WO2003074636A1

WO2003074636A1 - Fuel oils, lubricants for fuel oils and productive facilities for fuel oils

Info

Publication number: WO2003074636A1
Application number: PCT/JP2003/002435
Authority: WO
Inventors: Akira Ishiwada; Kohei Uchida; Wataru Kawamura; Yuji Oda; Hisashi Otsuka; Koji Kato; Mitsuhiko Takei; Junichi Yamada
Original assignee: Mitsubishi Gas Chemical Company, Inc.; Mitsubishi Heavy Industries, Ltd.; Itochu Corporation; Lion Corporation
Priority date: 2002-03-04
Filing date: 2003-03-03
Publication date: 2003-09-12
Also published as: CN1273570C; MY141973A; KR101257498B1; JP4282486B2; CN1639307A; JPWO2003074636A1; KR20040094763A; AU2003220860A1

Abstract

The invention aims at keeping the lubrication properties of a fuel oil containing dimethyl ether as the main component at a high level and thereby making dimethyl ether commercially serviceable as a fuel oil, thus providing fuel oils largely contributing to environmental conservation, lubricants for such oils, and productive facilities for the oils. The fuel oil of the invention comprises dimethyl ether and at least one member selected from among vegetable fats and oils and derivatives thereof. Examples of the vegetable fats and oils include coconut oil, palm oil and so on, while those of the derivatives include mono- to poly-hydric alcohol esters of the constituent fatty acids of the above vegetable fats and oils, adducts of these esters with alkylene oxides, and adducts of the constituent fatty acids with alkylene oxides. The lubricant of the invention for fuel oils containing dimethyl ether as the main component consists of at least one member selected from among the above vegetable fats and oils and derivatives thereof.

Description

Description Fuel oil, fuel oil lubricant and fuel oil production equipment

The present invention relates to a fuel oil containing dimethyl ether as a main component, which has a low environmental load, a fuel oil lubricant suitable for the fuel oil, and a fuel oil production facility. Background art

In recent years, dimethyl ether (hereinafter abbreviated as “DME”) has a high cetane number and contains oxygen atoms, so it emits smokeless fuel and other new gasoline, light oil, and heavy oil alternative fuels that have a low environmental impact. It is attracting attention.

For example, a diesel engine using DME as fuel can produce almost the same output as using diesel fuel, but unlike diesel fuel, DME has poor lubricity, so if it is used for a long time, the fuel injection system slides. It has been pointed out that the moving parts and the like become difficult to operate due to wear, and the use of DME as fuel oil has not yet been commercially successful.

On the other hand, in a light oil composition (diesel fuel) having an Io content of about 0.2% by weight or less and an aromatic hydrocarbon content of about 30% by weight or less, as a lubricity improving agent, the saturation and saturation derived from oily seeds of a plant were C ₅ alkyl esters ranging from 100 to 10000 p pm gas oil composition characterized by containing (by weight) is known (JP-a 7 62 363 No. of mixtures of linear fatty acids C ₁₂ ~ ₂₂ unsaturated Gazette) However, the gas oil compositions described in the above patent documents have an I.O.

In order to improve lubricity when using special diesel fuel compositions (diesel fuel) with less than 2% by weight and aromatic hydrocarbon content of less than about 30% by weight, the saturation derived from oily seeds of plants Of mixtures of unsaturated and unsaturated linear fatty acids A special amount of DME, which has different physical properties, lubricating properties, etc. from those for fuel oils mainly comprising DME of the present invention. Are completely different in their chemical structure. The present invention has been made in view of the above-mentioned conventional problems and the current situation, and has been made to solve the problem. An object of the present invention is to provide a fuel oil lubricant and a fuel oil production facility suitable for the fuel oil. Disclosure of the invention

The present inventors have conducted intensive studies on the above-mentioned conventional problems and the like, and as a result, by adding a specific component to DME as a lubricant, the fuel oil, the fuel oil lubricant, and the fuel oil manufacturing equipment described above were obtained. And found that the present invention was completed.

That is, the present invention resides in (1) to (10).

(1) A fuel oil comprising dimethyl ether and at least one selected from vegetable oils and fats and oil derivatives.

(2) The fuel oil according to the above (1), wherein the vegetable oil is palm oil.

(3) The fuel oil according to the above (1), wherein the vegetable oil derivative is a palm oil derivative.

(4) The fuel oil according to (3), wherein the palm oil derivative is palm oil fatty acid methyl ester.

