JPH07306197A - Determination device - Google Patents

Abstract

PURPOSE: To find a diluting liquid ratio to fluid by arranging a diluting liquid inlet, a static mixer, and a monitoring means in this order in the flow direction in each of a plurality of divided sections in a pipe, supplying the diluting liquid at equal flow rates to the respective sections, detecting transmitted light intensity of mixture liquid by means of the monitoring method, and deciding an aggregation point. CONSTITUTION: An oil sample in a line 40 is introduced via a duct 41 into a loop 41 by means of an inlet valve 42 and is returned to the line 40 by an outlet valve 43, and the oil sample is driven at a constant flow rate by means of a flow controller 45. In the loop 41, a part following an optical cell 25a , a static mixer 46b , and an optical cell 25b is divided into (n) pieces, and in each of which a static mixer 461 -46n and an optical probe 251 -25n are arranged. The flow of diluting liquid controlled by means of a flow rate controller 49 is transformed into (n) lines of equal flows in the constant flow rate divider 50 so as to converge in the respective corresponding parts of the loop 41. A mixture with a sample passes through the probes 251 -25n sequently, and aggregation of asphalt in the flow is observed as reduction of light intensity. In this way, an aggregation point is decided by means of a data logger 56, and process control is carried out in a microcomputer 57.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a device for controlling the stability of colloidal systems.

[0002]

Fuel heavy oils can be considered as colloidal systems, where high C / H ratio asphaltenes are peptized or colloidized as micelles in the oil phase. An important property that distinguishes such colloidal systems from true solutions is the presence of particles larger than the molecule. The stability of colloidal systems typically depends on their ability to keep the particles in solution and prevent aggregation and precipitation. This ability in fuel oil depends on the existing colloidation state P of alpha-ten, which is the colloidation (or solvent) power Po of the fuel oil medium and the asphaltene colloidation. (Or solubility) Pa.

Mr. Van Kerkvoort of the 4th International Conference on Chauffage Industriel held in Paris in 1952, No. 229 (hereinafter simply referred to as a paper) describes a method of evaluating the stability of fuel oil and the compatibility of fuel oil mixture by a coagulation ratio test method. As a result, when the test liquid mixture of aromatic and paraffinic hydrocarbons is added to the fuel oil at a predetermined dilution ratio, the lowest aromatic ratio that does not cause aggregation of asphaltene present in the fuel oil is set. Procedures are given to quantify. This lowest percentage of aromatics is called the agglomeration ratio.

In the above article, this agglutination ratio is quantified by performing time consuming and tedious batch measurements that require a "spot test". In contrast, the present invention provides a device for making similar measurements quickly and continuously. According to the above paper, the aggregation ratio (FR, that is, Flo
cculation Ratio) is the ratio of various dilution ratios (DR, or Dilution Rati) of a mixture of aromatic and non-aromatic hydrocarbons (ie toluene and n-heptane) to fuel oil.
o), after which the mixture of aromatic and non-aromatic hydrocarbons is used to avoid asphaltene agglomeration, ie the minimum aromatic content (FR) at which asphaltene is just colloidalized. ) And the degree of dilution of the fuel oil is obtained. The curve representing this relationship is the aggregation ratio to the reciprocal of the dilution ratio (ie 1
/ FR vs. DR) is conveniently plotted.
It has been experimentally demonstrated that such plots are linear over a wide range of residual fuel and fuel oil mixing. 1
A linear plot for / DR is preferred because the extrapolation method can be used with better accuracy than a non-linear plot for DR. An example of such a plot is shown in FIG. In FIG. 1, DR is represented as the volume (volume) of diluting liquid divided by the mass of fuel. The DR is sometimes expressed as the amount (volume) of diluted liquid divided by the amount (volume) of fuel, but there is no problem in converting between these two types of DR.

