JPH0115025B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a simple method and apparatus for quickly determining the nature of oil contaminants at the location of oil spills on water surfaces, beaches, coasts, etc.

When crude oil or petroleum components are poured onto a water surface, especially the sea surface, the oil remains on the surface and forms a continuous skin that has a tendency to spread. Such oily skins are naturally undesirable because they block the passage of oxygen and light necessary for life in the sea.

On the other hand, if these oleaginous bodies do not diffuse within a short period of time, they change over time or mix with seawater, usually forming a "thiokolate mousse".
It forms an emulsion called. This emulsion is virtually non-diffusible, creating later ecological problems.

The magnitude of such ecological problems depends primarily on the speed at which they are prevented by suitable means of removing such oil contaminants. However, implementation of appropriate measures for removing oil contaminants can only be carried out after certain characteristics of the oil contaminants to be treated have been determined.

However, such decisions are generally not made in the field, but in the laboratory, resulting in the loss of time due to transporting samples to be tested between the field and the laboratory.

In order to effectively remove oil contaminants, it is necessary and essential to obtain the information necessary to implement appropriate measures as soon as possible.

Because it is very difficult to transport laboratory materials and complex products to the field due to personnel and transportation constraints, special advances are needed to determine the key characteristics of the oil contaminants to be removed. What is needed is a simple and routine device and method that does not require laboratory processes.

One object of the present invention is to provide a method and apparatus that can quickly characterize oil contaminants using simple materials and methods and conventional equipment.

Another object of the present invention is to provide a method and apparatus that can be used directly in the field to quickly characterize oil contaminants.

The method according to the present invention for rapidly determining the properties of water-containing oil contaminants comprises: introducing a cup filled with a sufficient amount of a water-soluble oil-based solvent having a specific gravity significantly higher than water and a water-repellent synthetic agent; closing the upper opening of said tube with a plug; Shake the glass tube so that the mixture of oil and oil contaminants is completely dissolved in the solvent, and open the tap separating the upper part of the glass tube from the lower part to separate the mixture into aqueous and organic phases. Separating into two phases overlapping each other,
The zero scale of a plate pre-scaled to indicate the percentage of water and configured to be movable along the lower portion of the tube is aligned in front of the meniscus above the aqueous phase. knowing the water content of the mixture of water and oil contaminants from the scale of said plate located in front of the plate, and determining the water content of the mixture of water and oil contaminants by any proximate possible A container of known volume is suspended filled with a mixture of water and oil contaminant by a certified spring fitted into a glass tube mounted in place and closed by a cap latched onto the mounting rod of said spring. The specific gravity of the mixture of water and oil contaminants can be determined by reading the scale located in front of the adjustment mark of the verified spring on a fixed plate that has been given a specific gravity scale in advance and is attached to the glass tube. In a glass tube having a capping device at the top and a tap at the bottom, a sufficient amount of a mixture of water and oil contaminants and a sufficient amount of a water-soluble solvent of the glycol type to substantially absorb the oil contaminants are added. introducing a solvent that is not soluble in water to promote separation of the water from the mixture of water and oil contaminants, and proceeding to separate such mixture until an organic phase is formed above and an aqueous phase is formed below. To punish and
opening the tap to remove the aqueous phase;
then introducing into the glass tube a sufficient amount of a mixture of anhydrous calcium chloride and anhydrous sodium sulfate to completely remove the water present in the organic phase;
With the calcium chloride and sodium sulfate captured by the fritted glass at the bottom of the tube, the tap is opened to collect a water-free sample of the oil contaminant, and the first inclined tube containing the thermometer is opened. a branch pipe section and a second branch pipe section diametrically opposed to the first branch pipe section, the branch pipe section having two horizontal branch pipe sections connected to each other by a vertical branch pipe section; The second branch introduces the water-free oil contaminant sample into an apparatus formed by a glass tube, such as a glass tube with a vent at the top, and the second branch introduces the water-free oil contaminant sample through the various branches. a liquid plug ensuring reflux of the distillate into the glass tube, the one below the horizontal branch extending into the glass tube and preventing vapors from being discharged directly through the second branch; mounting such a device on a metal cylindrical enclosure formed around the burner of a welding torch equipped with a gas cylinder, and heating said glass tube until said reflux occurs. and determining a first boiling point of the oil contaminant by reading the temperature indicated on the thermometer when the reflux occurs.

