, but also the emissions of aldehydes and NOx, compared to the fuels containing only vegetable oil.

As described in detail and demonstrated above, the present invention provides a clean diesel fuel in which vegetable oil and carbonate compounds are added to low sulfur diesel. The clean diesel fuel of the present invention uses a carbonate compound instead of the acylated compound used as a dispersant in the conventional diesel fuel, and after combustion, emissions of aromatic polymers, unburned fine dust, carbon monoxide, hydrocarbons, etc. are significantly reduced. In addition, the emissions of aldehydes and NOx were also reduced compared to conventional fuels containing vegetable fats and oils. Therefore, the clean diesel fuel of the present invention may be widely used as an environmentally friendly fuel.

Claims (3)

Clean diesel fuel containing 0.004 to 6.0 parts by weight of vegetable oils and 0.004 to 5.0 parts by weight of a carbonate compound represented by the following general formula (I) in a low sulfur light oil having a sulfur content of less than 500 ppm, based on 100 parts by weight of the electric low sulfur light oil. : (Ⅰ) Where R ₁ and R ₂ are each saturated or unsaturated aliphatic hydrocarbons, aromatic hydrocarbons or alcohols having 1 to 22 carbon atoms; Or a compound having a carbon length of 1 to 22 carbon atoms and including an ester and an ether functional group therein. The method of claim 1, Vegetable oils are fatty acid methyl esters; Or a fatty acid monoglyceride content of 40% by weight or more and a mixture comprising fatty acid ethyl ester, fatty acid monoglyceride, fatty acid diglyceride and fatty acid triglyceride. Clean diesel fuel. The method of claim 1, The carbonate compound is dimethyl carbonate (dimethyl carbonate, DMC), diethyl carbonate (DEC), dipropyl carbonate (dipropyl carbonate, DPC), diphenyl carbonate (diphenyl carbonate, DPnC) or a carbonate represented by the general formula (II) At least one compound selected from the group consisting of compounds Clean Diesel Fuel: (Ⅱ) Where R ₃ and R ₄ are each hydrogen or a saturated or unsaturated aliphatic hydrocarbon, aromatic hydrocarbon or alcohol having 1 to 21 carbon atoms in carbon length; Or a compound having a carbon length of 1 to 21 carbon atoms and including an ester and an ether functional group therein.