JPH11508934A - Pretreatment methods to prevent hydrocarbon leakage - Google Patents

Abstract

(57) Abstract: A method is provided for reversibly coagulating a hydrocarbon for transport or storage and preventing leakage of the hydrocarbon. The method includes mixing a hydrocarbon with a sufficient amount of a hydrocarbon wax (eg, paraffin). When the obtained mixture is cooled, solidification occurs and a buoyant bonded mass is obtained. The minimum amount of hydrocarbon wax required to coagulate the oil depends on the type of crude oil, the type of wax used, and the temperature of the coagulum retained during transport. When transporting crude oil by ocean shipping, the crude oil can be pretreated with hydrocarbon wax in a storage tank room and the mixture can be transported in the solid state. The solidified joint mixture effectively prevents the leakage of crude oil in the event of a hull failure, and is not replaced by seawater. This buoyant solidified mixture prevents the ship from sinking if the hull is punctured. Hydrocarbon waste, such as contaminated PCBs, can be reliably solidified using higher levels of wax to solidify the oil. When transporting crude oil, wax can be recovered from the crude oil by heating and liquefying the mixture, and its components can be separated by fractional distillation.

Description

DETAILED DESCRIPTION OF THE INVENTION                  Pretreatment methods to prevent hydrocarbon leakage                                Field of the invention   The present invention provides for the reversible solidification of liquid hydrocarbons for transport or storage, The present invention relates to a method for preventing element leakage.                                Background of the Invention   It is well known that the transport and storage of hydrocarbons can cause disasters. It is. Crude oil is often transported via tankers or tank trucks. Cargo oil was frequently spilled due to disasters in vehicles transporting the. 30 to 40 ships per year It is estimated that some tankers release significant amounts of crude oil to the outside world. Marine smell In some cases, spilled oil tends to form a floating oil slick, which makes fish and birds the same. Will be forced to die. On land, spilled oil seeps into the soil Tends to contaminate groundwater. In either case, the liquid oil Is difficult and expensive to remove.   Various methods are used for both physical and chemical methods, Oil containment and removal of oil from the water surface have been promoted. Commonly used physics A typical method of confinement is to use floating materials to surround the oil slick and then pump up the oil It is. The disadvantage of this method is that the oil slick has to be removed because it tends to spread quickly. It has to be pumped in several parts and requires a lot of manpower and equipment Is a point. The difficulties encountered in strong winds and rough seas will be obvious to those skilled in the art. Ma In addition, this method makes it difficult to use technology far from the coast.   Various chemical methods have been proposed to purify spilled oil occupying a large surface area Came. Sohnius (U.S. Pat.No. 3,607,741) was made hydrophobic by pretreatment, By using a cellulosic material that has an affinity for oil, A method for recovering the same is disclosed. In one embodiment, the cellulosic material is oil Are included in a mesh-like net arranged on the surface of. Another embodiment In, the cellulosic material covers the surface of the pillar, and the pillar receives wind Oil is collected as it rotates across the oil slick trapped by the boom. Of this method The disadvantage is that a large number of protective materials and columns are required to purify a large oil slick. . Recovering oil from cellulosic materials is time consuming and expensive.   Alquist (U.S. Pat.No. 3,785,972) liquefies oil by spraying wax onto the oil slick surface. Raises the oil slick by raising the temperature above the water temperature to form a solid mass that can be scooped. It teaches how to purify. Spray the wax / hydrocarbon mixture over the oil slick Can be scooped up by burning and burning off light hydrocarbons from crude oil A method of forming a hard asphalt-like material is also taught. Bartha (U.S. Patent No. 5,112,495) discloses a method of spraying molten hydrocarbon wax on an oil slick surface. However, in this case, when the wax-coated oil film is cooled, it can be physically scooped up A solid mass forms.   Weinberg (U.S. Pat.No. 3,756,948) claims polystyrene for recovery and transport. Disclosed are methods and means for using crude oil to absorb crude oil. This patent is It relates to the method of physically absorbing oil, and the method of gelling or coagulating oil is It is quite different. Weinberg uses either chemical solvents or heat to The oil is recovered from polystyrene by dissolving the polystyrene.   