The invention also relates to an apparatus for determining such properties, comprising: an elongated cup of known volume; and two elongated cups connected end-to-end by external flanges. The upper tube has a diameter larger than the cup, the lower tube has a diameter smaller than the upper tube, and has a tap in the upper part and a bulb in the lower part. for rapidly determining the water content of a mixture of water and oil contaminants, comprising a placed glass tube and a movable plate movable along said lower tube, pre-applied with a scale representing the percentage of water; a vertically arranged first wire forming a hook at the upper part and introduced into a glass tube at the lower part; and a verification tester attached to the lower end of said first wire and having an adjustment mark at the lower end. a second wire attached to the lower end of the spring and whose lower end protrudes beyond the bottom of the glass tube; and a container filled with a mixture of water and oil contaminants and attached to the lower end of the second wire. , a fixing plate mounted on the outside of the glass tube and scaled with specific gravity so as to have a zero scale located in front of the adjustment mark of the spring when the container is empty; and a welding torch which is supplied with fuel from a gas cylinder, the horizontal tube of the welding torch is bent vertically to form the head of a burner at the top, and the burner head is made of metal. a heating device, such as a heating device placed in a cylindrical enclosure, and a vertically placed glass tube configured to contain the water-free oil contaminant to be tested, with a first sloping branch at the top thereof. a second branch having a tube section into which a thermometer is introduced so that its bulb reaches the axial position of the glass tube; and a second branch section for ensuring condensation and reflux of the distilled product. and has two horizontal branch pipe parts provided diametrically opposite to said first branch pipe part and connected to each other by a vertical branch pipe part, said vertical branch pipe part at its upper part. Forming a vent pipe, the upper part of the horizontal branch pipe faces the bulb of the thermometer, and the lower part of the horizontal branch pipe is located inside the glass tube and extends downward. The glass tube is placed in the metal enclosure, the bottom of which is always at the same level with respect to the burner flame, and the thermometer is placed in the metal enclosure. and a glass tube configured such that the scale is located outside the enclosure.

The determination of the various properties as described above by the method and apparatus of the invention makes it possible to easily select the reliable means to be used for the removal of oil contaminants.

For example, by determining the water content of the water and oil contaminant mixture, the most suitable type of recovery device can be selected. Determination of specific gravity allows determining the most suitable form of trawl process to ensure high recovery.

By determining the first boiling point of the oil contaminant, the temperature range that includes the flash point of the oil contaminant can be determined by using a diagram giving the flash point versus the first boiling point. Knowing this characteristic is very important in order to avoid the risk of explosion and make work safer.

Other properties can also be rapidly determined using simple materials methods. Examples include determining the viscosity with a bead drop viscometer or flow gauge if the liquid is very viscous, or determining the pour point or freezing point, or some other method. This includes determining the response of oil contaminants to common diffusion agents and anti-emulsification agents.

The invention will now be described in detail by way of example embodiments with reference to the accompanying drawings.

According to the apparatus shown in FIG. 1, the water content in the water and oil contaminant mixture is determined by filling the cup 10 to its brim with the water and oil contaminant mixture. The cup 10 can have any shape as long as it can be easily introduced into the glass tube 11 and can move freely within the glass tube.
Cup 10 filled with a mixture of water and oil contaminants is first introduced into glass tube 11 and tap 12 is closed. Thereafter, a solvent containing a synthetic agent which is a solvent for oily substances and which is substantially insoluble in water and whose specific gravity is higher than that of water and repels water is introduced into the glass tube 11. This solvent is a common solvent, usually chloroform or carbon tetrachloride. After that, the glass tube 11 is plugged into the plug 13.
The device is then shaken until the water and oil contaminant mixture is completely dissolved.
At this time, the tap 12 is open and the liquid inside is also allowed to flow into the tube 14 which has a bulbous part 15 at one end. The internal liquid is divided into two phases, an organic phase and an aqueous phase, and the aqueous phase is placed above the organic phase due to the difference in specific gravity. A movable plate 16 that can be slid along the tube 14 is slid and its 0 scale is aligned with the meniscus above the aqueous phase, and the scale opposite the meniscus below the aqueous phase gives the percentage of water. Movable plate 16
The scale of the percentage of water is engraved in advance. This scale is determined based on the volume of the cup 10 and the diameter of the tube 14 at the portion where the movable plate 10 is provided.