(5) A fuel oil-based lubricant comprising dimethyl ether as a main component, comprising at least one selected from vegetable oils and fat derivatives.

(6) The lubricant for a fuel oil according to the above (5), wherein the vegetable oil is palm oil.

(7) The lubricant for fuel oil according to the above (5), wherein the vegetable fat derivative is a palm oil derivative.

(8) The fuel according to the above (7), wherein the palm oil derivative is palm oil fatty acid methyl ester. Lubricants for oiling.

(9) A fuel oil production facility comprising a mixing facility for adding a predetermined amount of at least one selected from vegetable oils and fats and vegetable oils and fats to dimethyl ether to obtain fuel oil.

(10) A plant oil / fat derivative production facility for producing a vegetable oil / fat derivative from a vegetable oil / fat, and a predetermined amount of the vegetable oil / fat derivative obtained by the vegetable oil / fat derivative production facility is added to dimethyl ether to obtain a fuel oil. A fuel oil production facility comprising: BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic view showing a sliding section between a plunger and a plunger barrel of a fuel injection pump in a diesel engine in a sectional view. FIG. 2 (a) shows a fuel oil composed of DME alone in Comparative Example 1. FIG. 2B is a graph showing a change in clearance between a plunger and a plunger barrel with respect to an operation time when the fuel oil according to the first embodiment falls within the scope of the present invention. It is a graph which shows the change of each fuel injection maximum pressure at that time in comparison. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described in detail.

The fuel oil of the present invention is characterized by comprising dimethyl ether and at least one selected from vegetable fats and oils and vegetable fat derivatives.

Further, the lubricant for fuel oil containing dimethyl ether as a main component of the present invention is characterized by comprising at least one selected from vegetable fats and oils and vegetable fats and oils derivatives.

As the DME used in the present invention, for example, a synthesis gas mainly composed of carbon monoxide and hydrogen is obtained by reforming using natural gas as a raw material. DME. In this case, there are two methods, a direct synthesis method from the above synthesis gas, and a method by dehydration of the methanol from the synthesis gas once through methanol, and in the present invention, the DME obtained by either method is used. May be.

Furthermore, synthesis gas composed of carbon monoxide and hydrogen can be produced not only from natural gas but also from coal gasification gas, biomass, petroleum residues, industrial waste, etc. I don't care. In general, DME having a purity of 90% or more, preferably 99% or more, more preferably 99.9% or more can be obtained by each of the above methods.

DME used in the present invention may be any one obtained by the above methods.

Examples of the vegetable fats and oils used in the present invention include coconut oil, palm oil, rapeseed oil, olive oil, soybean oil, and the like, and these may be hydrogenated or non-hydrogenated. Preferably, palm oil and palm oil are used from the viewpoint of exhibiting further lubricating performance, and particularly preferably, palm oil having excellent compatibility with DME is desirable.

Further, the “vegetable fat / oil derivative” used in the present invention means a derivative derived by performing a chemical reaction on the above vegetable fat / oil. Specific examples include mono- to polyhydric alcohol esters of constituent fatty acids of vegetable fats and oils derivatives, alkylene oxide adducts thereof, and alkylene oxide adducts of constituent fatty acids. Examples of the monohydric to polyhydric alcohols of monohydric to polyhydric alcohol esters include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, butylene glycol, pentaerythritol, trimethylolpropane, sorbitol, and the like. Alcohol.

These esters can be produced by a usual production method such as a transesterification method of the fat or oil with a corresponding alcohol, or a direct esterification method with a constituent fatty acid.

Of these, monovalent alcohols with 1 to 5 carbon atoms in fatty acids that make up vegetable oils and fats Coal esters, preferably monohydric alcohol esters of palm oils having 1 to 5 carbon atoms, particularly methyl esters of palm oil fatty acids, are suitable.

Alkylene oxide adducts of monohydric to polyhydric alcohol esters or alkylene oxide adducts of constituent fatty acids of vegetable fats and oils derivatives can be prepared by conventional methods using the corresponding monohydric to polyhydric alcohol esters or the corresponding constituent fatty acids and alkylene oxide. It can be obtained by an addition reaction with an oxide.

Alkylene oxides include, for example, ethylene oxide, propylene oxide, and butylene oxide, with ethylene oxide and propylene oxide being preferred. These may be either single or a mixture. The number of moles of the alkylene oxide added is 1 to 100 moles per 1 mole of fats and oils or 1 mole of fatty acids, preferably 1 to 20 moles, and more preferably 1 to 5 moles. .

The vegetable oils and fats and vegetable oils and fats can be used alone (individually) or as a mixture of two or more.

The fuel oil of the present invention comprises the above-mentioned DME and at least one selected from vegetable fats and oils and derivatives as a lubricant, and the blending ratio thereof is preferably DME 10 0 parts by mass, at least one selected from vegetable oils and fats and oil derivatives is 0.001 to 100 parts by mass, more preferably 0.002 to 50 parts by mass. It is desirable that

In particular, palm oil fatty acid methyl ester is added to DME 100 parts by mass in the above range.

(0.001 to 100 parts by mass).

If the amount of at least one selected from the vegetable oils and fats is less than 0.01 parts by mass, the effects of the present invention cannot be exhibited. Exceeding the parts by mass does not change the effect of the present invention and increases the cost, which is not preferable. As described above, the fuel oil of the present invention comprises DME and at least one selected from vegetable fats and oils and vegetable fat derivatives as a lubricant as long as the effects of the present invention are not impaired. , Adding various optional components to the fuel oil, such as antioxidants, oiliness improvers, antioxidants, cleaning dispersants, friction modifiers, defoamers, flow improvers, viscosity index improvers, etc. Can be.

The fuel oil or the fuel oil lubricant of the present invention thus constituted is, for example, a fuel oil or a fuel oil for various uses such as power generation, private use, and diesel engine as a substitute for gasoline, light oil, and heavy oil. Although it can be used as a lubricant for fuel, it is particularly suitable as a fuel oil or a lubricant for fuel oil of diesel engines for trucks, ships, power generation, construction machinery and the like.

When the fuel oil of the present invention is used, for example, as a fuel oil for a diesel engine, if DME alone (DME only) is used, the sliding portion will be worn away. However, the fuel oil of the present invention can maintain normal operation without any problem even in continuous operation for a long time of several thousand to tens of thousands of hours.

Next, the fuel oil production facility of the present invention is characterized in that a predetermined amount of at least one selected from the above-mentioned vegetable oils and fats is added to DME obtained by each of the above-described methods and the like. Mixing equipment for obtaining fuel oil by adding 0.001 to 100 parts by mass of at least one selected from vegetable fats and oils and vegetable fat derivatives per 100 parts by mass of DME It is assumed that.

As this fuel oil production equipment, for example, the DME obtained by each of the above-mentioned methods and the like is supplied to a stirrer (tank) equipped with a mixer by a pipeline, and the above-mentioned vegetable oil and vegetable Examples include those equipped with a production facility for adding a predetermined amount of at least one selected from oil and fat derivatives and stirring and mixing.

Further, another fuel oil production facility of the present invention comprises a vegetable oil / fat derivative production facility for producing a vegetable oil / fat derivative from a vegetable oil / fat, And a mixing facility for adding a predetermined amount of the obtained vegetable oil / fat derivative to DME to obtain a fuel oil.

As the fuel oil production equipment, for example, a vegetable oil / fat derivative production equipment for producing a vegetable oil / fat derivative by performing a chemical reaction on the above-mentioned vegetable oil / fat, and a plant obtained by the vegetable oil / fat derivative production equipment And a mixing unit for supplying a predetermined amount of the oil-and-fat derivative and DME obtained by each of the above-described methods to a stirrer provided with a mixer and mixing them with stirring.

In each of the fuel oil production facilities of the present invention configured as described above, a predetermined amount of dimethyl ether and the above-mentioned lubricant are mixed by a facility equipped with a stirrer having an ordinary mixer, thereby achieving uniform integration. This makes it possible to easily produce the fuel oil of the present invention, which becomes a liquid. Therefore, it is preferable to install the fuel oil production facility of the present invention adjacent to the installation place of the vegetable oil (and derivative thereof) production facility, particularly in view of reduction in transportation cost. Example

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

(Example 1 and Comparative Example 1)

DME used in each fuel oil of Example 1 and Comparative Example 1 and the following vegetable oil derivatives as lubricants were used as test samples.

[DME]

A sample having a purity of 99.9% manufactured by Mitsubishi Gas Chemical Company was used as a test sample.

[Vegetable oil derivatives (palm oil fatty acid methyl ester)]

3.56 g of methanol and 3 g of sodium hydroxide were added to 110 g of palm oil, and transesterification was carried out at 70 ° C. for 60 minutes at 70 ° C. under a nitrogen gas atmosphere and at a pressure of IM pa G or more. . After cooling, glycerin was separated and 50 g of methanol was added. Then, 1 g of sodium hydroxide was added, and transesterification was performed at 60 ° C. for 10 minutes under normal pressure.

Next, 160 g of water was added, and after stirring, the mixture was allowed to stand and separated to remove glycerin, thereby obtaining methyl palm oil fatty acid. The resulting ester was topped at 155 ° C under normal pressure to remove water and methanol to obtain purified palm oil fatty acid methyl ester, which was used as a test sample.

In Example 1, a fuel oil composed of 100 parts by mass of the DME and 10 parts by mass of the vegetable oil / fat derivative (palm oil fatty acid methyl ester) was used.

In Comparative Example 1, the fuel oil composed of 100% by mass of DME was used.

Using the fuel oils of Example 1 and Comparative Example 1 described above, a diesel engine was subjected to an actual operation test and evaluated by the following evaluation method using a diesel engine having the following configuration.

〔Evaluation method〕

The diesel engine used was an industrial direct injection diesel engine.

In this diesel engine, the parts where the lubricity of fuel has a great effect are:

Sliding parts,

In addition to the sliding part between the barrels, there is a sliding part between the face cam and the roller, and a sliding part between the needle valve and the main body of the fuel injection valve which is shared in each case.

The wear condition of these parts greatly affects the fuel injection performance. If the wear exceeds a certain value, the fuel injection characteristics deteriorate, the engine performance is impaired, and in severe cases, engine operation may not be possible.

Therefore, in this evaluation, the engine was actually used as a new one between the case where the conventional fuel oil composed of DME alone was used (Comparative Example 1) and the case where the fuel oil according to Example 1 which was within the scope of the present invention was used. Operated for 200 hours using a fuel injection pump, and represented a plunger between the plunger and the plunger barrel, which has the most severe sliding conditions among these sliding parts. As shown in FIG. 1, the outer diameter (dpi) and inner diameter (db) were measured and the amount of wear was compared and evaluated. At the same time, the maximum fuel injection pressure was compared to evaluate changes in fuel injection performance.

Here, in the case of DME, aggressive wear that causes a problem can be evaluated in an extremely short time. Therefore, the operation time of 200 hours is set here. If no problem occurs within this time, it can be determined that this kind of problem does not occur even for a long time of several thousand to tens of thousands hours if the same conditions are maintained.

〔Evaluation results〕

Fig. 2 (a) shows the clearance between the plunger and the plunger barrel with respect to the operating time when using the fuel oil composed of DME alone in Comparative Example 1 and when using the fuel oil according to Example 1 that is within the scope of the present invention. Fig. 2 (b) shows an example of the change in C and a comparison of the example of the change in the maximum fuel injection pressure at that time.

An increase in the clearance indicates that the outer surface of the plunger or the inner surface of the plunger barrel is worn, and the maximum fuel injection pressure changes in the fuel injection performance due to the leakage of the compressed fuel due to the increase in the clearance (bad). The situation is shown.

As is clear from the results of Figs. 2 (a) and (b), when the fuel oil consisting of DME alone in Comparative Example 1 was used, the clearance of 10 m or more exceeded the allowable limit in a very short time. Although the wear progresses divergently, a problem occurs in the injection performance.However, when the fuel oil according to the first embodiment of the present invention is used, the wear due to slight penetration occurs at the initial stage. However, it can be seen that the clearance asymptotically approaches the allowable limit over time, the progress of wear is suppressed, and the injection performance is maintained.

The allowable wear limit 1 shown in this example is not necessarily a strict value, but varies depending on the engine type.However, if the clearance is at least 10 m or more, the injection performance will be affected. Are shown as an example. In the case of the fuel oil consisting of DME alone in Comparative Example 1,

Although it was observed that a vertical flaw was generated on the surface, when the fuel oil of Example 1 which falls within the scope of the present invention was used, generation of a vertical flaw that could be visually confirmed was not observed.

Therefore, by using the fuel oil of the embodiment 1 which is within the scope of the present invention, the wear of the fuel injection device which occurs when the fuel oil composed of the DME alone of the comparative example 1 is used is prevented, and the reliability which does not cause any practical problem It was found that the nature could be secured.

Here, the results are shown for an example between the plunger and the plunger barrel.However, there are also changes in the sliding parts between the face cam and roller in the distributive fuel injection pump and between the needle valve of the fuel injection valve and the main body. Although there is a difference in the time, it has been confirmed that the relationship between the amounts of wear is the same, and the effect of the present invention to ensure lubricity by the fuel oil is the same.

(Example 2 and Comparative Example 2)

Next, during a long-term operation, a part of the fuel oil may leak into the engine oil. Therefore, assuming such a case, the engine oil is used as a lubricant according to the present invention as follows. Regarding the deterioration of the engine oil in the case of containing the vegetable oil derivative (Example 2) and the case of containing the fatty acid type lubricant other than the vegetable oil derivative (Comparative Example 2), the oxidation stability test and the appearance were carried out by the following methods. Each evaluation was made.

The results are shown in Table 1 below.

(Test sample of Example 2)

Engine oil (lubricating oil for diesel engines manufactured by Nippon Oil Co., Ltd .; trade name “HD S-3”) was replaced with the vegetable oil derivative (purified oil fatty acid methyl ester) used in Example 1 above. Engine oil containing 1% by mass.

(Test sample of Comparative Example 2)

In place of the vegetable oil derivative of the test sample of Example 2 above, a fatty acid-based lubricant An engine oil prepared in the same manner as in Example 2 above, except that it contains 1% by mass of Chill Japan Co., Ltd .;

(Oxidation stability test, evaluation method of appearance)

Oxidation stability test is based on JISK 25 14-1996, Clause No. 4 of internal combustion engine lubricating oil oxidation stability (IS OT) test method, initial value, kinematic viscosity after 24 hours ( The evaluation was made at 40 ° (: 100 ° C.) The lower the change in the kinematic viscosity over time, the better the oxidation stability.

Regarding the appearance evaluation, the initial state and the state 24 hours later were visually evaluated by sensory evaluation. table 1

As is clear from the results in Table 1 above, the fuel oil lubricant (vegetable oil / fat derivative) of Example 2 which falls within the scope of the present invention is the fuel oil lubricant (Comparative Example 2) which falls outside the scope of the present invention. Compared to fatty acid-based lubricants), the change in kinematic viscosity of the engine oil after 24 hours was small, indicating excellent oxidation stability. In addition, no foreign matter was observed in the appearance. Industrial applicability

According to the fuel oil of the present invention, the fuel oil containing DME as a main component of the fuel oil contains at least one kind selected from vegetable fats and oils and derivatives thereof, particularly palm oil fatty acid methyl ester as a lubricant. This makes it possible to maintain a high level of lubricity, thus paving the way for commercial use of DME as a fuel oil, and further contributing significantly to environmental conservation. You.

Further, the fuel oil lubricant of the present invention does not promote deterioration of the engine oil even if it leaks into the engine oil.

Further, each fuel oil production facility of the present invention mixes a predetermined amount of DME and the above-mentioned lubricant by using a facility equipped with a stirrer having a usual mixer to thereby uniformly integrate the fuel oil of the present invention. It can be easily manufactured.

Claims

Range of request

1. A fuel oil comprising dimethyl ether and at least one selected from vegetable oils and fats and oil derivatives.

2. The fuel oil according to claim 1, wherein the vegetable oil is palm oil.

3. The fuel oil according to claim 1, wherein the vegetable fat derivative is a palm oil derivative.

4. The fuel oil according to claim 3, wherein the palm oil derivative is palm oil fatty acid methyl ester.

5. A fuel oil-based lubricant containing dimethyl ether as a main component, comprising at least one selected from vegetable oils and fat derivatives.

6. The fuel oil lubricant according to claim 5, wherein the vegetable oil is palm oil.

7. The lubricant for fuel oil according to claim 5, wherein the vegetable oil derivative is a palm oil derivative.

8. The fuel oil lubricant according to claim 7, wherein the palm oil derivative is palm oil fatty acid methyl ester.

9. A fuel oil production facility comprising a mixing facility for adding a predetermined amount of at least one selected from vegetable fats and oils and vegetable fat derivatives to dimethyl ether to obtain fuel oil.

10. A plant oil / fat derivative production facility for producing a vegetable oil / fat derivative from a vegetable oil / fat, and a predetermined amount of the vegetable oil / fat derivative obtained by the vegetable oil / fat derivative production facility is added to dimethyl ether to obtain a fuel oil. Fuel oil production equipment comprising a mixing equipment.