The disadvantage of these different approaches is that applying confinement to spilled oil can be costly and time consuming. Can occur in a short period of time, and leakage often occurs in remote areas. It is difficult to reach. Transport a large amount of wax to the spill site and heat to Special ships and Equipment is required. In addition, to transport large volumes of solid mixtures from spill sites, A special large tanker equipped with cargo handling equipment required for picking up and unloading solid mass is necessary.   To minimize the potential for oil spills, use safer and more robust transport vessels. Emphasis has been placed on production. The development of the double-hulled oil tanker is the development of such a transport ship. This is an example. In these transport vessels, the tank room or container storing the oil is damaged. To reduce the likelihood of oil leakage, Always tends to be expensive. In addition, all transport vessels are completely safe from disasters Not only is it the case, but if you have a very severe disaster Even if there is, there is a risk of damage.   Recently, the cost of mass transportation of crude oil has been increasing as the number of marine accidents has increased. Has increased. The premiums for insurance contracts for marine transportation of crude oil alone are at least Is tens of millions of dollars. Therefore, hydrocarbons are pre-treated before transportation, and oil slicks are formed during disasters. A method that significantly reduces the likelihood of being achieved is desired.   In this connection, waste oils and harmful hydrocarbons such as PCB (polychlorinated biphenyl) There are also problems with preserving compounds. Hydrocarbons are usually supplied on steel drums or barrels. And stored in a waste storage facility or buried cellar. For storage of hydrocarbons The drum used may be damaged due to corrosion and impact. Such damage When this happens, harmful compounds can be released and soil and groundwater can be contaminated. It is difficult to clean up spilled hydrocarbons, often by digging up the soil It needs to be removed. Hardened storage drums to reduce potential leaks Efforts have been made. Such high quality drums tend to be expensive.   Another method of storing waste oils and harmful hydrocarbon compounds is to solidify the material Things. In the solid state, leakage is not very problematic. Leak The recovery of the emitted hydrocarbons can be made easier if they are in the solid state. Coagulation reduces the likelihood of seepage into the soil and contamination of groundwater. Add a sufficient concentration of coagulant to coagulate the hydrocarbon and allow the mixture to solidify Or make a semi-solid mass. Coagulants usually tend to be expensive, Processing is often difficult or expensive to undo.   Weitzen (U.S. Pat.No. 4,341,078) is suspended in a cryogenic liquid such as liquid nitrogen. Discloses a method of coagulating a PCB by adding a slurry of crushed cryogenic polymer particles. ing. The coagulants used in Weitzen's method are expensive and, in addition, require special processing equipment. Is considered necessary. The solid obtained by the method of Weitzen is liquefied. Difficult and requires ionic radiation or high shear to liquefy. Derby (US (Patent No. 3,881,295) discloses a method of coagulating PCB by adding swellable polymer particles. Has been disclosed. The polymer particles swell by absorbing the PCB, forming a thick gel. D Erby does not disclose how to reconstitute the solidified PCB mixture. Burning of harmful substances It is desirable to make the coagulation process reversible to facilitate disposal. Good. Conner (U.S. Pat.No. 4,518,507) is a chemical coagulation of hazardous waste It discloses a method of encapsulation, in which the waste is coagulated and Encapsulate in a membrane such as ethylene.                                Summary of the Invention   The present invention provides a method for pretreating a hydrocarbon for transport or storage. This Involves mixing hydrocarbons and hydrocarbon waxes in an enclosed space to form a mixture. In this case, the mixture is set at a temperature within the solidification temperature range at which the mixture solidifies. Also keep at high temperature. For hydrocarbon waxes, the temperature of the mixture drops below the solidification temperature range When present, the mixture is present in an amount effective to substantially solidify. This The mixture substantially solidifies to form a hard mass. Solidified mixture Liquefies when heated to a temperature above the solidification temperature range.   