KR20040094763A - Fuel oils, lubricants for fuel oils and productive facilities for fuel oils - Google Patents

Abstract

INDUSTRIAL APPLICABILITY The present invention provides fuel oils and fuels that can be used commercially with dimethyl ether as a fuel oil and contribute to environmental protection by maintaining high lubricity for fuel oils containing dimethyl ether as a main component of fuel oil. Provides useful lubricants and fuel oil manufacturing equipment.

The fuel oil of this invention consists of dimethyl ether and at least 1 sort (s) chosen from the group which consists of vegetable fats and oils and vegetable fats and oils derivatives. Examples of vegetable fats and oils that can be used include palm oil, palm oil, and the like, and examples of the vegetable fats and oils derivatives include, for example, monovalent to polyhydric alcohol esters of constituent fatty acids of the above vegetable fats and oils and alkylene oxide adducts thereof. And alkylene oxide adducts of the constituent fatty acids. Moreover, the lubricating agent for fuel oils which contains the dimethyl ether of this invention as a main component consists of at least 1 sort (s) chosen from the group which consists of said each vegetable fats and oils and vegetable fats and oils derivatives.

Description

FUEL OILS, LUBRICANTS FOR FUEL OILS AND PRODUCT FACILITIES FOR FUEL OILS}

In recent years, dimethyl ether (hereinafter abbreviated as "DME") has attracted attention as a new alternative fuel for gasoline, diesel, and heavy oil, which has a high cetane, contains oxygen atoms, and is non-combustible.

For example, diesel engines powered by DME can produce almost the same power as diesel fuel.However, unlike diesel fuel, DME has poor lubricity. It is pointed out that the problem that the sliding parts and the like become worn and its operation is difficult, and the use of DME as fuel oil has not been commercially successful yet.

On the other hand, in diesel fuel compositions having a sulfur content of about 0.2% by weight or less and an aromatic hydrocarbon content of less than about 30% by weight, as a lubricity improver, saturation derived from oil seeds of plants and A light oil composition is known which contains from 100 to 10000 ppm (by weight) of C _1-5 alkyl esters of unsaturated linear C _12-22 fatty acid mixtures (Japanese Patent Laid-Open No. 7-62363 (1995)). report).

However, the light oil composition described in the patent specification is for improving the lubricity in the case of using a special light oil composition (diesel fuel) having a sulfur content of about 0.2% by weight or less and an aromatic hydrocarbon content of about 30% by weight. A specific amount of alkyl ester of a mixture of saturated and unsaturated linear fatty acids derived from oily seeds of plants is added, and the fuel oil mainly containing DME of the present invention has different physical properties and lubricating properties. Unlike those special diesels and DMEs, the chemical structure itself is quite different.

SUMMARY OF THE INVENTION The present invention is intended to solve this problem in view of the above-described conventional problems, the present situation, and the like, and is suitable for a fuel oil mainly containing a DME that does not cause operation deterioration such as a fuel injection system due to abrasion. It is an object to provide a lubricant for fuel oil and a fuel oil production facility.

The present invention relates to a fuel oil mainly composed of dimethyl ether having a low environmental burden, a fuel oil lubricant suitable for the fuel oil, and a fuel oil production facility.

1 is a schematic diagram showing in a cross-sectional state the sliding portion between the plunger and the plunger barrel of the fuel injection pump in a diesel engine;

Fig. 2 (a) shows the plunger for the operation time when the fuel oil made of the DME alone according to Comparative Example 1 is used and when the fuel oil made of the fuel oil according to Example 1 falls within the scope of the present invention. Graph showing change in gap between plunger barrels

Fig. 2 (b) is a graph showing comparisons of changes in the respective fuel injection maximum pressures in the above case.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining about the said conventional subject, the present inventors discovered that the fuel oil, the fuel oil lubricant, and fuel oil manufacturing facilities of the said objective are obtained by adding a specific component to DME as a lubricant, It was completed.

That is, the present invention relates to the following items (1) to (10).

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

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

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

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

(5) A lubricant for fuel oil containing dimethyl ether as a main component, the lubricant for fuel oil comprising at least one member selected from the group consisting of vegetable oils and vegetable oils and derivatives.

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

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

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

(9) A fuel oil production facility, comprising: a dimethyl ether, a mixing equipment for obtaining a fuel oil by mixing a predetermined amount of at least one selected from the group consisting of vegetable fats and oils and vegetable fats and oils derivatives.

(10) A vegetable fat or oil derivative manufacturing facility for producing vegetable fat or oil derivatives from vegetable fats and oils and vegetable oil derivatives obtained in the vegetable fat or oil derivatives manufacturing facility, wherein a predetermined amount is mixed with dimethyl ether to obtain a fuel oil. Fuel oil manufacturing equipment.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Below, embodiment of this invention is described in detail.

The fuel oil of this invention consists of dimethyl ether and at least 1 sort (s) chosen from the group which consists of vegetable fats and oils and vegetable fats and oils derivatives.

The lubricant for fuel oil mainly containing dimethyl ether according to the present invention is characterized in that it comprises at least one member selected from the group consisting of vegetable fats and oils and vegetable fats and oils derivatives.

As DME used by this invention, the DME obtained from the synthesis gas mainly consisting of carbon monoxide and hydrogen obtained by reforming using natural gas as a raw material is mentioned, for example. In this case, there are two methods, a direct synthesis method from the synthesis gas and a method of first generating methanol from the synthesis gas and dehydrating the methanol. However, in the present invention, DME obtained from any method can be used.

Moreover, the synthesis gas which consists of carbon monoxide and hydrogen can be manufactured not only from natural gas but also from coal gasification gas, biomass, petroleum residue, industrial waste, etc., The synthesis gas obtained using these as a raw material may be sufficient. Usually, by each of the above methods, it is possible to obtain a DME having a purity of 90% or more, preferably 99% or more, more preferably 99.9% or more.

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

Examples of the vegetable fats and oils used in the present invention include palm oil, palm oil, rapeseed oil, olive oil, soybean oil, and the like, but these may be hydrogenated or non-hydrogenated.

Preferably, it is palm oil or palm oil from the point which exhibits another lubrication performance, Especially preferably, it is palm oil excellent in compatibility with DME.

In addition, the vegetable oil or fat derivative used by this invention means the derivative derived by performing chemical reaction with the said vegetable oil or fat. Specifically, the monohydric to polyhydric alcohol esters of fatty acids (hereinafter simply referred to as "constituent fatty acids") constituting the vegetable fat or oil derivatives, alkylene oxide adducts thereof, alkylene oxide adducts of the constituent fatty acids, etc. may be mentioned. Can be.

Examples of the monohydric to polyhydric alcohols of the monohydric to polyhydric alcohol esters include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, butylene glycol, pentaerythritol, triethylol propane, and sorbitol. Can be mentioned.

The production of these esters can be produced by conventional production methods such as transesterification of the fats and oils with a corresponding alcohol, and direct esterification of fatty acids constituting the fats and oils.

Among them, monohydric alcohol esters having 1 to 5 carbon atoms of fatty acids constituting vegetable oils, preferably monohydric alcohol esters having 1 to 5 carbon atoms of palm oil fatty acids, and especially methyl esters of palm oil fatty acids are suitable.

The alkylene oxide adduct of the monovalent to polyhydric alcohol ester of the fatty acid which comprises a vegetable fat or oil derivative, or the alkylene oxide adduct of the said constituent fatty acid is the said monovalent to polyhydric alcohol ester or the said constituent fatty acid and alkylene. It can be obtained by addition reaction with oxides.

As alkylene oxide, although ethylene oxide, a propylene oxide, butylene oxide is mentioned, for example, Preferably, they are ethylene oxide or a propylene oxide. These may be either single substances or mixtures.

The added mole number of these alkylene oxides is 1-100 mol, preferably 1-20 mol, More preferably, 1-5 mol per 1 mol of fats and oils or fatty acids.

In addition, the said vegetable oil and vegetable oil derivatives can be used individually or in mixture of 2 or more types, respectively.

The fuel oil of the present invention comprises at least one selected from the group consisting of the above-mentioned DME and vegetable oils and vegetable oil-derived derivatives as lubricants, but these blending ratios are preferably per 100 parts by mass of DME, vegetable oils and fats and oils. It is preferable to make at least 1 sort (s) chosen from the vegetable fats and oil derivatives into 0.001-100 mass parts, More preferably, you may be 0.002-50 mass parts.

In particular, palm oil fatty acid methyl ester is preferred because it is freely dissolved in 100 parts by mass of DME within the range (0.001 to 100 parts by mass) to form a homogeneous liquid.

Moreover, if the compounding quantity of at least 1 sort (s) chosen from the group which consists of the said vegetable oil and vegetable oil derivative is less than 0.001 mass part, it is not possible to exhibit the effect of this invention. On the other hand, when it exceeds 100 mass parts, since the effect of this invention does not change and cost becomes high, it is not preferable. Therefore, even if it is less than 0.001 mass part and exceeds 100 mass parts, it is not preferable.

As described above, the fuel oil of the present invention is composed of at least one selected from the group consisting of DME, vegetable oils and vegetable oil derivatives as lubricants, and various types of fuel oils added to the fuel oil within a range that does not impair the effects of the present invention. It is possible to add an optional component, for example, an antioxidant, an oil enhancer, a rust preventive agent, a cleaning dispersant, a friction modifier, an antifoaming agent, a fluidity improving agent, a viscosity index improver, and the like.

The fuel oil and fuel oil lubricant of the present invention configured as described above can be used as a lubricant for fuel oil or fuel oil for various uses, such as for power generation, household, diesel engine, etc. as a substitute for gasoline, light oil and heavy oil. In particular, it is suitable as a lubricant for fuel oil or fuel oil of diesel such as trucks, ships, power generation, construction equipment.

When the fuel oil of the present invention is used as fuel oil of a diesel engine, for example, in the case of DME only (DME alone), the engine is damaged in a short time of about 10 to 20 hours due to abrasion of the sliding part. In the fuel oil of the present invention, it is possible to maintain normal operation without any problem even in a long continuous operation such as thousands to tens of thousands of hours.

Next, the fuel oil production equipment of the present invention mixes a predetermined amount of at least one selected from the group consisting of the vegetable fats and oils and vegetable fats and oils derivatives to the DME obtained by the above-described methods, specifically, per 100 parts by mass of the DME. And at least one selected from the group consisting of vegetable fats and oils and vegetable fats and oils derivatives is provided with a mixing facility for obtaining fuel oil by mixing 0.001 to 100 parts by mass.

As this fuel oil production facility, the DME obtained by each said method is supplied to the stirring apparatus (tank) equipped with a mixer through a pipeline, for example, and it consists of the said vegetable oil and vegetable fat derivatives in this stirring apparatus. The thing provided with the manufacturing equipment which adds the predetermined amount at least 1 sort (s) selected from the group, and stir-mixes is mentioned.

In addition, another fuel oil production facility of the present invention is a mixture obtained by mixing a vegetable oil derivative production facility for producing a vegetable oil derivative from vegetable oil and a vegetable oil derivative derived from the vegetable oil derivative production facility with a predetermined amount in DME to obtain a fuel oil. It is characterized by the installation of equipment.

As this fuel oil manufacturing equipment, for example, the vegetable fats and oils derivative manufacturing plant which chemically reacts with the said vegetable fats and oils and manufactures a vegetable fats and oils derivative, the vegetable fats and oil derivatives obtained by this vegetable fats and oils derivative manufacturing facility, and the said each method obtained The thing provided with the mixing apparatus which supplies each predetermined amount of DME to a stirring apparatus provided with a mixer, and stir-mixes is mentioned.

In each of the fuel oil production facilities of the present invention configured as described above, the fuel oil of the present invention, which is a uniformly integrated liquid, is easily mixed by mixing a predetermined amount of the lubricant with dimethyl ether by a facility equipped with a stirring device having an ordinary mixer. It becomes possible to manufacture easily. Therefore, it is preferable to install the fuel oil production facility of the present invention adjacent to the installation location of the production facility for vegetable oils and fats (and derivatives thereof), in particular in view of reducing the transmission cost.

Next, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited to the following Example.

Example 1 and Comparative Example 1

The following were used as a test sample about the DME used for each fuel oil of Example 1 and the comparative example 1, and the vegetable fats and oils derivative as a lubricant.

[DME]

A DME having a purity of 99.9% manufactured by Mitsubishi Gas Kagaku Co., Ltd. was used as a test sample.

[Vegetable fat or oil derivative (palm oil fatty acid methyl ester)]

356 g of methanol and 3 g of sodium hydroxide were added to 1014 g of palm oil, and a transesterification reaction was carried out for 60 minutes at a pressure of 0.1 MPaG or more and 70 ° C under a nitrogen gas atmosphere. After cooling, glycerin was separated, and 50 g of methanol and 1 g of sodium hydroxide were added, followed by transesterification at 60 캜 for 10 minutes at atmospheric pressure.

Subsequently, 160 g of water was added, and after stirring, the mixture was left still to separate glycerin to remove crude palm oil fatty acid methyl ester. The ester thus obtained was topping at 155 ° C. under atmospheric 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, fuel oil consisting of 100 parts by mass of the DME and 10 parts by mass of the vegetable oil or fat derivative (palm oil fatty acid methyl ester) was used.

In the comparative example 1, the fuel oil which consists of said DME 100 mass% was used.

Using the fuel oil of the said Example 1 or the comparative example 1, and the diesel engine of the following structure, the actual operation test of the diesel engine was done by the following evaluation method, and the said fuel was evaluated.

[Assessment Methods]

An industrial direct injection diesel engine was used for the evaluation.

In this diesel engine, as a part of the fuel lubricity, the sliding portion between the plunger and the plunger barrel in the jerk type fuel injection pump and the plunger barrel between the plunger and the plunger barrel in the distribution type fuel injection pump. The sliding portion between the face cam and the roller together with the sliding portion, and also the sliding portion between the needle valve and the main body of the fuel injection valve which are shared in any of these cases.

The wear state of these parts greatly affects the fuel injection performance, and if the wear is greater than any value, the fuel injection characteristics deteriorate, the engine performance is impaired, and in some cases, engine operation may be impossible.

Therefore, in this evaluation, when the fuel oil made of the conventional DME alone was used (Comparative Example 1) and when the fuel oil manufactured in Example 1, which is the scope of the present invention, was used, the engine was actually used. The fuel injection pump was operated for 200 hours, and among the sliding parts, assuming that the plunger and the plunger barrel having the most sliding condition were the representative parts for evaluation, in each case as shown in FIG. The outer diameter d _p 1 and the inner diameter d _b of the plunger barrel were measured to evaluate the amount of wear. At the same time, the maximum fuel injection pressure was compared to evaluate the change in fuel injection performance.

In the case of DME, aggressive wear as a problem can be evaluated in a very short time. Therefore, an operating time of 200 hours is set here. If a problem does not occur within this time, it can be judged that this kind of problem does not occur even for a long time of several thousand to tens of thousands of hours as long as the conditions are maintained.

[Evaluation results]

2 (a) between the plunger and the plunger barrel for the operation time when the fuel oil made of the DME alone used in Comparative Example 1 and the fuel oil used in Example 1, which is the scope of the present invention, are used. An example of change in clearance C is shown, and an example of change in each fuel injection maximum pressure in this case is shown in FIG. 2B for comparison.

The increase in the gap indicates that the outer surface of the plunger or the inner surface of the plunger barrel is worn, and the maximum fuel injection pressure is changed due to the leakage of compressed fuel due to the increase in the gap. ) Indicates the situation.

As apparent from the results shown in Figs. 2 (a) and 2 (b), when the fuel oil made of the DME alone used in Comparative Example 1 was used, it became a gap of 10 µm or more exceeding the allowable limit in a very short time and abrasion. When the fuel oil produced in Example 1 in the scope of the present invention is used, the wear caused by the adjustment of the machine slightly occurs initially. However, as time passes, it gradually approaches the gap within the allowable limit, and it can be seen that the progress of wear is suppressed and the spraying performance is also maintained.

The wear tolerance of 10 µm shown in this example is not necessarily a universal value and may vary depending on the engine type. In the case of a gap of at least 10 µm or more, the spraying performance may be hindered, and this is shown as an example.

In addition, in the case of the fuel oil made of the DME alone used in Comparative Example 1, it was observed that the scratches in the longitudinal direction were clearly generated on the surface of the plunger, but using the fuel oil produced in Example 1, which is the scope of the present invention. In this case, no visible longitudinal scratches were observed.

Therefore, by using the fuel oil manufactured in Example 1, which is within the scope of the present invention, wear of the fuel injection device generated when the fuel oil made of the DME alone used in Comparative Example 1 is prevented, and practical problems are eliminated. It can be seen that it is possible to secure reliability that does not occur.

In addition, although the result was shown about the example of the site | part between a plunger and a plunger barrel here, a change is also made to the sliding part between the face cam and roller in a distribution type fuel injection pump, and the needle valve and main body of a fuel injection valve. Although there is a difference in time, it has been confirmed that the relationship between the amount of wear is the same, and in these cases, the effect of securing lubricity by the fuel oil of the present invention is similarly obtained.

Example 2 and Comparative Example 2

Next, when a long period of operation, part of the fuel oil may leak into the engine oil, assuming such a case, when the vegetable oil derivative as a lubricant according to the present invention is added to the engine oil (Example 2) And deterioration of the engine oil observed when fatty acid-based lubricants other than the vegetable oil and fat derivatives were added (Comparative Example 2), each evaluation was performed for the oxidation stability test and the appearance by the following method.

These results are shown in Table 1 below.

Test Sample of Example 2:

To the engine oil (lubricant for diesel engines manufactured by Nippon Oil Corporation; trade name "HDS-3"), the vegetable fat or oil derivative (palm oil fatty acid methyl ester) used in Example 1 was added at a ratio of 1% by mass with respect to engine oil. Manufactured by engine oil.

Test sample of Comparative Example 2:

The same method as in Example 2, except that a fatty acid-based lubricant (ethyl japan company name: "High Tech 4140") was added at a rate of 1% by mass, in place of the vegetable fat or oil derivative used for the test sample of Example 2. An engine oil was prepared.

Oxidation stability test and evaluation method:

The oxidation stability test evaluated the kinematic viscosity (40 degreeC, 100 degreeC) in the initial state and after 24 hours according to the test method of the lubricating oil oxidation stability (ISOT) for the internal combustion engine of Article 4 of JISK2514-1996. In addition, the lower the change in the numerical value of the kinematic viscosity with time, the better the oxidation stability.

In addition, about the external appearance evaluation, the initial state and the state after 24 hours were performed by the sensory evaluation by visual observation.

Example 2 Comparative Example 2 Measuring time Initial value 24 hours later Initial value 24 hours later Oxidation Stability Kinematic Viscosity (40 ° C) ² / s 90.5510.77 93.2210.94 94.6510.98 113.412.98 Exterior Uniformity and transparency Uniformity and transparency Uniformity and transparency Minute foreign bodies observed

As is apparent from the results of Table 1, the lubricant for fuel oil (vegetable oil and fat derivative) used in Example 2, which is the scope of the present invention, is a lubricant for fuel oil (fatty acid-based lubricant) used in Comparative Example 2 outside the scope of the present invention. Compared with this, since the change of the kinematic viscosity of the engine oil is small after 24 hours, it turns out that it is excellent in oxidative stability. In addition, no foreign matter was observed in appearance.

According to the present invention, the lubricity is highly maintained by adding at least one selected from the group consisting of vegetable fats and oils and vegetable fats and oils derivatives, especially palm oil fatty acid methyl ester, as a lubricant to fuel oils containing DME as a main component of fuel oil. Therefore, the present invention can develop a route which makes DME a fuel oil commercially available, and contributes greatly to environmental conservation.

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

Moreover, each fuel oil manufacturing facility of this invention can easily manufacture the fuel oil of this invention which was uniformly integrated by mixing a predetermined amount of the said lubricant with DME by the installation provided with the conventional stirring apparatus with the mixer. Do.

Claims (10)

A fuel oil comprising dimethyl ether and at least one selected from the group consisting of vegetable oils and vegetable oil derivatives. The fuel oil according to claim 1, wherein the vegetable oil or fat is palm oil. The fuel oil according to claim 1, wherein the vegetable oil or 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. A fuel oil lubricant having a dimethyl ether as a main component, the lubricant for fuel oil comprising at least one member selected from the group consisting of vegetable oils and vegetable oils and derivatives. 6. The lubricant for fuel oil according to claim 5, wherein the vegetable fat or oil is palm oil. The lubricant for fuel oil according to claim 5, wherein the vegetable oil or fat derivative is a palm oil derivative. 8. The lubricant for fuel oil according to claim 7, wherein the palm oil derivative is palm oil fatty acid methyl ester. A fuel oil production facility, comprising: a dimethyl ether, a mixing equipment for obtaining a fuel oil by mixing a predetermined amount of at least one selected from the group consisting of vegetable oils and vegetable oils and derivatives. Production of a vegetable oil derivative manufacturing facility for producing vegetable oil derivatives from vegetable oil and a plant for producing a fuel oil characterized in that the mixing equipment for obtaining a fuel oil by mixing a predetermined amount of vegetable oil derivatives obtained in the vegetable oil derivatives manufacturing equipment to dimethyl ether equipment.