An important and informative feature of the plot of FR against 1 / DR is that the state of colloidation, P, is defined by the intercept on the ordinate axis (FR _max ) and the intercept on the abscissa axis (DR _min ).
The colloid forming force Po and the dissolution performance Pa are given according to the following formulas. Po = FR _max (DR _min +1) Pa = 1-FR _max P = Po / (1-Pa) = DR _min +1

In addition, what is of particular practical importance when mixing is required is that Po and Pa are additive.
Therefore, the stability / compatibility of the fuel oil mixture can be calculated from the values of Po and Pa of the components used. For example, in the case of a two-element blend, the following equation is valid: (1) Po _blend = V ₁ Po ₁ + V ₂ Po ₂ (2) Pa _blend = (V ₁ M ₁ Pa ₁ + V ₂ M ₂ Pa ₂ ) /
(V ₁ M ₁ + V ₂ M ₂ ) (3) P _blend = Po _blend / (1-Pa _blend ) where V is the volume fraction of each mixed component and M is its asphaltene content.

The physical meaning of quantities in the above equation is summarized as follows. FR (Agglomeration Ratio): The lowest aromatic content that a mixture of aromatic and non-aromatic hydrocarbons should have in order to dilute the fuel oil to the amount of DR without causing asphaltene agglomeration. -DR: A value of the amount of diluting liquid per amount of fuel oil phase (dispersion of asphaltene). FR = f (DR): This curve represents the aggregation ratio (FR) as a function of the degree of dilution (in aromatic / nonaromatic mixtures at various rates). This curve gives the limiting conditions for fuel oils in which asphaltene can maintain its colloidalization in asphaltene dispersions. · DR _min: Fuel oil may be diluted without asphaltene aggregation (FR = 0), the maximum amount of non-aromatic hydrocarbons.

For infinite dilution of asphaltene dispersions with aromatic / non-aromatic hydrocarbon mixtures: FR _max : aromatic content of the diluent required to keep the asphaltene colloidal (infinite At dilution, the power of colloidalization of the fuel oil medium is determined only by the diluent). 1-FR _max : non-aromatic content at infinite dilution that can be tolerated without asphaltene agglomeration. -Pa: defined as the solubility of asphaltene, 1
-Corresponds to FR _max . The better the solubility of asphaltene, the higher the 1-FR _max . Po: Fuel oil, which is the aromatic component of an aromatic / non-aromatic hydrocarbon mixture having the same colloidalizing power as the fuel oil, which is the colloidalizing power of the fuel oil medium, expressed as a volume percentage. Can be defined as the aromatic equivalent amount of. P: Colloidalization state of asphaltene in fuel oil, corresponding to Po / (1-Pa). The better the colloidalization state, the higher the colloidalization power of the fuel oil medium. It shows that asphaltene can be colloidized satisfactorily. In the case of P> 1, the fuel oil (mixture) is in a state without dry sludge (a stable fuel in which asphaltene is colloidal), and in the case of P <1, the asphaltene is agglomerated (impacted). Stable fuel oil).

In assessing the stability and stability limits of fuel fuel oils, and their compatibility with other fuel oils and cutter stocks, under any conditions, flocculation such as asphaltene precipitation. It is necessary to know if agglomeration or formation of matter will occur. The conventional method for determining the occurrence of agglomeration is Designation No. D, "Standard Method for Testing Fuel Oil Mixture Compatibility by Spot Testing".
2781 ASTM spot test, or a variation of that test. These conventional methods were time consuming and tedious as they required the production of large numbers of solutions, all of which were checked for the occurrence of aggregation.

[0010]

SUMMARY OF THE INVENTION The present invention provides a continuous ratio of diluent to colloid fluid suitable for the analysis of rapid, accurate and continuous on-line processes where agglomeration occurs in the colloid fluid / diluent mixture. It is an object of the present invention to provide a determination device that makes a positive determination.

[0011]

According to the present invention, the above-mentioned object is to continuously change the ratio of the diluent to the colloid fluid at the point where aggregation occurs in the mixture of the colloid fluid and the diluent as follows. This is achieved by a decision device that makes a positive decision. That is, the conduit is provided with means for supplying a colloidal fluid at a predetermined flow rate, and the conduit is divided into a plurality of sections in the longitudinal direction, and each of the sections has an inlet for receiving a diluent to be mixed with the colloidal fluid. Upstream, followed by a static mixer, and downstream of the static mixer with monitoring means to provide equal flow of diluent for each section of the conduit, Distributor means for diluting liquid is provided, and each monitor means has a light emitting means and a light receiving means and outputs a signal representing the transmitted light intensity of the colloidal fluid / diluent mixture, and all the output signals from each monitor means. Accordingly, a determining device comprising means for calculating the ratio of diluent to colloidal fluid at the point where aggregation occurs in the mixture of colloidal fluid and diluent.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The apparatus of the present invention is described in particular detail in the "Continuous Measurement" section of the following description. Radiation-Object Interaction When the radiation from a light source passes through a sample of an optically dense object, the transmitted radiation is the incident radiation and the radiation absorbed or dispersed by the sample. Corresponds to the difference between. The absorbed radiation is either converted to heat or emitted as fluorescence. The incident radiation is (Rayleigh dispersed) by the molecules of the sample,
Alternatively, it is dispersed by small particles or heterogeneous components in the sample (Tindal dispersion).

The transmission of radiation in a colloidal solution depends on the absorption and the dispersion state of the medium, due to the absorption properties and the refractive index of the colloidal particles and of the aggregates formed from them, and , Determined by the size of the particle with respect to the wavelength of the incident radiation. With the selection of a radiation source of the appropriate wavelength, significant changes in the transmitted radiation can lead to instability of the colloidal solution (eg fuel oil) or to large particle sizes (eg asphaltene) due to aggregation. To be observed.

Laboratory or batch measurements The optical probe described in detail below provides a fast and accurate observation of the occurrence of aggregates, ie the formation of aggregates, on the basis of the absorption or dispersion of light by the asphaltene which precipitates, and FR
Used in the titration procedure to determine the desired value of The description below relates to a reduction in the intensity of the transmitted radiation as an indicator of aggregation, but aggregation is also indicated by an increase in the intensity of scattered radiation.

Prior art relating to the present invention can be found in the following publications and their bibliography: Copyrighted by G.Hotier and M.Robin 19
January 12, 1983, "French Fuel Association Review (Revu
e de 1'Institute Franeaisdu Petrole) "magazine No. 38
Vol. 1, "Action de divers diluants sur le
s produits petroliers ". The present invention relates to improvements in the apparatus for observing the occurrence of agglomeration.

According to the recorder graph shown in FIG.
It is shown how each point was obtained for plotting the value of FR against 1 / DR as in FIG. 1 for a given visbreaker tar fuel. A small amount of heptane was added stepwise to 22 grams of fuel. An optical probe was used to observe the intensity of light transmitted through the diluted fuel as it was mixed with the fuel in increasing amounts of n-heptane. As more dilute solution was added, the intensity of the transmitted light increased in steps until the turning point of the intensity of the transmitted light (the point indicating that aggregation had occurred). The point at which the maximum increase in transmitted light intensity is reached is just before the aggregation point. In the lower curve shown in Figure 2, the freezing point occurred when 8 milliliters of n-heptane were mixed with 22 grams of fuel. Thus, DR = 0 ml / 22 g, ie, DR = 0.36 ml / g, FR = 0 ml aromatic / 8
Milliliter aromatic + paraffin family, ie FR
= 0. This pair of values was then plotted in FIG. 1 with FR = 0 and 1 / DR = 22/8 = 2.75.

The upper curve of FIG. 2 was then plotted using 5.5 ml of toluene and 11.4 grams of the starting mixture of fuel. The observations with the optical probe were again made with increasing n-heptane and mixing with the toluene fuel mixture. Aggregation was observed to occur immediately after the addition of 9 milliliters of n-heptane. Thus, DR = 14.5 ml / 11.
4 grams, ie DR = 1.27 ml / gram, FR = 5.5 ml aromatic / 14.
5 milliliters of aromatic + paraffin hydrocarbons, ie FR = 0.38. This pair of values is then FR
= 0.38 and 1 / DR = 11.4 / 14.5 = 0.79
Is plotted in FIG.

Similarly, a third pair of values for FR and DR were obtained and plotted in FIG. 1 using a mixture of toluene and fuel in different starting proportions. Fuels other than the bisbreaker tar fuel represented by FIGS. 1 and 2 were observed with an optical probe as shown in FIG. 5 (a), and several different curves were obtained. Each gives a pair of values for FR and DR which is a plot of FR values against 1 / DR as in FIG.
The P value and the agglomeration ratio curve are important indicators of the "stability margin" (excess stability) of fuel oil. Such information is particularly useful for optimizing conversion in visbreaking and tar stability.

The article gives a Po value of 0 for n-heptane and also gives negative values for higher aliphatic hydrocarbons (C ₆ -C ₁₆ ). Aromatic compounds have much higher Po values (1.
Up to 5), while naphthene has Po values between aliphatic and aromatic. Po value for mineral oil is 0.12
It is said to range from (poor aromatic) to 1.3 (certain aromatic extracts).

If the values of Po, Pa and P of the residual fuel and the value of Po of the cutter stock are known, the solubility state P of the intermediate fuel oil mixture can be calculated by the above formula.

In order to observe the occurrence of agglomeration based on the absorption and dispersion of light by the precipitated asphaltene, an appropriate radiation source must be selected for measuring the intensity of transmitted light in fuel oil. Based on the absorption spectra of the diluted fuel samples, it was decided to use a near infrared light source. The absorption spectrum showed a minimum absorption at 730 nm, a high absorption in the ultraviolet and a moderate absorption in the infrared band. To avoid interference from ambient light, the near infrared band was chosen rather than the other spectral bands. It has been found that a GaAs: Si light emitting diode element (IR-LED), which is an inexpensive light source of near-infrared radiation that emits mainly at about 950 nm, is effective for this purpose. The light emitting diode device must have a high luminous flux and a small emission angle. A silicon phototransistor, such as the Phillips BPX25, is used as a light receiving element for infrared radiation transmitted through the fuel oil sample. Siemens BP1 as an alternative
Silicon photodiodes with IR filters such as 04 can also be used with appropriate optics. The optical system is designed to produce a narrow beam of radiation when the probe is immersed in fuel, a high index non-test medium.

The optical probe 15 shown in FIG.
It is an example of a probe suitable for observing the occurrence of agglomeration in fuel oil (especially for use in a laboratory). Another embodiment, shown as 25 in FIG. 6, is suitable for a continuous monitor-like process analyzer. The electrical circuitry for the operation of either optical probe embodiment is not shown in the figure as it is a standard circuit for the operation of the IR-LED and phototransistor and is not part of the present invention. The IR-LED emits light when the applied voltage exceeds the forward voltage of the diode (typically 1.4 volts). The current is properly limited by the use of input resistors. Light is detected by the phototransistor and the voltage developed across the resistor in its output circuit is proportional to the intensity of the detected light.

The probe 15 in FIG. 5A is an IR
Includes a stainless steel housing 13 which serves as a support for the LEDs 10 and phototransistors 11 and their lead wire guides. The IR-LED 10 is located at the lower end of the housing 13 and includes a window 19a, a sample slit 12,
Infrared rays are emitted upward to the phototransistor 11 through the window 19b. These elements are all set and held in the housing in a fixed positional relationship with each other by casting a resin 17 that can use epoxy or acrylate. Epoxy is often suitable, but for use in highly aromatic solvents at high temperatures, it is also necessary that it be all glass or glass-metal systems. An alternative arrangement of these elements is to place the IR-LED 10 on top of the phototransistor 11 and beyond it across the sample slit 12, ie the opposite of the arrangement shown in FIG. 5 (a). The phototransistor 11 is arranged at a lower end of the housing 13. However, there are advantages to arranging the elements as illustrated in Figure 5 (a). This is because the arrangement achieves good heat distribution and dissipation within the probe. Heat is IR
The arrangement as produced in the LED 10 and its input resistance, winding resistor 14, as shown in FIG. 5 (a), provides greater spacing between these heat producing circuit elements. To do. The radiation performance of the IR-LED 10 and the sensitivity of the phototransistor 11 are temperature dependent. Maintaining a constant temperature is important to avoid fluctuations in the radiation force and detector sensitivity during the measurement. Since the probe will be partially immersed in a thermostatically controlled oil bath, as described below, this requirement is shown in FIG. 5 (a).
This is achieved by improving the distribution and dissipation of heat within the probe, as in the arrangement of

Sample slit 12 in this embodiment
Form an optical path approximately 2 mm long. In embodiments based on scattered radiation rather than transmitted radiation, the radiation detector (ie, phototransistor) is laterally aligned to receive scattered light rather than a linear arrangement of source, sample, and radiation detector. Will be placed.

FIG. 5 (b) shows in detail the structure of an assembly consisting of a light emitting element such as an IR-LED, a slit and a light receiving element such as a phototransistor. Is shown to be surely protected. The IR radiation is emitted from the IR-LED 10 and is filled in the sample slit 12 through the glass lens 9a of the IR-LED 10, the air space 6a, and the translucent window 19a such as glass (fuel) which is a test object. Go inside. Therefore, these constitute a light emitting unit. Then, the light passing through the medium passes through the window 19b, which is transparent like glass, the other air space 6b, the optical transistor glass lens 9b, and the optical transistor 11
To reach. The IR-LED 10 is housed in the tubular housing 7a, and the phototransistor 11 is housed in the tubular housing 7a.
It is stored in b. Made by casting resin,
The inner seal 17a and the outer seal 17b, which seal the slit 12, cooperate with the light-transmitting light-emitting portion window 19a and light-receiving portion window 19b and the housing to form components (IR-LED 10 and phototransistor) and light-emitting portion space. The space 6a and the light receiving space 6b are sealed and protected from direct contact with the medium, that is, fuel oil.
FIG. 5B also shows a seal 17c that protects the printed circuit board 8 at the slit 12 from the electrical connection between the light emitting portion window 19a and the light receiving portion window 19b. Exposure to aromatic fuel oil first occurs in glass windows 19a and 19a.
b and the outer cast resin seal 17b filling the edge of the stainless steel housing 13,
These outer seals 17b can be easily replaced. If such a seal failure occurs, it does not result in a probe failure. This is because the probe optoelectronic component is protected by the inner seal 17a that serves as a backup.

FIG. 5 (b) also shows the optical characteristics of the probe. Near-infrared (IR) light is condensed and projected into a cone light beam with a small irradiation angle from the light emitting portion, and is condensed into a cone light beam with a small incident angle in the phototransistor. By focusing the available IR radiation into a small cross section and maximizing the IR radiation per unit area, the maximum signal to noise (S / N) ratio can be achieved. It will be appreciated that it is desirable to narrow the IR light beam for this purpose. This is especially desirable when sensing radiation transmitted through highly absorbent media such as fuel oil. Furthermore, it is possible to reduce the perspective angle of the phototransistor by concentrating all of the emitted IR light into a small cross section, and the smaller the perspective angle of the phototransistor, the more scattered and reflected it is. This is advantageous because it reduces the unwanted side effects that result from ghost light such as radiation. A further advantage of limiting the angle of the IR cone light beam emitted from the light emitting part is that it minimizes the angle of incidence of the IR light on the glass window and also the amount of light reflected from the glass window surface. To reduce the ghost light. It is desirable to reduce such ghost light as much as possible because it causes a disadvantage in that a current similar to a dark current is passed through the phototransistor to limit the operating range of the probe.
Further, some light leaks from the edge portion of the light emitting portion window 19a, and a part of this light becomes ghost light reaching the light receiving portion. This ghost light is transmitted to the seals 17c, 17b, 1 for the slits.
The light reaches the transistor 11 via 7a. Therefore, it is important to minimize the light reaching by such "ghost" paths. To provide additional protection against light transmitted by such "ghost" paths, slit seals are said to be strongly absorbing (ie by adding carbon black to the epoxy sealant). It

Air space 6 between lens 9a and window 19a
a acts as an "air lens" and serves to make the function of the lens 9a more effective in narrowing the light beam. If the light emitting portion space 6a as the "air lens" does not exist and the light generated from the lens 9a directly enters the sample oil having a high refractive index, the characteristic of thinning the beam of the lens 9a is invalid. I will be disappointed. For the same reason,
The same applies to the light receiving portion space 6b as the "air lens" of the phototransistor 11.

The printed circuit board 8 is also shown in FIG. 5 (b). The use of probe 15 in making laboratory measurements of fuel oil stability is illustrated in FIG. The lower end of the probe 15 is dipped into the fuel oil sample 30 so that the fuel oil can lodge in or flow through the slit 12. The occurrence of agglomeration in the fuel oil in the slit 12 is I
Observed as a decrease in the intensity of the light transmitted from the R-LED 10 to the phototransistor 11. Figure 5 shows the electrical connection
This is done for the IR-LED 10 and the phototransistor 11 as shown in (a). 16a is an IR-LED 10
And 16b indicates a lead to the phototransistor 11.

The stability of the fuel oil, as indicated by the conditions required to initiate agglomeration, is determined by the fuel oil contained in a container 31 surrounded by a water bath 32, as shown in FIG. Sample 30 of fuel oil / diluent mixture
It is determined by immersing the probe 15 in the. The water bath 32 is placed on a hot plate 34 and maintained at a predetermined temperature by monitoring the temperature with a thermometer 35. To fill the slit 12 of the optical probe with a representative sample, the sample 30 is continuously stirred by means such as a magnetic stirrer 33. A suitable titration fluid such as n-heptane is added using a titration billet 36. The power supply 37 supplies electric power for operating the IR-LED. The recorder or millivolt voltmeter 38
The output from the optical transistor 11 of the optical probe 15 is measured.

Continuous Measurement The optical probe and titration procedure described above for determining the stability characteristics of fuel oils is also useful for continuous monitoring process analysis. FIG. 6 shows an optical cell 25, which is an embodiment of an optical probe suitable for process analysis. As shown in FIG. 6, the optical probe for monitoring the process analysis, that is, the optical cell 25 is an IR-light corresponding to the IR-LED 10 and the phototransistor 11 in the optical probe 15 of FIG. It includes an LED 20 and a phototransistor 21. Optical cell 25 comprises a short glass pipe section with an end having a flange-like means for attachment to a sample conduit for process analysis, the IR portion on one side of which is a narrowed or slit section 22.
The LED 20 and the phototransistor 21 on the other side. Infrared radiation from the IR-LED 20 traverses the fuel oil sample in the slit 22 and reaches the phototransistor 21. Again, the occurrence of agglomerates in the fuel oil stream in the optical cell 25 is observed as a decrease in the intensity of light transmitted from the IR-LED 20 to the phototransistor 21. IR-LED20 support 23
Supported therein, its electrical leads are shown at 26a. The phototransistor 21 is supported in a phototransistor housing 28, the electrical leads of which are shown at 26b.

FIG. 8 shows such a process analyzer
A method of monitoring the stability of fuel oil passing through the line 40 will be described. The oil sample in line 40 is continuously flowed as a constant flow sample stream A via a sample loop or conduit 41. The sample is drawn into the loop via inlet valve 42 and exits the loop via outlet valve 43 back to line 40. The loop sample is
It is driven at a constant flow rate by the pump 44 under the control of the flow controller 45. The sample is then probe (as shown in FIG. 6) or optical cell 25a, static mixer 46b, optical cell 25b, static mixer 46 (1), optical probe 25 (1), ... To the static mixer 46 (n) and the optical probe 25 (n).

The non-aromatic diluent is pumped to line 47 by pump 55. The flow of the non-aromatic diluting liquid is divided into two streams, one of which is a flow controlled by a flow controller 49 which increases the dilution liquid, and the other is a flow controller 48 for performing dilution beforehand. It is a controlled flow. The flow controlled by the flow rate controller 49 flows at a constant flow rate C, and n equal flows 1, 2, ... N-1, n shown in FIG.
Into the constant flow distributor 50, which is a branching device that creates the flow of Each of the n equal streams is introduced into loop 41 at its individual location as described below. Stream 1 joins the sample in loop 41 out of the optical probe 25 (b) and into the static mixer 46 (1). Stream 2 is also the optical probe 25
Enter the loop between exiting (1) and entering the next static mixer. The flow rates of the non-aromatic diluent added at each stage are all equal, and finally the sample flow in bypass loop 41. Then, it is completely mixed with the sample in the loop, and the mixed solution is mixed with the optical probes 25 (1) ... 2
5 (n) are sequentially passed. The conduit can be considered in several sections, each section containing n equal streams 1,
An inlet for receiving one of 2 ... n-1, n, a static mixer following the inlet, and an optical probe downstream of the static mixer are included.

Similar to using the laboratory-use embodiment shown in FIGS. 5 (a) and 7, the process analysis loop 41
The occurrence of agglomeration of asphaltene in the flow at is optically observed as a decrease in the intensity of the transmitted light, as observed in some optical cells 25. Data is collected regarding the observation of the transmitted light intensity, and the aggregation point is determined based on the maximum flow rate determined from the transmitted light intensity, as described above for laboratory or batch measurements. To a data logger 56 programmed to do so. The output of the data logger 56 can also be communicated to a microcomputer 57 which is programmed to allow process control (i.e., control of the pyrolyzer temperature).

If it is desired to preset the sample flowing in the loop 41 to a state where the aggregation point occurs within the range of the n-step increase, the flow of the non-aromatic diluent in the line 47 is performed. Can also be added as a constant flow B from the branch controlled by the flow controller 48. A constant flow B is added in the loop before the sample exits the optical probe 25 (a) and enters the static mixer 46 (b).

If desired, bypass with an aromatic diluent.
To clean the entire loop 41, a cleaning fluid inlet valve 52
A cleaning fluid line 51 with is also provided. The wash line 51 can also be used for pre-dilution of the sample in loop 41 with aromatic diluent.

After being analyzed, the sample flowing in loop 41 can be returned to fuel line 40 via outlet valve 43, and sloped via slop (dirty liquid) outlet valve 54. It can be put back in line 53.

Again, a process analysis to quantify the stability margin of the fuel or residual oil quality improvement stock or product, which was adapted to automatically adapt the laboratory-type optical probe and titration procedure described above, FIG. 8 will be described. A process analyzer is a process or feed line bypass
Can be mounted on the loop. The constant flow rate A of the flow to be analyzed is the optical probe or cell number (a,
b, 1-n), each containing the same basic elements used in the laboratory procedure described above. After being pre-diluted with a constant flow rate B of non-aromatic diluent, the mixture is passed through a static mixer to homogenize the fluid and allow the required reaction time. The light transmitted through the undiluted fuel is checked by the optical cell 25 (a) and the pre-diluted fuel is checked by the cell 25 (b). After cell 25 (b), the fuel is
The non-aromatic diluent is constantly diluted in each step at a constant flow rate C / n. After each dilution step, after passing through the static mixer associated with that step, the fuel undergoes a check of the intensity of the light transmitted by the optical cell associated with that step. Increasing the size of the asphaltene particles (causing agglomeration) results in increased absorption of light. Coagulation points are marked when, after dilution with a non-aromatic diluent, the intensity of the transmitted light is reduced compared to the normal intensity of light during sequential dilution of the fuel. For fuels showing asphaltene precipitation at the reciprocal of the dilution ratio equal to A divided by the quantity B + 9 (C / n), the typical transmitted light intensity levels detected by the optical cell are shown in FIG. Is shown in. The aggregation point thus quantified is a value obtained by dividing A by the quantity B + 8 (C / n) [precipitation does not occur, the reciprocal of the dilution ratio] and A is quantity B + 9 (C / n).
and the value divided by n).

Viscosity mixing optical probes are useful in determining the amount of diluent that can be mixed with heavy fuel oil without exceeding stability limits.
FIG. 3 shows a titration curve for transmitted light intensity as measured by the probe against the amount of gas oil added to the heavy fuel oil. The onset of aggregation is marked by reaching the maximum slope or slope in the titration curve (maximum power increase between two successive additions, which was used in FIGS. 1 and 2). Same criteria).

Storage Stability and Compatibility The storage stability of residual fuels, their compatibility with other fuel oils, and with gas oils, is dependent upon the asphaltene colloids present in such systems. It is mainly determined by the state of conversion P. The state of colloidalization depends on the solubility Pa of asphaltene and the colloidal force Po of the oil matrix. These parameters can be derived from the linear relationship between the aggregation ratio (FR) and the reciprocal of the dilution ratio (DR).

Another simple way to derive these parameters is by using the linear relationship shown in the toluene-heptane graph of FIG. The intercept on the n-heptane axis gives the fuel oil safety margin (DR _min ). The slope of the safety line depends only on the asphaltene solubility Pa. Slope = (1-Pa) / Pa In practice, a slope close to 1 is usually found. (Pa = about 0.5). For fuel oil without stability margin (DR _min = 0; P = 1), a straight line through the origin is obtained in the toluene-heptane plot.

[Brief description of drawings]

FIG. 1 is a diagram for explaining a procedure of plotting as a graph for determining the property of stability of a colloidal system from the measurement by the device of the present invention.

FIG. 2 is a diagram for explaining the procedure of plotting as a graph for determining the stability property of a colloidal system from the measurement by the apparatus of the present invention.

FIG. 3 is a diagram for explaining a procedure of plotting as a graph for determining the stability property of a colloidal system from the measurement by the device of the present invention.

FIG. 4 is a diagram for explaining a procedure of plotting as a graph for determining the property of stability of the colloidal system from the measurement by the device of the present invention.

FIG. 5 shows details of a probe or cell that can be used in laboratory or batch measurements.

FIG. 6 shows a probe or cell used for monitoring in the continuous measurement of the present invention.

FIG. 7 shows a device that can be used in a laboratory or batch measurement.

FIG. 8 illustrates an apparatus of the invention for making continuous measurements such as in on-line process control.

FIG. 9 shows data obtained by the device of FIG. 8 from which the stability profile of the colloidal system can be determined and used for process control.

[Explanation of symbols]

6a, 6b ... Space, 9a ... Lens for light emitting element, 9b ... Lens for light receiving element, 10 ... Light emitting element (IR-LED), 11 ... Light receiving element ( Optical transistor), 12 ... Slit, 13 ... Housing, 15 ... Probe, 17a, 17b, 17
c ... Sealing means, 19a ... Light emitting part window, 19
b ・ ・ ・ ・ Reception part window, 30 ・ ・ ・ ・ Sample, 31 ・ ・
・ ・ Container, 32 ・ ・ ・ ・ Water bath, 33 ・ ・ ・ ・ ・ ・ Magnetic stirrer, 34 ・ ・ ・ ・ Hot plate, 35 ・ ・ ・ ・ Thermometer, 56 ・ ・ ・ ・ ・ ・ Data logger, 57 ・ ・ ・Microcomputer.

Claims (1)

[Claims] 1. A determination device for continuously determining the ratio of diluting liquid to colloidal fluid at the point where aggregation occurs in a mixture of colloidal fluid and diluting liquid, the colloidal fluid being supplied to a conduit at a predetermined flow rate. Means (45), the conduit being longitudinally divided into a plurality of sections, each section having upstream an inlet for receiving a diluent to be mixed with the colloidal fluid, followed by a static Has a static mixer (46), and monitoring means is provided downstream of the static mixer (46).
(25), and is provided with a diluting liquid distributor means (50) for supplying an equal flow rate of diluting liquid to each section of the conduit, wherein each of the monitoring means includes a light emitting means and a light receiving means. And outputs a signal indicating the transmitted light intensity of the colloidal fluid / diluent mixture, and the colloidal fluid at the point where coagulation occurs in the mixture of the colloidal fluid and the diluent according to all the output signals from the respective monitoring means. Means for calculating the ratio of diluent to (56,57)
A determining device comprising: