JP2016045078A - Sampling device of heavy oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sampling device capable of sampling a high viscosity fluid such as a heavy oil highly accurately by a simple method by using a four-way valve.SOLUTION: In a device for sampling a heavy oil flowing in a pipe, sampling of a heavy oil is performed by switching a passage in a four-way valve. The four-way valve has a valve part inside capable of switching a passage by rotation, and a first passage is switched to/from a second passage by rotation of the valve part, and a peripheral part of a through hole on the outer surface of the valve part is brought into contact with a seal material before/after switching of the two passages.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a heavy oil sampling device.

  Coal tar, which is a heavy oil, and coal tar pitches, which are coal tar derivatives (soft pitch, medium pitch, hard pitch, etc.), are produced as by-products when carbonizing coal in a coke oven. Including the pitch obtained from the process). In the oil refining process, there is a petroleum pitch that is generated as heavy oil when crude oil is distilled to obtain naphtha, kerosene, light oil and the like. Since these coal tar pitches and petroleum pitches have high viscosity, they tend to adhere to the sampling nozzle and the sample can and are difficult to handle.

  Conventionally, since these samplings are extracted directly from the manufacturing process, they are collected at a scale of kg, and an amount of about 1000 times or more of the sample amount required for performing the analysis is sampled. On the other hand, in recent years, due to the improvement in accuracy of analytical instruments, the amount of test samples has been reduced, but it is difficult to accurately weigh small amounts of heavy oil that has high viscosity and solidifies at low temperatures. A great deal of effort is expended to obtain a sample amount for use in an analytical instrument. In the past, a method of sampling a small amount of coal tar pitches has been proposed in order to measure solvent-insoluble components in plants (processes) that handle coal tar and coal tar pitches.

  For example, combine two three-way valves, let coal tar pitches flow, fill the pipe connecting the three-way valves with one end coal tar pitch, and switch the flow path of the two three-way valves A method of sampling with a fluid (solvent) that is soluble in coal tar pitch has been proposed (Patent Document 1).

JP 2012-251998 A

In patent document 1, since the capacity | capacitance of the piping which connects between two three-way valves becomes a sampling amount, it was difficult to perform very small samplings, such as 1 cm < ³ > or less. In addition, when the sampling amount increases, coal tar pitches that are not washed away by the solvent may remain in the pipe, or when measuring the solvent insoluble matter, two more diluted solutions after sampling are used. Since it is necessary to sample and dilute using a way valve, there is a problem that high sampling accuracy cannot be secured.

  On the other hand, after coal tar pitches are passed through the four-way valve and the flow path of the four-way valve is filled with the coal tar pitch, the flow path is switched and dissolved in the coal tar pitch, etc. A method of sampling by flushing with a fluid exhibiting the property can be considered.

In the method using a four-way valve, the coal tar pitch of the flow path in the four-way valve can be used as a sample, so that the sampling amount can be a very small amount of 1 cm ³ or less. With this method, it is expected that errors due to coal tar pitches remaining in the piping and errors due to not being swept away by the solvent are eliminated. However, when the sampling amount is reduced, a new problem arises that the sampling amount itself varies and the error increases. For this reason, there is a problem that a high sampling accuracy cannot be ensured by using only a four-way valve.

  Therefore, the present invention uses a four-way valve, a high-viscosity fluid such as coal oil, coal tar pitches or heavy oil containing petroleum-based pitches generated from petroleum, etc. in a simple method, and It is an object of the present invention to provide a sampling device capable of sampling with high accuracy.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a sampling accuracy because the viscosity of heavy oil is high by using a four-way valve in which the valve portion is in contact with the sealing material in any direction. The present inventors have found that even a sample that is difficult to raise can be sampled with a very small amount accurately, and have completed the present invention.

That is, the gist of the present invention resides in the following [1] to [10].
[1] A device for sampling heavy oil flowing in a pipe, wherein the sampling of the heavy oil is performed by switching the flow path of a four-way valve, and the four-way valve has four pipe connection ports. In addition, a valve portion that can switch the flow path by rotation is provided inside, and the valve portion has a through hole that penetrates the inside, and each of the through holes has the four pipe connection ports. The two pipes connected to the two pipe connection ports can be communicated to form the first flow path, and by rotating this valve portion, the through-hole is formed in the four pipes. Two pipes connected to the other two pipe connection ports among the connection ports can be communicated to form the second flow path, and before and after the two flow paths are switched by the rotation of the valve portion. In, the through hole in the outer surface of the valve portion Peripheral portion, the sampling device of heavy oil, characterized in that in contact with the sealing member.

[2] The seal material is a member that fills a space between the valve portion and a housing that houses the valve portion, and rotates the four pipe connection ports of the four-way valve and the valve portion. The heavy oil sampling device according to [1], wherein the member is a member having a hole formed in a portion through which an operation shaft for passing is passed.
[3] A structure in which the four-way valve is sandwiched between the two open / close valves by disposing an open / close valve in each of two pipes constituting the first flow path [1] or [2] ] The heavy oil sampling device as described in the above.

[4] The heavy oil sampling device according to [3], wherein the heavy oil is transferred through the first flow path and the solvent is transferred through the second flow path. .
[5] The heavy oil to be sampled is shut off from the line by closing the two on-off valves while the heavy oil is transferred to the first flow path, and the heavy oil to be sampled The heavy oil sampling device according to [4], wherein the amount of the quality oil is 1 cm ³ or less.
[6] By closing the two on-off valves, the heavy oil stored in the through-hole is switched to the second flow path by switching the four-way valve by rotating the valve portion, The heavy oil sampling device according to [5], wherein the heavy oil sampling device has a structure of being transferred together with a solvent.

[7] The heavy oil sampling device according to any one of [1] to [6], which is used for sampling heavy oil having a viscosity at 100 ° C. of 15000 mPa · s or less.
[8] The heavy oil according to any one of [1] to [7], wherein the heavy oil contains any one selected from coal tar, coal tar pitch, and petroleum pitch. Sampling device.
[9] The heavy oil sampling device according to any one of [4] to [8], wherein the solvent contains quinoline.
[10] The heavy oil sampling device according to any one of [1] to [9], wherein an inner diameter of the pipe is 10 mm or less.

  In the sampling of heavy oil, the present invention uses a four-way valve in which the valve part (ball) of the four-way valve is in contact with the sealing material in any direction, and is collected from the valve part (ball) of the four-way valve. By extruding heavy oil with a solvent, a very small amount of heavy oil with high viscosity can be sampled accurately.

(A) Partial sectional view showing an example of a four-way valve used in the heavy oil sampling device of the present invention, (b) Perspective view showing an example of a sealing material used in the four-way valve of the present invention (A) Partial sectional view of the four-way valve shown in FIG. 1 (a), (b) Partial sectional view consisting of the bb section of (a) Process diagram showing an example of sampling and measurement processes using the heavy oil sampling device of the present invention (A) Perspective view of sealing material used for conventional 4-way valve, (b) Partial cross-sectional view showing an example of a conventional 4-way valve, (c) Partial cross-sectional view consisting of cc cross-section of (b)

Hereinafter, the present invention will be described in more detail with reference to the embodiments. However, the present invention is not limited to these embodiments as long as the gist thereof is not exceeded.
The present invention is a sampling device that performs sampling of high-temperature and high-viscosity heavy oil flowing in a pipe by switching the flow path of a four-way valve, and more accurately samples a minute amount.

[Heavy oil]
The heavy oil is not limited as long as it is generally called heavy oil. Specifically, coal tar, coal tar pitches that are coal tar derivatives (soft pitch, medium pitch, hard pitch, and other various processes) In addition to the pitch obtained from the petroleum refining process, and the coal tar, the coal tar pitch, and the petroleum pitch are generated from the coal tar refining process or the petroleum refining process. Also included is a mixture of light oil (fraction other than heavy oil). The coal tar is preferably coal tar obtained by gradually cooling a coke oven gas produced in a coke oven for crude steel and condensing one having a high boiling point. The coal tar pitches are obtained by removing light aromatic components by distillation of coal tar, preferably coal tar obtained from the above-mentioned coke oven.

  The petroleum-based pitches generated from the petroleum refining process are preferably atmospheric distillation residual oil or vacuum distillation residual oil in the petroleum refining process, including residual oil obtained by treating these residual oils with a fluid catalytic cracking apparatus. It is. These pitches and the like may contain aromatic components, alkyl side chains, heterocyclic compounds, sulfur, nitrogen, oxygen and the like.

The heavy oil to be sampled in the apparatus of the present invention preferably contains at least one selected from coal tar, coal tar pitches, and petroleum pitches, and may be a mixture thereof. . Further, it may be a mixture of a plurality of coal tars, a mixture of a plurality of coal tar pitches, or a mixture of a plurality of petroleum pitches.
Moreover, as a measurement sample, pitches etc. and arbitrary compounds other than a solvent and a single-piece | unit may be contained.

(Viscosity of heavy oil)
The viscosity of the heavy oil is not limited, but in order to prevent clogging of the piping, the viscosity at 100 ° C. is preferably 15000 mPa · s or less, more preferably 13000 mPa · s or less, and even more preferably 10000 mPa · s or less. desirable. Here, the viscosity of heavy oil refers to a value measured with a B-type viscometer.

[solvent]
The sampling apparatus of the present invention can use a solvent when sampling the heavy oil. Here, the “solvent” does not need to dissolve the heavy oil uniformly, and may be a suspension in a mixed state with the heavy oil. It is preferable that at least a part of the components to be dissolved is dissolved.
Examples of the solvent include quinoline, toluene, N-methylpyrrolidone, pyridine, acetone, hexane, nitrobenzene, morpholine, chloroform, alcohol, and the like, preferably quinoline, toluene, pyridine, N-methylpyrrolidone, Quinoline is more preferable from the viewpoint of high solubility in heavy oil.
The method of using the solvent in the sampling apparatus of the present invention is not limited, and may be used to dilute the heavy oil to be sampled in advance, or extrude the heavy oil inside the pipe or inside the valve as described later ( May be used to wash out). Further, it may be used for cleaning the inside of the sampling apparatus.

[Sampling method of heavy oil]
As a sampling method of the above heavy oil, there are generally a method of sampling by liquid feeding by a metering pump or switching a flow path of heavy oil and a solvent by combining three-way valves. Since the viscosity of heavy oil is high, it is difficult to stably feed a small amount of heavy oil. Furthermore, since the sludge contained in heavy oil bites into the cylinder part which controls quantitativeness, there is a problem that the probability of failure is high. In sampling using a three-way valve, the sampling amount is determined depending on the length and diameter of the pipe connecting the two three-way valves. For this reason, in order to reduce the sampling amount, it is necessary to shorten the length of the pipe. However, since the distance between the connection portion of the three-way valve and the pipe is required, it is not less than a certain length. Although the sampling amount can be reduced by reducing the pipe diameter, there is a problem in that the pipe is blocked by pitch sludge if the pipe diameter is reduced. Therefore, since the sampling amount exceeds 1 cm ³ , it is necessary to perform dilution when analyzing the sampled heavy oil, and it cannot be said that the sampling is a small amount.
On the other hand, the method of sampling by switching the flow path of heavy oil and a solvent using a four-way valve is mentioned. In sampling using a four-way valve, the volume of the valve part (ball) of the four-way valve becomes a sampling volume, so that a small amount of sampling of 1 cm ³ or less is possible, which is desirable.

[4-way valve]
By the way, this four-way valve 1 has four pipe connection ports 5a, 5b, 5c, 5d as shown in FIG. 1 (a) and FIG. 2 (a) (b), and four pipes 5a ′, 5b ', 5c', and 5d '. Further, a flow path (a first flow path F flowing from the pipe 5a ′ to the pipe 5b ′ and a second flow path S flowing from the pipe 5c ′ to the pipe 5d ′) is rotated in the housing 2 of the four-way valve 1. It has a valve part (ball) 3 that can be switched, and this valve part 3 has a through hole 3a that penetrates through the inside. The through holes 3a are connected to the two pipe connection ports 5a and 5b among the four pipe connection ports 5a, 5b, 5c and 5d, respectively, and the pipes 5a 'and 5b' are communicated with each other. One flow path F can be formed, and by rotating the valve portion 3, the through hole 3a is connected to the other two pipe connection ports 5c and 5d among the four pipe connection ports. The second flow path S is configured by connecting the pipe 5c ′ and the pipe 5d ′.

  In FIG. 2B, the through hole 3a is formed in a straight line, but the through hole 3a has a structure in which a flow path is formed by piping adjacent to the valve portion in the direction of 90 degrees. There may be. That is, a structure in which the first flow path F is formed by the pipe connection ports 5a and 5c and the second flow path S is formed by the pipe connection ports 5b and 5d in FIG. However, with such a structure, when the flow path of the valve unit 3 is switched, leakage or leakage into the second flow path is likely to occur, so that an error may occur in the sampling amount. This is a structure in which the through hole 3a is connected to the pipe in the direction of 90 degrees. In order to switch the flow path, a rotation of 180 degrees is necessary. This is because the second flow path and the other end are in contact with the first flow path. For this reason, it is preferable that the through-hole 3a is formed linearly.

  By the way, in a normal four-way valve, a ring-shaped sealing material 6 having a thickness as shown in FIG. 4A is used. As shown in FIGS. 4B and 4C, the seal material 6 is connected to the end edges of the pipe connection ports 5 a and 5 b so that the pipe connection ports 5 a and 5 b communicate with the through hole 3 a of the valve portion 3. Provided. For this reason, in the state where the through hole 3a of the valve portion 3 communicates with the first flow path F, the peripheral edge portion of the outer surface of the through hole 3a is in close contact with the sealing material 6, but is in communication with the second flow path S. Then, the peripheral part of the outer surface of the through-hole 3a will be in the state where the sealing material 6 is not arranged. For this reason, if sampling is repeated using this four-way valve, the rotation of the valve portion 3 is repeated, and the heavy oil is placed in the gap portion between the housing 2 and the valve portion 3 inside the sealing material 6. There is a problem that sampling accuracy deteriorates due to the accumulated heavy oil.

  In this invention, before and after the two flow paths (the first flow path F and the second flow path S) are switched by the rotation of the valve section 3, the peripheral edge of the through hole 3a on the outer surface of the valve section 3 The part should be in close contact with the sealing material. Thereby, even if the rotation of the valve portion 3 is repeated, it is possible to prevent heavy oil from being accumulated in the gap portion between the housing 2 and the valve portion 3.

  As an example of this sealing material, the sealing material 7 as shown in FIG. 1B, that is, the inner shape of the housing 2 in which the valve portion 3 of the four-way valve 1 is accommodated as an outer diameter, The valve portion 3 can be accommodated and has a gap portion that can be in contact with the valve portion 3 on the entire surface, and further, the position connected to the four pipe connection ports 5a, 5b, 5c, and 5d, and the valve portion 3 is rotated. This is a member in which a hole is made in a portion through which the operation shaft 4 passes. This sealing material 7 is in a state of filling the space between the housing 2 housing the valve portion 3 and the valve portion 3.

  When this sealing material 7 is used, the valve part (ball) 3 of the four-way valve is placed on the outer surface of the valve part 3 before and after the two flow paths (first flow path F and second flow path S) are switched. Since the peripheral edge of the through-hole 3a is in intimate contact with the sealing material 7, there is no reservoir in which the heavy oil can be accumulated in the gap between the housing 2 and the valve 3, and the quantitative accuracy is improved. Can demonstrate.

When the material and shape of the housing 2 have a function as a sealing material, the sealing material 7 may be replaced by the housing 2 itself. That is, the housing 2 and the sealing material 7 may be inseparably integrated. In other words, a structure in which the housing is formed by the structure itself as shown in FIG.
Moreover, there is no restriction | limiting in the shape and structure of a valve in a 4-way valve. As the structure of the valve, as shown in FIG. 1 (a), a valve portion 3 having a through hole formed in a ball shape may be used, or a disc-shaped valve is rotated by an operation shaft 4. There may be. However, in the present invention, since it is preferable that the heavy oil stored in the valve can be pushed away by switching the flow path, a ball-shaped valve is preferable.

[Temperature and viscosity of heavy oil]
The temperature of the heavy oil flowing through the four-way valve is preferably 100 to 300 ° C. for the purpose of lowering the viscosity. However, the resistance of the heavy oil flowing through the pipe is reduced by reducing the resistance when the pipe is passed through. For the purpose of lowering, the temperature is preferably 120 to 260 ° C, more preferably 130 to 200 ° C.

(Viscosity at the time of heavy oil transfer (at transfer temperature))
When flowing heavy oil through the four-way valve, the viscosity of the heavy oil at the temperature at that time is not limited, but is preferably 15000 mPa · s or less, more preferably 13000 mPa · s or less, in order to prevent clogging of the piping. More preferably, it is desirable that the pressure be 10,000 mPa · s or less. Here, the viscosity measurement is a value measured with a B-type viscometer, but it is difficult to directly measure the viscosity of heavy oil flowing in the four-way valve. What is necessary is just to measure with a B-type viscometer as the same conditions as the inside of a valve.

[Measurement sample]
The heavy oil sampled by the sampling device of the present invention is usually subjected to some analysis (measurement) as a measurement sample.
Although the method for mixing the solvent and the heavy oil is not particularly limited, it is preferable to mix the heavy oil with stirring because the heavy oil has high viscosity.
Alternatively, a part of the solution obtained by the stirring may be extracted, and a solution obtained by further diluting the extracted solution may be used as a measurement sample. Here, the “solution” is not limited to a solution that is uniformly dissolved by a solvent, but also includes a suspension.

[Measuring means]
The measurement sample is subjected to analysis as it is or after distillation and / or filtration for the purpose of dissolution or solvent removal depending on the analysis method to be performed. As an example of this measuring method, a method of measuring absorbance can be mentioned as an example.

When the method for measuring absorbance is adopted, the content ratio of the solvent-insoluble matter contained in the mixed solution (measurement sample) of the heavy oil and the solvent is in the range from the wavelength of visible light to the wavelength range of infrared light. It can be calculated using an absorptiometer capable of measuring absorbance.
The absorptiometer preferably includes a sensor that simultaneously measures the absorbance at the measurement wavelengths in two or more wavelength regions.

That is, irradiating the measurement sample with a predetermined one light in the wavelength region of infrared light from the wavelength of visible light, measuring the absorbance at that wavelength, and calculating the content ratio of the solvent-insoluble content from the absorbance. Can do.
In addition, the measurement sample is irradiated with light in the wavelength region from visible light to near-infrared light and infrared light, the absorbance at each wavelength is measured, and the solvent-insoluble content is contained from the ratio of absorbance. The percentage can be calculated.

  By using an absorbance measurement sensor based on visible, near infrared, or infrared spectrum, it can be applied to coal tar pitches with color tone changes that are not good for light and laser measurement methods. In addition, it can be used for measuring the absorbance of a solution containing multiple components. An example of such an absorbance measurement sensor is Chino Co., Ltd .: IM series Model 3192.

The sample measurement cell used in the method of the present invention may be any cell that is usually used for the measurement sample. For example, if the measurement sample is liquid, a commercially available liquid cell for visible and infrared analysis (cell length 0) is used. 0.02 to 10 mm) can be used.
Moreover, it is also possible to install a flow cell in a spectroscope and to continuously measure the solvent insoluble content in the sample by passing the sample continuously therethrough. By adjusting the width of the cell, the measurement sample can be continuously circulated without staying in the cell even when the flow cell is used. It is also relatively easy to use a cell that can withstand high-temperature and high-pressure conditions that are often required during continuous analysis. Any conventionally used flow cell can be used.

  The distance between the spectroscope and the measurement sample need not be limited as long as the absorbance can be calculated, but is preferably 20 to 400 mm, more preferably 100 to 300 mm.

  When the method for measuring absorbance is employed, it is preferable to use 400 to 1500 nm and 1700 to 2500 nm as the measurement wavelength region. Specifically, the measurement sample is irradiated with either one wavelength (λ1) selected from at least 400 to 1500 nm or one wavelength (λ2) selected from 1700 to 2500 nm, and a spectrum transmitted through the measurement sample is detected. The absorbance is calculated from this.

  Among the above measurement wavelengths, the visible light to near infrared light region is preferably 700 to 1300 nm, more preferably 900 to 1100 nm, and even more preferably 950 to 1050 nm. When quinoline is used as a solvent and the quinoline insoluble content is measured, if a wavelength of less than 700 nm is used, it tends to be susceptible to a change in absorbance due to deterioration of quinoline.

  Among the above measurement wavelengths, the infrared light region is preferably 1800 to 1900 nm or 2000 to 2150 nm. In the infrared light region, when a region other than these wavelength regions, specifically, a wavelength exceeding 1400 to 1600 nm, 1910 to 1990 nm, and 2200 nm is used, quinoline is used as a solvent and quinoline insoluble matter is measured. The absorbance tends to change under the influence of moisture absorption.

  When obtaining the absorbance, usually, a solvent or air is measured in advance as a reference sample, and the absorbances Kλ1 and Kλ2 corresponding to the respective wavelengths are calculated from the measured value of the sample and the measured sample, for example, from the formula (I).

  Then, the solvent-insoluble content ratio can be measured from the absorbance (Kλ1, Kλ2) at λ1 or λ2. Further, the solvent-insoluble content ratio can be calculated from the ratio (Kλ2 / Kλ1) of the absorbance at λ1 (Kλ1) and the absorbance at λ2 (Kλ2).

  Kλ1, which is the absorbance in the visible light to near infrared light region, is associated with the absorbance of the solvent, and Kλ2, which is the absorbance in the infrared light region, can be associated with the absorbance of the solvent insoluble matter. For this reason, if the measurement wavelengths of λ1 and λ2 are appropriately selected, the influence of temperature in infrared absorption can be reduced by using these ratios (Kλ2 / Kλ1) as a scale, and the content ratio of solvent-insoluble matter can be further increased. It can be measured accurately.

  When calculating the content ratio of the solvent-insoluble component from the above ratio (Kλ2 / Kλ1), it is preferable to target the measurement sample having the ratio of 0.01 to 1, preferably 0.015 to 0.8. Is more preferably 0.02 to 0.6, and further preferably 0.025 to 0.4.

  The content of the solvent-insoluble component contained in the measurement sample is preferably 0.1% by weight to 70% by weight, and more preferably 1% by weight to 30% by weight. If the solvent-insoluble content is too low, there may be a problem that it is not possible to obtain sufficient absorbance to measure the solvent-insoluble content of the measurement sample. On the other hand, if the content ratio of the solvent-insoluble component is too high, there may be a problem that the infrared rays to be irradiated do not reach the light receiving unit.

  Although the specific gravity of the said measurement sample is not specifically limited, Preferably the specific gravity in 15 degreeC of temperature is 0.7-1.8, More preferably, it is 1.0-1.6. If the specific gravity is too large, the visible light and infrared rays to be irradiated may not easily reach the flow cell.

  The spectrum of a predetermined wavelength transmitted from the light source of the infrared spectrometer reaches the light receiving portion while being attenuated and attenuated by molecules in the sample solution. Since the infrared transmitted light reaching this light receiving part is proportional to the solvent-insoluble content in the sample solution, the absorbance is calculated from the measured transmitted light, and the solvent-insoluble content is determined from the obtained absorbance. Can be calculated.

[Sampling method]
Next, an example of a measurement method will be described in detail with reference to FIG. 3 showing the configuration of the sampling device.
In FIG. 3, an infusion (process) line of heavy oil a or a sample line taken out from the line is connected to the branch pipe 11 via an on-off valve V1. One process line 11a of the branch of the branch pipe 11 is connected to the heat exchanger 12, and the other process line 11b is connected to the waste liquid process W via the open / close valves V2, V10, or the open / close valve V2, Return to the infusion (process) line via V11.
The flow path of the heavy oil from the on-off valve V1 to the on-off valve V11 is not particularly limited, but it is desirable to install it vertically in order to prevent bubble accumulation in the flow path of the four-way valve 1.

  The process line 11c from the heat exchanger 12 is connected to the four-way valve 1 which is a device for sampling heavy oil.

  The process line 11c is connected to the pipe connection port 5a of the four-way valve 1 as a pipe 5a ', and the pipe connection port 5b is connected to a discharge line 11d as a pipe 5b' for discharging pitches and the like a. One flow path is formed. The discharge line 11d is connected to the process line 11b and further connected to the waste liquid process W.

In addition, the two pipes constituting the first flow path, that is, the pipe 5a ′ and the pipe 5b ′ are provided with opening / closing valves V3 and V4, respectively, and the four-way valve 1 is sandwiched between these two opening / closing valves. . Thus, the supply amount and the discharge amount of the heavy oil a are adjusted. Further, since the flow is stopped when the heavy oil is transferred by switching the valve portion 3 to the second flow path, the heavy oil flowing in during the switching of the valve portion 3 can be prevented.
Further, the process line 11c is provided with a bypass line 11e that bypasses the four-way valve 1 and is directly connected to the discharge line 11d, and the flow rate of the bypass line 11e is adjusted by the open / close valve V5.
By the way, it is desirable in terms of operation that the distance between the open / close valves V3 and V4 having the structure sandwiching the four-way valve 1 is as close as possible within a range that does not adversely affect the operation. Moreover, it is desirable to install the opening / closing valve V3, the four-way valve 1 and the opening / closing valve V4 vertically for the purpose of preventing bubble accumulation in the flow path.

  On the other hand, a tank D2 of a solvent b such as quinoline is connected to the four-way valve 1 through a pump P2 and one through an open / close valve V6. In addition, the tank D2 has a circulation mechanism via the on-off valve V12, and can adjust the amount of the solvent b sent to the four-way valve 1. It is also possible to control the solvent supply to the four-way valve 1 by opening / closing the opening / closing valve V6.

  The process line 11f passing through the on-off valve V6 is connected to the pipe connection port 5c of the four-way valve 1 as a pipe 5c ', and the process line 11g is connected to the pipe connection port 5d as a pipe 5d' for discharging the solvent b. Thus, the second flow path is formed. And this process line 11g may be connected to the dilution dissolution tank 15, or may be directly connected to the sampling container etc. from the process line 11g (not shown). When the process line 11g is connected to the dilution / dissolution tank 15, the process line 11h as a discharge line from the dilution / dissolution tank 15 is connected to the opening / closing valve V7 via the opening / closing valve V8.

  The heavy oil a collected in the through hole 3a of the valve portion 3 in the four-way valve 1 is diluted and dissolved by the solvent b sent from the solvent tank D1 by the pump P1 via the tank D2 and the opening / closing valve V6. Or may be directly connected to a sampling container or the like from the process line 11g (not shown). The amount of the solvent b to be fed is not limited as long as the heavy oil a collected in the four-way valve 1 can be swept away into the dilution / dissolution tank 15 or the sampling container, but is heavy in the four-way valve 1 and the process line 11g. For the purpose of preventing the oil a from remaining, the solvent may be fed about 5 times, preferably about 2 to 3 times the volume of the flow path between the four-way valve 1 and the dilution dissolution tank 15. desirable.

  The pump P2 may be a centrifugal pump, a plunger pump, a diaphragm pump, or the like as long as it is a pump. However, when the four-way valve 1 is passed through an opening / closing valve, the plunger pump uses an opening / closing valve V3, Since a safety valve is required as a safety measure when V4 is abnormally closed, a centrifugal pump or a diaphragm pump is preferable. It is also possible to control the solvent supply to the four-way valve 1 only by opening / closing the opening / closing valve V5 by using the opening / closing valve V4 as a pressure reducing valve, providing resistance, reducing the flow rate circulating to the solvent tank D1. It is. Moreover, the opening and closing of each opening / closing valve can be automatically sampled by using an automatic valve.

  Since the measurement sample (a mixture of heavy oil and solvent) is transferred to the dilution / dissolution tank 15, the material thereof is a container made of stainless steel, glass, or Teflon (registered trademark) in consideration of solvent resistance. It is desirable that

  The pipe through which heavy oil a passes in the sampling device is preferably maintained at the same temperature as the process line by steam tracing in order to prevent blockage of heavy oil a and to suppress the density difference due to the temperature difference. .

  The temperature setting in the tank D2 is arbitrary, but it is preferable that the temperature is kept at 75 ° C., which is the temperature at the time of pitch melting specified in JIS-K2425. Although the temperature setting in the dilution dissolution tank 15 is arbitrary, it is preferable that the temperature is maintained at 75 ° C., which is the temperature at the time of pitch dissolution specified in JIS-K2425. In the dilution / dissolution tank 15, the heavy oil a is diluted with the solvent b and mixed with a motor-driven stirring blade.

  The inner diameter of each of the above pipes is preferably 10 mm or less, and preferably 6 mm or less from the viewpoint of the amount of sample provided to the sampling device. If the inner diameter of the pipe is larger than 10 mm, the inner diameter of the through-hole 3a inside the four-way valve 1 is increased accordingly. Therefore, the amount of sample provided to the sampling device increases, which is not desirable for the purpose of sampling a small amount. The lower limit of the inner diameter is preferably 3 mm or more and preferably 4 mm or more from the viewpoint of transporting heavy oil. If the inner diameter of the pipe is thinner than 3 mm, heavy oil may be clogged.

  This analyzer has the above-described configuration, and all the devices such as the open / close valve and the pump are automatically controlled. Next, the sampling action will be described.

First, by opening the on-off valve V1, high-temperature heavy oil a is sent to the heat exchanger 12 through the branch pipe 11 and the process line 11a. The heavy oil a is cooled to about 140 ° C. by the heat exchanger 12 and transferred to the four-way valve 1.
At this time, the valve portion 3 of the four-way valve 1 is rotated so that the first flow path communicates, the open / close valves V3 and V4 are opened, and the heavy oil a can be transferred between the open / close valves V3 and V4. Thus, the heavy oil a is introduced into the through hole 3 a in the four-way valve 1. Then, by closing the on-off valves V3 and V4, the heavy oil a to be sampled is cut off from the line, and a certain amount of heavy oil a is stored in the through hole 3a in the four-way valve 1. When this four-way valve 1 is used, since the heavy oil a in the through hole 3a is sampled, its capacity is 1 cm ³ or less, preferably 0.3 cm ³ or less, more preferably 0. The amount can be as small as 2 cm ³ or less.

  On the other hand, the solvent b is sent from the tank D1 to the tank D2 via the pump P1 and stored. Then, the solvent b is sent from the tank D2 to the four-way valve 1 through the pump P2. At this time, the on-off valves V3 and V4 are closed, the valve portion 3 of the four-way valve 1 is rotated, the second flow path is switched, and the solvent is transferred from the process line 11f (pipe 5c ′) to 11g (pipe 5d ′). Let b flow. Then, the opening / closing valve V6 is opened. Thus, a certain amount of heavy oil a stored in the through hole 3a in the four-way valve 1 can be transferred together with the solvent b from the process line 11g to the dilution / dissolution tank 15 or the sampling container. At this time, the amount of the solvent b fed to the four-way valve 1 can be adjusted by the opening / closing amount of the opening / closing valve V12 or the opening / closing valve V6 of the circulation line and the rotational speed of the pump P2. Further, the rotation of the four-way valve 1, that is, the speed at which the flow path is switched is not particularly limited, but within 1 second to prevent heavy oil from flowing into the solvent-side flow path during the flow path switching. It is desirable to switch to

The dilution ratio of the solvent b with respect to the heavy oil a at this time is preferably about 1000 to 3000 times, and more preferably 1200 to 2000 times. If the dilution factor is too low, the amount of transmitted light may be reduced, making it impossible to measure the absorbance. If the dilution factor is too high, the content of solvent-insoluble components in the sample solution will be below the detection limit and measurement will not be possible. May cause problems.
When only sampling is performed, the amount of the solvent b to be sent is not particularly limited as long as the sampled heavy oil a is washed away and can be collected in a sampling container or the like, but considering the analysis after sampling, 400 ml The following is desirable.

  The liquid sent to the dilution / dissolution tank 15 is sufficiently mixed. Then, it is sent to the measuring section 16 by the pump P3 via the open / close valves V8, V7, and the absorbance in the wavelength region of the visible, near infrared, or infrared light is measured, and the ratio of the absorbance (Kλ2 / Kλ1) or its absorbance at a single wavelength to quinoline insoluble (QI). When sampling directly into a sampling container or the like without sending it to the dilution / dissolution tank 15, the target analysis may be performed using the solution sampled in the container.

  The measurement of the absorbance in the visible, near infrared, or infrared wavelength region is repeated, as necessary, by alternately sending and discharging to the measuring unit 16 in order to increase the measurement accuracy, and the measurement is completed. , Move to cleaning operation. In the cleaning operation, first, the solution in the dilution / dissolution tank 15 is sent to the waste liquid process by the pump P3 via the measuring unit 16, and the open / close valve V9 is opened to introduce steam or cleaning liquid into the branch pipe 11. The remaining heavy oil a is sent to the waste liquid process W through the open / close valves V2 and V3. The cleaning liquid is preferably the same as the solvent b such as quinoline.

  In addition, the steam or cleaning liquid from the on-off valve V9 is passed through the process line 11a, the heat exchanger 12, the process line 11c, the four-way valve 1, the bypass line 11e, and the like to clean these pipelines. And these washing | cleaning liquids are sent to the waste liquid process W through the discharge line 11d.

  Further, from the tank D2 through the pump P2, through the four-way valve 1, the dilution dissolution tank 15 is charged with an amount of solvent b equal to or larger than the amount used at the time of measurement, and the cleaning solvent b is used as heavy oil. The liquid level of the liquid a reached by the dilute solution is reached and the liquid level is cleaned. In order to increase the dissolving power (detergency), the dilution dissolution tank 15 may be kept at 75 ° C. Thereafter, the solution in the dilution dissolution tank 15 is sent to the waste liquid process W through the measurement unit 16 by the pump P3.

  Furthermore, the solvent b is passed through the measuring unit 16 from the tank D2 via the pumps P2 and P3, and the measuring unit 16 is cleaned. Then, the solvent b is sent to the waste liquid process W.

  The above QI measurement and cleaning action are performed, for example, every 20 minutes to 1 hour, and the manufacturing process is controlled based on the real-time QI measurement value.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. In the present invention, the sampling accuracy was measured by the following method.

[Sampling of heavy oil]
A sampling method according to the measurement process shown in FIG. 3 was adopted, and the pipe inner diameters of 5a ′, 5b ′, 5c ′, and 5d ′ were 4 mm.
Coal tar pitch (viscosity at 100 ° C .: 500 mPa · s) is used as heavy oil, and this is placed in a container adjusted to 140 ° C. and stirred so that the concentration does not change. , 11d.
The heavy oil sampling was performed according to the following procedure.
(1) The flow path of the four-way valve is set to the solvent side (second flow path), the solvent (quinoline) is allowed to flow, and the pipes up to the four-way valve are filled with the solvent (quinoline).
(2) Next, the flow path of the four-way valve is switched to the heavy oil side (first flow path).
(3) The coal tar pitch whose temperature is adjusted to 140 ° C. is passed through the four-way valve to push the quinoline inside the through-hole 3a, and the coal tar pitch channel is filled with the coal tar pitch.
(4) Close the on-off valves V3 and V4 before and after the four-way valve.
(5) The flow path of the four-way valve is switched to the solvent (quinoline) side (second flow path).
(6) The solvent (quinoline) is pumped to the 4-way valve at 120 cm ³ / min for 50 seconds with the pumps P 1 and P 2, and the coal tar pitch and the quinoline are collected in a beaker arranged at the position of the dilution dissolution tank 15. .

[Measurement of quinoline insoluble matter in heavy oil]
(A) The solution collected by the above method is placed in an oil bath at 75 ° C. and heated for 30 minutes while stirring the beaker to dissolve the sample.
(B) The solution of (A) is poured into a filter (W2) that has been precisely weighed in advance, and suction filtration is performed.
(C) Pour 10 cm ³ of a solvent (quinoline) at 75 ° C. into the filtration residue, dissolve and wash. Repeat this operation three times.
(D) The filter carrying the filtration residue is put into a dryer at 110 ° C. and dried for 60 minutes.
(E) The filter carrying the filtration residue is taken out of the dryer and allowed to cool in a desiccator for 30 minutes, and then its weight is precisely weighed (W3).
(F) A solvent insoluble content is calculated by the following formula.
Solvent insoluble content (% by weight) = (residue weight after dissolution / sampling weight) × 100 = ((W3−W2) / W1) × 100
Sampling weight (W1) = 4-way valve through-hole volume × heavy oil density (140 ° C.)
(The density of heavy oil was measured based on JIS K2425.)

Example 1
Sampling described in [Heavy oil sampling] was performed using a ball valve (FIG. 1 (a)) having a four-way valve having a sealing material having the shape shown in FIG. 1 (b).
Sampling was performed by the following two methods, and the average value, standard deviation, and coefficient of variation (value obtained by dividing the standard deviation by the average value and multiplying by 100) were calculated.
<Sampling 1>
Sampling was repeated every 30 minutes, and this was continued for 4 hours for a total of 8 times.
<Sampling 2>
Sampling was performed once a day, and this was repeated for 8 days.
Table 1 shows the results of measuring the quinoline insoluble content of each sampled sample by the method described in [Measurement of quinoline insoluble content of heavy oil] above.

(Comparative Example 1)
The above [Heavy oil sampling] is performed in the same manner as in Example 1 except that a four-way ball valve (FIGS. 4B and 4C) having a sealing material having the shape shown in FIG. Table 1 shows the results of the above [Measurement of heavy oil quinoline insoluble content] in the same manner as in Example 1.
The heavy oil used in Comparative Example 1 is not the same as the heavy oil used in Example 1.

As described above, since the heavy oil used in Comparative Example 1 and the heavy oil used in Example 1 are not the same, there is no meaning in comparing the average value itself, and there is a variation in numerical values when repeatedly sampled ( Standard deviation, coefficient of variation) must be compared.
As is clear from Table 1, compared with Comparative Example 1 using a four-way valve having a sealing material having the shape shown in FIG. 4A, a four-way valve having a sealing material having the shape shown in FIG. In the first embodiment, it is clear that the error when repeated sampling is significantly small.

1 4-way valve 2 Housing 3 Valve (ball)
3a Through-hole 4 Operation shaft 5a, 5b, 5c, 5d Pipe connection port 5a ′, 5b ′, 5c ′, 5d ′ Pipe 6 Sealing material 7 Sealing material 11 Branch pipe 11a, 11b, 11c, 11f, 11g, 11h Process line 11d Discharge line 11e Bypass line 12 Heat exchanger 15 Dilution dissolution tank 16 Measurement part a Heavy oil b Solvents V1, V2, V3, V4, V5, V6, V7, V8, V9, V10, V11, V12 Open / close valve P1, P2, P3 Pump D1, D2 Tank F First flow path S Second flow path W Waste liquid process

Claims (10)

A device for sampling heavy oil flowing in piping,
The heavy oil sampling is performed by switching the flow path of the four-way valve,
This four-way valve has four pipe connection ports, and has a valve part that can switch the flow path by turning inside,
The valve portion has a through-hole penetrating the inside thereof, and the through-hole communicates two pipes connected to two pipe connection ports among the four pipe connection ports, respectively. A flow path can be formed, and by rotating this valve portion, the through hole communicates two pipes connected to the other two pipe connection ports among the four pipe connection ports. The second flow path can be configured,
The heavy oil sampling device, wherein a peripheral portion of the through hole on an outer surface of the valve portion is in contact with a sealing material before and after the two flow paths are switched by the rotation of the valve portion.   The sealing material is a member that fills a space between the valve part and a housing that houses the valve part, and four piping connection ports of the four-way valve, and for rotating the valve part 2. The heavy oil sampling device according to claim 1, wherein the sampling unit is a member having a hole in a portion through which an operation shaft passes.   3. The weight according to claim 1, wherein the four-way valve is sandwiched between the two open / close valves by disposing an open / close valve in each of two pipes constituting the first flow path. Quality oil sampling device.   The heavy oil sampling device according to claim 3, wherein the heavy oil is transferred through the first flow path and the solvent is transferred through the second flow path. The heavy oil to be sampled is shut off from the line by closing the two on-off valves while the heavy oil is transferred to the first flow path, and the heavy oil to be sampled The heavy oil sampling device according to claim 4, wherein the amount is 1 cm ³ or less.   By closing the two open / close valves, the heavy oil stored in the through-hole is switched to the second flow path by the rotation of the valve portion, and is transferred together with the solvent. 6. The heavy oil sampling device according to claim 5, wherein   The heavy oil sampling apparatus according to claim 1, wherein the heavy oil sampling apparatus is used for sampling heavy oil having a viscosity at 100 ° C. of 15000 mPa · s or less.   The heavy oil sampling device according to any one of claims 1 to 7, wherein the heavy oil contains any one selected from coal tar, coal tar pitch, and petroleum pitch.   The heavy oil sampling device according to any one of claims 4 to 8, wherein the solvent contains quinoline.   The heavy oil sampling device according to any one of claims 1 to 9, wherein an inner diameter of the pipe is 10 mm or less.

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