According to a preferred embodiment of the invention, cup 10
is elongated so that it can be easily introduced into the glass tube 11. The device consists of three separable parts: a central part with a glass tube 11 and a tap 12, and a tube 14;
It is preferable to have a tube section 17 connected to the tube 1 and a tube section 18 connected to the tube 14. Tube 14 is also connected to tube 11 to increase the accuracy of readings.
Preferably it has a smaller diameter.

The specific gravity of the mixture of water and oil contaminants is determined by the apparatus shown in FIG. First, the container 20 is filled with the mixture and the cap 21 is closed. A rigid wire 22 is attached to the cap. The upper part of this wire 22 is introduced into a glass tube 23, and the uppermost end of the wire is attached to the lower end of the certified spring 24. The lower end of the certified spring 24 has an adjustment mark 25, which is attached to the wire 2
When nothing is hung on 2, it faces the 0 scale of the fixed plate. This fixing plate has standard specific gravity scaled in advance and is fixed to the outside of the glass tube 23. The upper end of the certified spring 24 is always inside the glass tube 23 and is attached to the lower end of a rigid wire 26. The upper part of the wire 26 protrudes from the glass tube 23 and is curved into a hook shape.

The length of the certified spring 23 within the glass tube 23 is determined to obtain good measurement accuracy. This length is about 10 cm for specific gravity in the range of 0.1 to 1.

The apparatus shown in FIG. 3 determines the initial boiling point of a water-free oil contaminant. Removal of water from the mixture of water and oil contaminants is accomplished by the apparatus shown in FIG. This water removal is accomplished by applying a sufficient amount of the water and oil contaminant mixture to a lower tube having a tap 41 at the lower end, along with a water-soluble solvent that is substantially insoluble in the oil contaminants. This is done by introducing the glass tube 40 into a glass tube 40 having a fritted glass portion 42. The solvents to be used are of the glycol type, especially propylene glycol. Solvents of this type do not present problems in determining the primary boiling point of the oil contaminant since its boiling point is substantially higher than the boiling point of the light components contained in the oil contaminant. Glass tube 40 is then closed, as is tap 41, and the device is shaken to extract the water from the oil contaminants. The mixture separates into an aqueous phase containing water and solvent and another phase containing oil contaminants. Next, tap 41 is opened and the aqueous phase is allowed to flow out. Anhydrous calcium chloride and anhydrous sodium sulfate are introduced into the tube 40 in order to remove all the water present in the oil contaminants. The mixture is then stirred, after which the liquid phase is recovered. This liquid phase consists of water-free oil contaminants, while calcium chloride and sodium sulfate are retained on the fritted glass 42. The recovered oil contaminants are then processed in the apparatus shown in FIG.

The water-free oil contaminant is introduced into a vertical glass tube 30. This glass tube includes a first branch pipe section 31 extending upwardly and a second branch pipe section 3 extending diametrically opposite to the first branch pipe section.
2. The second branch pipe section 32 has two horizontal sections 33 and 34 connected by a vertical branch pipe section 35, above which a vent pipe 36 is provided. Branch pipe portion 34 extends into pipe 30;
Its extension is oriented vertically downward and its diameter is gradually reduced to act as a liquid plug during distillation of the product. The branch pipe portion 32 is the pipe 3
It is designed to ensure condensation and reflux of the distilled product through 0. A thermometer 3 is installed in the branch pipe section 31.
7 is inserted, and the bulb portion of the thermometer is located at the axial center of the tube 30 and at the front of the branch tube portion 33.

The device is secured by fixing clips 39 onto a vertically placed cylindrical metal enclosure 50.

The oil contaminants are distilled off by being heated by the burner 51 of the welding torch 52. The torch is supplied with gas from a small gas cylinder 53. Connected to the gas cylinder 53 is a horizontal pipe 54 which bends vertically towards the head of the burner 51 and places it within the enclosure 50.