In another embodiment of the present invention, the hydrocarbon is pretreated for transport by ship. A method is provided. This method involves the use of hydrocarbons and hydrocarbons in the enclosed space of a ship. Mixing with wax to form a mixture and storing the mixture (provided that the mixture is Keeping the mixture at a temperature above the solidification temperature range at which the mixture solidifies) . When the temperature of the mixture drops below the freezing temperature range, the hydrocarbon wax It is present in an amount effective to substantially solidify. This allows the mixture to be substantially When the mixture solidifies and is heated to a temperature above the solidification temperature range, the mixture Liquefies. The solidified mass is transported to the destination by ship, and hydrocarbon wax is recovered from oil. I do.   The present invention also provides a method for encapsulating a liquid hydrocarbon for storage. This method involves mixing a liquid hydrocarbon with paraffin wax to form a mixture. Process is included. Paraffin wax is said to have reduced the temperature of the mixture below the solidification temperature range. The mixture is present in an amount effective to substantially solidify. If you do this The solidified mixture substantially forms a solid mass.                             BRIEF DESCRIPTION OF THE FIGURES   Next, the method of the present invention will be described with reference to the drawings, but this is merely an example. Only.   FIG. 1 shows various oil / paraffin mixtures and oil / paraffin / water at 25 ° C. 5 is a plot of% solidification versus% paraffin wax for the mixture.   FIG. 2 shows various oil / paraffin mixtures and oil / paraffin / water at 20 ° C. 5 is a plot of% solidification versus% paraffin wax for the mixture.   FIG. 3 shows various oil / paraffin mixtures and oil / paraffin / water at 15 ° C. 5 is a plot of% solidification versus% paraffin wax for the mixture.   FIG. 4 shows various oil / paraffin mixtures and oil / paraffin / water at 10 ° C. 5 is a plot of% solidification versus% paraffin wax for the mixture.   FIG. 5 shows various oil / paraffin mixtures and oil / paraffin / water mixtures at 4 ° C. 5 is a plot of% coagulation versus% paraffin wax for the compound.   FIG. 6 shows various oil / paraffin mixtures and oil / paraffin / water mixtures at 0 ° C. 5 is a plot of% coagulation versus% paraffin wax for the compound.   FIG. 7 shows an oil / paraffin wax mixture containing 9% paraffin wax and an oil / paraffin wax. 3 is a plot showing the effect of temperature on the solidification of a wax / water mixture.   FIG. 8 shows% solidification versus time for a mixture of crude oil and 9% paraffin wax at 20 ° C. It is a plot.   FIG. 9 shows viscosities versus paraffins for different mixtures of crude oil / paraffin wax at 20 ° C. It is a plot of a fin wax.   Figure 10 shows the percentage of solidification versus paraffin wax percentage for gasoline and diesel fuel. It is.   FIG. 11 shows a solidified and encapsulated hydrocarbon / hydrocarbon wax mixture in accordance with the present invention. This is shown in a perspective view.   FIG. 12 (a) shows the results of infrared analysis of the mixture encapsulated as shown in FIG. Is shown.   FIG. 12 (b) is an infrared analysis of the oil contaminated with PCB.                             Detailed description of the invention A)Pretreatment of hydrocarbons for transport   According to the present invention, to reversibly solidify hydrocarbons such as crude oil for transportation First, the oil is mixed with the coagulant. The coagulant is preferably a hydrocarbon wax . In one embodiment of the method, the wax is melted and mixed with the oil. A homogeneous mixture Some agitation of oil and wax may be required to obtain. Mixing is carried out on the transport ship itself This may be done before the oil is supplied to the carrier, but in this case the solution It is necessary to keep the temperature higher than the solid temperature.   In this specification, the term mixture is to be interpreted in the broadest sense and is intended to mean two or more components. Substance (Webster's New World Dictionary, second college edition) ). That is, while coagulating the hydrocarbon, the hydrocarbon wax is coagulant Use as The identity of the resulting mixture of hydrocarbons and wax is unknown . Because a mixture of several types (for example, a homogeneous solution in which all the waxes are dissolved, Saturated solution containing precipitated wax, elongated gel, colloidal suspension, or a combination thereof This is because there is a possibility that it exists as a combination. Thus, the term mixture includes: It is to be understood that all of these possibilities are included. Similarly, solidification means " Solidify, firm, harden, or bond. '' It is justified. As a result, the use of the term solidification translates into an effective amount of hydrocarbon wax. Can describe the formation of a strongly bonded mixture when added to hydride . The present invention formed by mixing an effective amount of a hydrocarbon wax with a liquid hydrocarbon. The solidified mixture described in the text shows that the mixture has a significantly higher viscosity than liquid hydrocarbons. In this case, the free flow of the mixture is suppressed.   Transporting crude oil in a solidified state after the mixture of oil and coagulant has been loaded on board the ship If desired, the mixture can be cooled to a temperature below the solidification temperature of the mixture. Good. In this case, depending on the amount of hydrocarbon wax and the properties of the crude oil, the solidification temperature is the ambient temperature. May not require any elaborate cooling mechanisms. This This will be described in more detail below. Surround the ship if the ship is sailing The wax and its amount so that at water temperature the mixture is sufficiently cooled to its solidification temperature It is preferable to select Thus, the coagulated oil / wax mixture is safely transported. It becomes possible. In addition, the mixture can be kept liquefied during transport However, in this case, when water comes into contact with the mixture due to cracks in the hull, The mixture is selected such that it solidifies and prevents leakage of the mixture.   Depending on the type of wax used, the concentration of wax required to obtain the desired coagulation temperature range May change. Hydrocarbon waxes exhibit some solubility in oil The oil acts as a solute and lowers the melting point of the wax. As a result, the melting of the wax The higher the point, the more the solidification temperature range will be obtained if solution formation is an important mechanism It is estimated that the concentration of the wax required for this will be lower.   In one embodiment of the present invention, the hydrocarbon wax is not It is a paraffin wax that is biologically and chemically inert for the above purposes. Dissolution The concentration of wax used in the body is generally between 1.0% and 15% by volume. Wax concentration Is adjusted according to the type of crude oil being transported and the desired coagulation temperature of the solution. viscous Crude oil generally requires a higher concentration of paraffin wax than light crude oil. Low. If higher coagulation temperatures are required, increase the concentration of paraffin wax. Pa If the volume percentage of the raffins exceeds 15%, the solidification temperature will increase regardless of the grade of crude oil used. No significant increase is seen. Based on one gallon, the type of crude oil Depending on the concentration of paraffin wax in the mixture, from about 2 oz to about 8 oz per gallon The present inventor has found that crude oil coagulates effectively at the time.   Depending on the type of crude oil and the quality of the paraffin wax, the solution has a certain coagulation temperature. May not be. The solidification temperature is considered as the range in which the mixture transitions from the liquid phase to the solid phase. Is done. Beyond this range, the mixture will all be in the liquid phase, below this range. Then, the entire mixture becomes a solid phase. During the mixing process, both paraffin wax and oil Must be above the solidification temperature range of the mixture. About paraffin wax It has a melting point of 55 ° C., which is above the solidification temperature of the mixture. Therefore, the oil temperature If the temperature is slightly higher than the solidification temperature, paraffin wax and oil can be mixed. You. If the oil temperature is too low, the paraffin wax will solidify immediately upon contact with the oil, Incomplete mixing with raffin wax. Incomplete mixing of oil and wax can lead to transport vessels May create pockets of liquid oil inside.   The data shown in FIGS. 1-10 show that crude oil and other coal It was obtained from a series of experiments to study the reversible coagulation of hydrogen hydride. this The crude oil selected for their research was light sweet crude from Pennsylvania. What is known. These experiments were performed to determine the crude oil settling at various temperatures. The required concentration of molten or liquefied paraffin wax was determined.   Crude oil is mixed with various concentrations of molten or liquefied paraffin wax and placed in a 60 ° C water bath. The paraffin was completely melted for 入 れ minutes to 5 minutes to obtain a homogeneous mixture. Next, The mixture was set at the desired temperature in a water bath and kept warm for 48 hours, and the experimental results summarized in FIGS. I got a fruit. The% solidification is determined by monitoring the change in the slope of the cooling curve over time. Was determined by measuring the freezing point. Oil containing liquefied paraffin in the presence of water In order to examine the solidification behavior of The mixture was suspended.   The data shown in Figures 1 to 6 show that paraffin wax solidifies oil and This shows that the paraffin concentration required for coagulation depends on the oil temperature. In addition, When these experiments were performed in the presence of water, the paraffin wax% required for coagulating the oil was significantly lower. This is indicated by the shift of the curves to the left in FIGS. Is done.   The results plotted in FIGS. 1-6 show that the solidification of paraffin-containing oils is dependent on temperature. It is a phenomenon that exists. That is, as the temperature increases, the mixture Increases the concentration of paraffin required to cause coagulation of the paraffin. Of oil by paraffin 4 ° C is optimal for coagulation, but it will be around 20 ° C if water is mixed in the coagulation process (Fig. 7 and And Table 1). In other words, paraffin-containing oils are Coagulation is more beneficial than coagulation in the absence of water.   The coagulation of oil in paraffin is a time-dependent phenomenon, Depends on the paraffin concentration. FIG. 8 shows the results for paraffin 9% It represents the time course of coagulation of oil, and optimal coagulation occurs in 30 to 40 hours, Oil coagulation does not occur in the absence of paraffin.   Viscosity is a measure of the resistance of a fluid to flow generated under shear stress. Para Different crude / paraffin wax blends to characterize the coagulation process using fin wax The viscosity of the product was measured. A homogeneous mixture of oils with various paraffin concentrations was described earlier. Prepared as described and use an Ostwald viscometer to increase the viscosity of these mixtures at 200 ° C. It was measured. FIG. 9 shows that oil viscosity increases with paraffin concentration . When the concentration of paraffin wax exceeds 7%, the viscosity increases rapidly and at around 15% the oil flow Mobility disappears. These results show earlier results for the solidification behavior shown in FIGS. Consistent with findings.   To investigate the coagulation of petroleum hydrocarbons other than crude oil using paraffin wax, Phosphorus and diesel fuel were chosen. Both of these hydrocarbons are converted to varying concentrations Mix with molten or liquefied paraffin to prepare a homogeneous mixture, solidify at 20 ° C Movement was measured. FIG. 10 shows that with the appropriate concentration of paraffin wax, gasoline and This indicates that all diesel fuels solidify. Gasoline and diesel The optimal concentration of paraffin wax required to coagulate And 20%.   The rate of solidification depends on the rate of cooling and the initial temperature of the mixture. Complete large amounts of mixture It is considered that a long time is required for complete coagulation. Oil tanker on the voyage If the temperature of the surrounding seawater is low enough, the mixture is cooled down It is estimated that Even if the cargo oil does not solidify enough, the mixture will Where the mixture comes into contact with the cold walls of the hull, it forms a solidified "skin" It is expected that the kin will take up the liquid mixture inside. The solidified skin is damaged Occasionally the mixture should be prevented from flowing out of the cargo hold. Due to such damage Any leaking liquid will come into direct contact with seawater. Ocean shipping vessel sails At most latitudes, the seawater temperature is low enough that the spilled mixture solidifies Will do.   The solidification of the mixture also makes the tanker safer for the crew. Benefits. A strong buoyant mixture in the ship's cargo hold may Is not replaced by water, even if the hull has holes and is lower than the waterline. If so, the ship will remain floating.   The mixture may be heated to facilitate removal of the mixture from the cargo hold of the ship. Once liquefied, the mixture is pumped from the ship and placed in storage tanks. Or it can be piped to a refinery. Paraffin wax is well known to those skilled in the art. It can be recovered from hydrocarbons using recovery techniques such as fractional distillation. blend Paraffin wax recovered from coal is reused as a coagulant for transporting oil over and over again. Can be used. Recycle paraffin to purchase additional paraffin The overall cost of the oil transportation method of the present invention is reduced since the need for Can be lowered.   Oil transport per tanker decreases depending on the concentration of wax in the solution. Dissolution Tanker transport per voyage is reduced by 4% if the body contains 4% by volume of wax Results. It is necessary to consider the volume of liquefied wax added to the tanker. Liquefied wax Pumping oil into tanker if oil is pumped into tanker with oil The capacity can be corrected by adjusting the speed. The higher the paraffin concentration, the more The coagulation process due to the addition of the raffin takes place quickly and the resulting coagulated mass becomes hard.   As described above, paraffin wax is introduced into crude oil in a molten or liquefied state and mixed. May be combined. In addition, a temperature suitable for the crude oil to melt or liquefy paraffin , It is also possible to introduce paraffins in crude or solid form in crude oil. It is believed that there is. Specific persons who introduce paraffin wax and mix with hydrocarbons The law may also depend on the processing conditions as it is loaded on the transport vehicle.   Those skilled in the art will recognize that other waxes may be used in addition to paraffin wax. Would. For example, suitable coagulants include the broader range of low melting paraffin waxes; Uva wax; saturated fatty acids such as palmitic acid (m.p. 63 ° C) and stearic acid (m.p. 70 ° C) And ozokerite, a naturally occurring mineral wax containing a mixture of solid hydrocarbons; Can be The preferred concentration of a particular wax is, in part, a wax for a particular grade of crude oil. Of the mixture, the melting point of the wax, and the temperature of the mixture retained during transport.   Based on the studies summarized in FIG. 10, the hydrocarbon wax disclosed herein was used. Be able to coagulate other hydrocarbon liquids in addition to crude oil Will be quite obvious to those skilled in the art.   In another embodiment of the present invention, the mixing of the coagulant with the oil may cause a disaster Not performed until immediately before. Store the coagulant in a liquid state in a separate tank chamber and transport the oil When the ship is at risk of damage, mix the coagulant and oil immediately to form a mixture. To achieve. Contact with cold seawater quickly solidifies and forms a buoyant mass, This prevents excessive loss of crude oil. Only when there is a risk of disaster If a coagulant is added to crude oil, the cost of collecting the coagulant in the event of a disaster does not increase. Be reduced.   The method for pre-treating crude oil or other hydrocarbons according to the present invention uses the prior art spill The reason why it is extremely advantageous over the purification method is that the pretreatment method There is no need for material or other purification equipment used at the spill site. Hydrocarbon wax / raw The oil mixture can be easily separated. Because wax is a natural substance contained in crude oil Because it can be separated using existing purification equipment. is there. Further, the hydrocarbon wax can be reused. Similarly, the molten hydrocarbon wax Coagulating crude oil using It is quite advantageous. The reason is as described above. B)Treatment of contaminated oil   To encapsulate harmful hydrocarbons such as waste oil or PCBs for storage, first First, the hydrocarbon and the molten hydrocarbon wax are mixed to form a mixture. Wax and blend The temperature of the compound is kept above the solidification temperature. The mixture is contained in a container such as a drum While in, the mixture is cooled to a temperature below the solidification temperature. The curd obtained in this way A solid solid can be stored forever.   Paraffin wax or other waxes having a similar melting point can be used. mixture The concentration of wax in the product depends on several factors, such as the type of hydrocarbon being encapsulated I do. The higher the weight percentage of wax present, the higher the coagulation temperature of the coagulation mixture.   In the mixing stage, the temperature of the hydrocarbon is kept above the solidification temperature range. continue The concentrated solution can be added to the hydrocarbon. Rich wax solution and hydrocarbons Stirring may be required for thorough mixing.   The leachate was examined to evaluate the efficacy of the encapsulation method. At this time, waste oil (PCB) is Encapsulated with raffin wax. Table I shows several samples BH (but not samples). Le A is a paraffin wax). About the procedure This is described below.Leachate test procedure   Total PCB Amount: Using Soxhlet extraction procedure, sample (9 .938 g). The dichloromethane was replaced with 245 mL of iso-octane. Extract Was further diluted 1000 times, and a gas chromatograph (GC / ECD) He with an electron capture detector was used. Analysis was performed using wlett Packard GC / ECD 5890 Series II. Column is 30 meters DB 5 (phenyl 5%).   Leachate testing procedures are subject to Rule 347 (Revised Ontario 1990; Environmental Protection Law). (Modified from Ontario Rules 183, 240, 501, 555/92). (Gener al-Waste Management) November 1982, p.113-118.   PCB amount in water: Extract a water sample with dichloromethane and extract in iso-octane Concentrated. Next, the sample was analyzed using GC / ECD.   The area measured for the compound was converted to abundance using the calibration factor (cf). The calibration factor is calculated during the calibration experiment using the following equation:   Cf of component (X) = amount of standard (X) / area of standard (X) The saved calibration coefficients are then used in subsequent analysis experiments to finalize using the following equation: Compute the result:   Amount in sample (X) = Area in sample (X)^*Component (X) cf Typical calculation (sample: H):   A sample of paraffin wax + PCB oil (0.500 g) was sonicated for 12 minutes with hexane: Extract with 210 mL of acetone (1: 1) mixture to determine the total amount of PCB. The extract is GC / ECD Analyze using Standard 2.00ng / μL Standard area 2000321 Sample (H) area 1120202 Ingredient (X) cf 9.9982 × 10^-7 Amount in diluted sample 1.12ng / L or 1.12μg / μL Dilution factor 10mL Total PCB amount in 0.50g sample = 1.120 × 10                                   = 11.20μg Total PCB amount in sample = 11.20μg / 0.50g                                   = 22.4ppm   The solidification temperature of the mixture depends on the type of hydrocarbon to be encapsulated, paraffin wax Depends on quality and purity, and the concentration of paraffin wax. A place to encapsulate oil In such a case, the solidification temperature may not be specified, and may range over several degrees Celsius. Wax The purity of ip and hydrocarbons all affect the magnitude of this range.   When coagulating crude oil, the coagulation rate depends on the initial temperature and cooling rate of the mixture I do. In this case, the solidification rate is not a critical factor. Because the mixture is This is because it is generally stored in a storage container for a while before transportation.   In the event of a containment breach, harmful hydrocarbon spills may result in solidification of the mixture. More suppressed. Harmful if containers are buried or placed underground The likelihood of hydrocarbon leakage is similarly reduced.   In one example of solidifying PCB waste (but not limited to this example) ), Heat the paraffin wax to 54 ℃ ~ 60 ℃, PCB temperature above room temperature To hold. 2 cups (16 oz) of liquid natural paraffin wax, 14 cups (112 oz) (1) to the container containing the PCB waste oil, and solidify the resulting homogeneous mixture to about 1 g Ron forms a solidified PCB.   In a scaled-up example, 6.5 gallons of liquefied paraffin at 54 ° C to 60 ° C ~ 7 gallons were added to a standard drum containing about 48 gallons of PCB waste oil and the resulting The mixture is stirred to form a uniform mass. This mass solidifies on cooling. For applications However, up to 50% by volume of paraffin can be used to achieve virtually complete waste oil uptake. It can be carried out.   Referring to FIG. 11, encapsulated according to the methods disclosed herein. A mixture of PCB and hydrocarbon wax 11 is indicated generally at 10. Paraffin The neutralized layer 12 containing encapsulates the solidified mixture 11 and The outer seal layer 14 containing the component forms a hard supportive outer protective layer. Fig. 12 (a) The infrared analysis shown in FIG. 11 is for the structure 10 of FIG. First, this structure The body is encapsulated in a container, then the structure is removed and divided, and the layers 12 and 14 An analysis was performed for each. The wavelength scan 20 measures the inside portion of the neutralization layer 12. The scan 22 was measured on the inner part of the seal layer 14. You. FIG. 12 (b) is superimposed on FIG. 12 (a). Figure 12 (b) shows a sample of oil mixed with PCB , And a characteristic PCB peak appears. FIG. 12 (a) and FIG. 12 (b This technique did not detect PCBs in layers 12 and 14. You can see that. From these results, as disclosed herein, paraffin It is supported that the solidification method of sealing PCB waste using a thin film is effective.   If hazardous hydrocarbons are to be permanently disposed of by incineration, etc. The solution can be liquefied by heating the solution to a higher temperature . Subsequently, the liquefied solution can be fed as it is into an incinerator. Other If it is desired to transfer the oil to another container, the mixture is liquefied and then transferred .   The use of paraffin wax for the pretreatment of hydrocarbons before transport Although described in connection with certain research, the scope of the invention disclosed herein It will be apparent to those skilled in the art that various modifications of the method of the present invention can be readily performed without departing from You will understand. For example, as mentioned earlier, other hydrocarbon-based waxes are used. The same effect as paraffin wax can be obtained by using it. Volume% is determined for each type of hydrocarbon solidified against the type of wax used However, the optimum value can be easily determined by those skilled in the art using a conventional method. Will.

────────────────────────────────────────────────── ─── Continuation of front page    (81) Designated countries EP (AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, M C, NL, PT, SE), OA (BF, BJ, CF, CG , CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (KE, MW, SD, SZ, UG), AM, AT, AU, BB, BG, BR, BY, CA, C H, CN, CZ, DE, DK, EE, ES, FI, GB , GE, HU, IS, JP, KE, KG, KP, KR, KZ, LK, LR, LT, LU, LV, MD, MG, M N, MW, MX, NO, NZ, PL, PT, RO, RU , SD, SE, SG, SI, SK, TJ, TM, TT, UA, UG, US, UZ, VN

Claims (1)

[Claims]   1. A method of pretreating a hydrocarbon for transport or storage, comprising: Closed while maintaining a temperature above the solidification temperature range where the hydrocarbon wax mixture solidifies Mixing hydrocarbons and hydrocarbon waxes in space to form a mixture. When the temperature of the mixture falls below the solidification temperature range, the mixture is The hydrocarbon wax is present in an amount effective to qualitatively solidify, whereby the mixture Substantially coagulated, and the coagulated mixture is above the coagulation temperature range. The above method, wherein the mixture liquefies when heated to a temperature.   2. The hydrocarbon is crude oil and the temperature of the crude oil during the addition of the hydrocarbon wax; Is maintained above the coagulation temperature range of the mixture.   3. The method of claim 2 wherein said hydrocarbon wax has a melting point above about 50 ° C.   4. 4. The method according to claim 3, wherein said hydrocarbon wax is a paraffin wax.   5. The coagulated mixture is heated to a liquid and subsequently the liquid is removed from the enclosed space. Claiming the mixture from the enclosed space by pumping the body 4. The method according to 4.   6. The paraffin wax is recovered from the crude oil by fractional distillation of the mixture. 6. The method of claim 5, wherein   7. The hydrocarbon is crude oil, and the hydrocarbon wax is paraffin wax, 2. The method of claim 1 wherein said element is selected from the group consisting of nauba wax, palmitic acid, and ozokerite. The described method.   8. The concentration of the paraffin wax in the mixture ranges from about 2 ounces per gallon of crude oil to 5. The method of claim 4, wherein the weight is about 8 ounces.   9. The concentration of the paraffin wax in the mixture is from about 1% to about 30% by volume. The method of claim 4.   10. A method of encapsulating a liquid hydrocarbon for storage, said method comprising: Mixing hydrogen and paraffin wax to form a mixture. When the temperature of the mixture falls below the solidification temperature range, The solidified mixture is substantially solidified. The above method of forming a body mass.   11. The liquid hydrocarbon is a solution of polychlorinated biphenyl; The method of claim 10, wherein the concentration of the wax is about 50% by volume.   12. A method of pretreating a hydrocarbon for transport by ship, comprising:   a) mixing the hydrocarbon and the hydrocarbon wax in the enclosed space of the ship to form a mixture; A step of storing the mixture [however, during the mixing, the mixture is allowed to solidify to form a solid; Keeping the temperature higher than the solidification temperature range; the hydrocarbon wax will maintain the temperature of the mixture at the solidification temperature Below the temperature range, the mixture is present in an amount effective to substantially solidify the mixture. And thereby substantially solidifies the mixture; and further, the solidified mixture is Liquefies when heated to a temperature higher than the solidification temperature range),   b) transporting the mixture on the vessel to a destination; and   c) recovering the hydrocarbon wax from the mixture; The method comprising:   13. The hydrocarbon wax is present in the mixture in an amount from about 1% to about 30% by volume. 13. The method according to claim 12, which is a paraffin wax.