JPH05296926A - Measuring method for insoluble component contained in engine oil for ship - Google Patents

Abstract

PURPOSE:To measure insoluble components contained in engine oil for ships by measuring the absorption coefficient at a specific wavelength by using an infrared absorption spectrum. CONSTITUTION:The A-method pentane insoluble components specified by the standard of the Japanese Petroleum Institution (JPI) can be analyzed indicectly from the absorption coefficient of 1800-2200cm<-1>, especially 1960cm<-1> of an infrared absorption spectrum. Five samples respectively containing the used oil of a ship engine by 100%, 50%, 33.3%, 22.9%, and 16.2% are prepared by diluting the used oil with new oil and the relation between the 1960cm<-1> absorption coefficient and the concentration of the used oil is checked. An excellent correlation (linear relation) exists between the concentration of the used oil (the concentration of particles composed mainly of soot) and the 1960cm<-1> absorption coefficient. When the composition of the particles composed mainly of soot is the same, the containing level of the particles composed mainly of soot can be analyzed as an insoluble mater from the 1960cm<-1> absorption coefficient of the used oil. A total of 50 samples can be analyzed by one time of continuous operation when an automatic system provided with an auto-sampler is used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for measuring insoluble matter which is a measure of the degree of pollution of marine engine oil when the marine engine oil is actually used in a marine engine.

[0002]

2. Description of the Related Art The insoluble matter test together with the viscosity, flash point, total base number, water content, etc. of marine engine oil is an important item as a standard for knowing the pollution degree of marine engine oil when it is actually used for marine engine. .. In the method A of insoluble matter test according to the Japan Petroleum Institute standards (hereinafter referred to as JPI), the solvent of n-pentane (hereinafter abbreviated as pentane) is used to perform fractionation of insoluble matter, centrifugation, etc., but all are manual work. Therefore, it is a very complicated work that takes time and effort.

[0003]

Therefore, there is a demand for the development and establishment of a method for measuring insoluble matter in marine engine oil, which is easier and quicker than the insoluble matter test method according to the Japan Petroleum Institute standards. The present invention provides a method for measuring the insoluble content in marine engine oil, which is remarkably simple and quick in operation as compared with the conventional insoluble content test by JPI and can be continuously measured.

[0004]

Heretofore, there has been no known method for obtaining insoluble matter in marine engine oil by an infrared absorption spectrum (hereinafter referred to as IR) method. As a result of studying whether or not the IR method can be a method for measuring insoluble matter in marine engine oil, the present inventors found that the absorption coefficient at a certain specific wavelength and the value measured by the insoluble matter test by JPI were favorable. They found that there was a correlation, and completed the present invention. That is, the present invention relates to a method for measuring insoluble matter in marine engine oil, which uses an infrared absorption spectrum.

The present invention also relates to an infrared absorption spectrum of 180
The present invention relates to a method for measuring insoluble matter in marine engine oil, which comprises measuring an extinction coefficient at ⁰ to 2200 cm ^-1 .

The present invention is also directed to injecting marine engine oil and new oil into separate cells, measuring the respective transmittances, and correcting the oil transmittance based on the new oil transmittance. Characterize.

Furthermore, the present invention is also characterized by using an infrared absorption spectrum spectrophotometer by an automatic system with an autosampler attached.

The structure of the present invention will be described in detail below.

When an insoluble substance in pentane in the oil used is observed with an electron microscope, it is 0.1 to 10 as shown in the photograph of FIG.
Particles of about μm are observed. Light sources often used in the field of spectroscopic analysis include UV light, visible light, and IR light. FIG. 2 is a model of a state in which when soot-like particles are irradiated with light, the light is shielded by the difference in size of the particles.

The particle size of soot produced by the combustion of oil is initially said to be less than 0.1 μm, but gradually aggregates with the lapse of operating time, and as shown by an electron microscope observation photograph, 1 μm or more. Coarsening to 10 μm.
UV light with a wavelength of 0.25 μm, 0.5 μ
m of visible light and 5 μm of IR light are irradiated.
In the case of 1 μm particles, the wavelength is longer than the particle diameter, so that any light is transmitted.

When this becomes a particle of 1 μm, the particle diameter becomes U.
Since the wavelength is larger than the wavelength of V light or visible light, UV light and visible light are blocked and only IR light is transmitted. Further, when the particle size is 10 μm, any light is blocked and cannot be transmitted. Therefore, it is considered that the generation level of relatively large particles in the oil used can be investigated by using IR light having a wavelength of about 5 μm.

In the present invention, there is no absorption of oil itself, 1800
~ 2200 cm ^-1 , especially 1960 cm ^-1 (5.1 μm)
Was selected, the cell thickness was corrected according to the following equation, the extinction coefficient was determined, and the correlation with the A method pentane insoluble matter by JPI was examined.

Absorption coefficient (ABSORBANCE / c
m): log I _θ / I × 1 / b I _θ : transmittance of fresh oil at 1960 cm ⁻¹ I: transmittance of used oil at 1960 cm ⁻¹ b: cell thickness (cm)

For the measurement, an automatic system with an auto sampler attached was used. In addition, the used oil and the new oil are directly injected into separate fixed cells without solvent dilution, and the used oil is compensated with the new oil in two measurements (the transmittance of the used oil is corrected based on the transmittance of the new oil). Was used. The thickness difference between the fixed cells was corrected at the time of data processing by software for automatic correction.

Extinction coefficient by IR method and A by JPI
As a result of examining the correlation with the method pentane insoluble matter, the oil concentration used (concentration of soot-based particles) and 1800-2200
cm ^-1, a good correlation (linear relationship) is obtained in particular between extinction coefficient of 1960cm ^-1. This result 1800-22
00cm ^-1, especially JPI from extinction coefficient of 1960cm ^-1
According to the method A, pentane insoluble matter can be indirectly analyzed.

[0016]

EXAMPLES Examples of the present invention are shown below, but the present invention is not limited to the following examples. (Example 1) Table 1 shows the specifications of the IR spectrophotometer used in the present invention. It is an automated system with an auto sampler, which was devised by the present inventors.
The sample can be processed. The thickness of the fixed cell is usually 0.05m
Although the thickness can be arbitrarily selected within the range of m to 0.150 mm, a thickness of 0.096 mm to 0.104 mm was used.

[0017]

[Table 1]

The used oil and the new oil are directly injected into separate fixed cells without being diluted with a solvent, and the used oil is compensated with the new oil by two measurements (based on the transmittance of the new oil, the transmittance of the used oil To correct) was used. The difference in thickness between fixed cells was corrected at the time of data processing by the software for automatic correction according to the development of the present inventors. The measurement area was set to 4600 to 400 cm ^−1, and the absorption coefficient of the designated wave number could be measured by inputting the wave number required as data to the computer.

The samples used for the analysis were low sulfur fuel, medium sulfur fuel, high sulfur fuel, and cylinder dedicated oil, which serve as system oil and cylinder oil.

First, the relationship between the extinction coefficient at 1960 cm ^{-1 and} the particle concentration in oil was examined. HDS30 for marine engine oil
The oil used (manufactured by Nippon Oil Co., Ltd.) is diluted with fresh oil to obtain a used oil concentration of 100%, 50.0%, 33.3%, 22.9.
% And 16.2% of 5 samples were prepared, and 1960 cm ^-1
When the relationship between the extinction coefficient and the oil concentration used was investigated, Fig. 3
was gotten. FIG. 3 shows that there is a good correlation (linear relationship) between the oil concentration used (concentration of soot-based particles) and the absorption coefficient at 1960 cm ^−1. If they are the same, the oil used is 1960 cm ^-1
It is shown from the extinction coefficient of 1 that the content level of the particles mainly containing soot as an insoluble component can be analyzed.

(Embodiment 2) Next, the influence of wear metal was examined. It is considered that the wear metal powder present together with soot in the oil is separated as insoluble matter, but in order to confirm this, the metal content of the oil used before and after the insoluble matter test by the JPI method was analyzed and compared. .. ICP for metal analysis equipment
(Inductively coupled plus
ma) Using an emission spectrophotometer, the amount of wear metals in the oil used is Fe, Cr, Ni, Cu, Pb, Sn, Al, Na.
And the total of Si.

The analysis results are shown in FIG. According to this result, it was found that most of the wear metals in the oil used were not separated into the insoluble matter regardless of the amount, and remained in the oil after removing the insoluble matter.

Next, a quantitative analysis of wear metal in the insoluble matter obtained by the insoluble matter test was carried out. Results are shown in FIG. It was found that the proportion of wear metal in the insoluble matter tended to be high when the insoluble matter was small and was low when the insoluble matter was large, but in each case, it was found to be less than 4%.

Initially, it was thought that the wear metal has a large density, so even if the number of particles is small, it has a large effect on the weight of the insoluble matter. The metal content is very small and the wear metal is JP
It was found that the error factor in obtaining the correlation between the insoluble content by the method I and the extinction coefficient at 1960 cm ^-1 is not a large factor.

Example 3 Next, the effect of calcium sulfate was examined. Calcium sulfate is a neutralization product of sulfuric acid generated by combustion of a sulfur compound contained in fuel oil and a detergent contained in engine oil. Marine engine oils are selectively used according to the sulfur content in fuel oil, and the engine oil for high-sulfur fuels produces more calcium sulfate.

FIG. 6 shows various oils used before and after the insoluble matter test of the JPI method, as in the case of examining the effect of wear metals.
The absorption coefficient at 1150 cm ⁻¹ , which is the characteristic absorption of calcium sulfate, was determined and comparatively analyzed. from this result,
It was found that there was almost no change in the absorption coefficient at 1150 cm ⁻¹ regardless of the amount of calcium sulfate produced before and after the insoluble matter test. It is considered that most of calcium sulfate is not separated as an insoluble matter and is dispersed in the oil used as ultrafine particles.

However, the insoluble matter determined by the JPI method is considered to be such that a small part of the insoluble matter contained in the oil used is captured, as is clear even in the case of the metal of FIG. From the result of FIG. 6, it cannot be concluded immediately that it is not contained in the insoluble matter.

(Example 4) 1960 cm ^{-1 of} various oils used
The relationship between the extinction coefficient of A and the pentane insoluble matter in Method A by JPI was examined. The relationship between the insoluble content and the extinction coefficient at 1960 cm ⁻¹ was investigated for 59 types of engine oils that were actually collected from ships in transit. Four samples of marine engine oil, Super MDL UX, MX, SX, and HDS (all manufactured by Nippon Oil Co., Ltd.) were used as samples, and were randomly selected for analysis. The analysis result is shown in FIG. 7. The relationship between the two is linear, and the correlation coefficient is 0.9 when statistically analyzed.
3 was a good result. In addition, in 59 samples, although there was a high level of calcium sulfate to a low level of calcium sulfate, no deviation was considered to be due to the effect of calcium sulfate.

From the above results, it was found that the insoluble matter can be indirectly measured by obtaining the absorption coefficient at 1960 cm ^-1 . Further, it was confirmed that the accuracy of the insoluble matter test obtained from the IR method was within the tolerance of the test accuracy of the JPI method insoluble matter in most cases.

Example 5 An example of control analysis of oil used by the IR method is shown below. FIG. 8 shows the results of comparison of the pollution control analysis of the TES engine trial oil (trial manufactured by Nippon Oil Co., Ltd.) by the JPI method insoluble matter test and the IR method. This result shows that the change in the amount of insoluble matter with the replenishment of oil and the operation time is in good agreement with the transition of the absorption coefficient at 1960 cm ^-1 , and the IR method can be sufficiently used as a pollution control analysis method instead of the insoluble matter method. It is shown that.

FIG. 9 shows an example of the IR spectrum of the oil used, which is compensated with fresh oil. In this way, the IR method shows the level of pollution and at the same time oxidative deterioration products, nitrate esters, and sulfuric acid in the oil. The production level of calcium and the like can also be analyzed.

[0032]

INDUSTRIAL APPLICABILITY The method for measuring insoluble matter in marine engine oil by the IR method of the present invention shows good correlation with the method A for measuring pentane insoluble matter by the JPI method and is simpler and faster than the JPI method. There is also a method that can be continuously measured.

[Brief description of drawings]

FIG. 1 is an electron micrograph of oil used in a marine engine.

FIG. 2 is a model diagram when black particles block light.

FIG. 3 is a diagram showing the relationship between the HDS30 oil concentration and the 1960 cm ⁻¹ extinction coefficient.

FIG. 4 is a diagram showing metal components contained in oil used before and after an insoluble matter test.

FIG. 5 is a diagram showing a worn metal component contained in an insoluble component.

FIG. 6 is a diagram showing changes in an absorption coefficient of 1150 cm ^{−1 of} oil used before and after an insoluble matter test.

[Fig. 7] Insoluble matter of oil used and 1
It is a figure which shows the relationship of 960 cm < ^-1 > absorption coefficient.

FIG. 8 is a diagram showing a pollution degree management analysis result (1) of a TES engine trial oil.

FIG. 9 is a diagram showing an example of an IR spectrum of a used oil compensated with fresh oil.

Claims (5)

[Claims] 1. A method for measuring insoluble matter in marine engine oil, which comprises using an infrared absorption spectrum. 2. Infrared absorption spectrum 1800-220
The method for measuring insoluble matter in marine engine oil according to claim ¹ , wherein an extinction coefficient at 0 cm ^-1 is measured. 3. The marine engine oil used and the new oil are injected into separate cells, the respective transmittances are measured, and the used oil transmittance is corrected based on the new oil transmittance. The method for measuring insoluble matter in marine engine oil according to claim 1 or 2. 4. The method for measuring insoluble matter in marine engine oil according to claim 3, wherein the difference in thickness between the cells of the used oil and the fresh oil is automatically corrected. 5. The method for measuring insoluble matter in marine engine oil according to claim 1, wherein an infrared absorption spectrophotometer by an automatic system equipped with an autosampler is used.