As the oil contaminants in tube 30 are heated, steam rises in tube 30 and condenses on thermometer 37 and in branch tube 33. The branch pipe 33 is constantly cooled by a wet cotton wrapping. Branch pipe parts 35 and 34
The condensate flowing through the tube 30 ensures a reflux and forms a liquid plug so that vapor cannot rise directly through the branches 34, 35, 36. Once such reflux is established and a droplet is deposited on the bulb 38 of the thermometer 37, the distillation is in steady state and the temperature can be read on the thermometer 37. This temperature value is converted to a flash point value on a diagram showing the flash point range of the oil contaminant versus its boiling point.

The following examples are included not to limit the scope of the invention, but to better explain the invention.

Example The following experiment was conducted on an oil contaminant containing 22% crude oil and 78% water. This oil contaminant was present as an inverse emulsion of the tyokolate mousse type. The specific gravity of the water and oil contaminant mixture was 1.01, and the flash point of this oil contaminant was 36°C. These properties are precisely determined values.

The method and apparatus according to the invention were then used to determine other properties of this oil contaminant.

First the cup was filled to the brim with a mixture of water and oil contaminants. This cup was introduced into the glass tube shown in FIG. 100 ml of chloroform, to which were added two drops of primary oleate amine acetate as a water-repellent synthetic agent, was then introduced into the glass tube. The mixture was allowed to flow through the tap into the lower tube and the water content of the water and oil contaminant mixture was determined by the method described above.
The water content was thereby found to be 72%.

The container shown in Figure 2 was then filled with a mixture of water and oil contaminant to determine its specific gravity.

The container, filled to its brim, was attached to the apparatus shown in Figure 2, and the specific gravity was found to be 1.03. 40 ml of this water and oil contaminant mixture was then poured into a tank along with 60 ml of polypropylene glycol. It was introduced into the glass tube shown in Figure 4.

After the mixture separated into two layers, the aqueous phase was removed. 20 g of a 4:1 mixture of CaCl ₂ and Na ₂ SO ₄ was introduced into the same tube. The mixture was stirred and the water-free oil contaminant was collected.

The thus recovered water-free oil contaminant was introduced into the glass tube shown in FIG. 3, the burner of the welding torch was ignited, and the oil contaminant was distilled. When reflux was established, a droplet dripped onto the bulb of the thermometer. The temperature indicated by the thermometer is
It was 105℃.

This temperature was converted to the flash point using the diagram in FIG. The flash point corresponding to this temperature was 39°C.

It will be appreciated that the determination of the properties of oil contaminants by the method of the present invention is of sufficient accuracy to select means for performing the work to remove the oil contaminants.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of an apparatus for determining the water content of a mixture of water and oil contaminants. FIG. 2 is a schematic diagram of an apparatus for determining the specific gravity of water and oil contaminants.
FIG. 3 is a schematic diagram of an apparatus for determining the first boiling point of oil contaminants. FIG. 4 is a schematic diagram of an apparatus for removing water from a mixture of water and oil contaminants. Fifth
The figure is a diagram giving the flash point versus the first boiling point of the oil contaminant. 10...Cup, 11...Glass tube, 12...
Tap, 13...Plug, 14...Tube, 15...
Ball portion, 16...Movable plate, 17, 18...Pipe, 20
... Container, 21 ... Cap, 22 ... Wire, 2
3... Glass tube, 24... Spring, 25... Adjustment mark, 26... Wire, 33, 34, 35... Tube part, 37... Thermometer, 38... Ball part of thermometer, 3
9...Fixing clip, 40...Glass tube, 41...
...tap, 42... fritted glass, 50
...Enclosure, 51...Burner, 52...Welding torch, 53...Gas cylinder, 54...Pipe.

Claims (1)

[Scope of Claims] 1. A mixture of water and oil contaminants and a sufficient amount of an oily solvent which is substantially water-soluble and has a specific gravity sufficiently higher than that of water are added to the upper part of a glass tube whose lower part is separated by a tap. introducing a cup filled with a volume and a water-repelling synthetic agent; closing the upper opening of the tube with a plug; Shake the tube, open the tap separating the upper part of the glass tube from the lower part to separate the mixture into two phases, an aqueous phase and an organic phase, and indicate the percentage of water. The 0 scale of a plate pre-scaled and configured to be movable along the lower portion of the tube is positioned in front of the meniscus above the aqueous phase and in front of the meniscus below the aqueous phase. determining the water content in the mixture of water and oil contaminants by knowing the water content of the mixture of water and oil contaminants from the scale of said plate; and the glass mounted at any accessible location. Suspending a container of known volume filled with a mixture of water and oil contaminants by means of a certified spring fitted into the tube and closed by a cap latched onto the mounting rod of said spring, and with a predetermined specific gravity scale. determining the specific gravity of the mixture of water and oil contaminants by reading a scale located in front of the adjustment mark of the certified spring on a fixed plate mounted on the glass tube and fixed to the glass tube; A glass tube having a capping device and a tap at the bottom contains a sufficient amount of a mixture of water and oil contaminants and a sufficient amount of a water-soluble solvent of the glycol type which is substantially insoluble in the oil contaminants. introducing a mixture of water and oil contaminants to promote the separation of water from the mixture of water and oil contaminants, and allowing the separation of such mixture to proceed until an organic phase is formed above and an aqueous phase below;
opening the tap to remove the aqueous phase;
then introducing into the glass tube a sufficient amount of a mixture of anhydrous calcium chloride and anhydrous sodium sulfate to completely remove the water present in the organic phase;
With the calcium chloride and sodium sulfate captured by the fritted glass at the bottom of the tube, the tap is opened to collect a water-free sample of the oil contaminant, and the first inclined tube containing the thermometer is opened. a branch pipe section and a second branch pipe section diametrically opposed to the first branch pipe section, the branch pipe section having two horizontal branch pipe sections connected to each other by a vertical branch pipe section; The second branch introduces the water-free oil contaminant sample into an apparatus formed by a glass tube, such as a glass tube with a vent at the top, and the second branch introduces the water-free oil contaminant sample through the various branches. a liquid plug ensuring reflux of the distillate into the glass tube, the one below the horizontal branch extending into the glass tube and preventing vapors from being discharged directly through the second branch; mounting such a device on a metal cylindrical enclosure formed around the burner of a welding torch equipped with a gas cylinder, and heating said glass tube until said reflux occurs. determining a first boiling point of the oil contaminant by reading the temperature indicated on the thermometer when said reflux occurs; How to decide. 2 comprising an elongated cup of known volume and two tubes connected end-to-end by external flanges, the upper tube having a constant diameter larger than said cup and the lower tube connecting said upper tube; a vertically placed glass tube of smaller constant diameter and having a tap in the upper part and a bulb in the lower part, and a graduated scale representing the percentage of water moved along said lower tube; an apparatus for rapidly determining the water content of a mixture of water and oil contaminants, comprising a movable plate that can be moved vertically forming a hook at the top and introduced into a glass tube at the bottom; a certified spring attached to the lower end of the first wire and having an adjustment mark on the lower end; and a second wire attached to the lower end of the spring and having a lower end protruding from the bottom of the glass tube. a container filled with a mixture of water and oil contaminants and attached to the lower end of the second wire; and a container attached to the outside of the glass tube and located in front of the adjustment mark of the spring when the container is empty. an apparatus for rapidly determining the specific gravity of a mixture of water and oil contaminants, comprising a fixed plate having a specific gravity scale with a zero scale; and a welding torch supplied with fuel from a gas cylinder. The horizontal tube of the welding torch is bent vertically to form the head of the burner at the top, which contains a heating device such as that placed in a metal cylindrical enclosure and a water-free oil contamination to be tested. A glass tube configured to contain a substance and placed vertically, having a first inclined branch section at the top thereof, and a thermometer within the branch section, with its bulb section positioned at the axis of the glass tube. a second branch pipe section diametrically opposed to said first branch pipe section, which is introduced to ensure condensation and reflux of the distilled product; The vertical branch has two horizontal branch pipes connected to each other, the vertical branch forming a vent pipe at its upper part, and the upper horizontal branch pipe is connected to the bulb of the thermometer. The horizontal branch pipes facing each other and below the horizontal branch pipes are located inside the glass tube and have portions whose diameters gradually vary downward.The glass tube is made of the metal. a glass tube placed in an enclosure, the bottom of which is always placed at the same level as the flame of the burner, and the scale of the thermometer is located outside of the enclosure; Apparatus for rapidly determining the first boiling point of a mixture of water and oil contaminants, characterized in that the apparatus comprises: