JPH0117518B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to natural substances such as oil gas, crude oil, bitumen, oil extracted from oil sand or oil shale, tar extracted from tar sand, and oil reservoirs derived from these natural substances. All petroleum or petroleum fractions (hereinafter referred to as petroleum and/or related substances), including fractions and streams and products during the petroleum refining process, are brought into contact with and contained in the added asphaltenes. This relates to a new method for recovering oil (and/or gas) containing the above components at reduced concentrations by precipitating them together with asphalt components and/or non-hydrocarbon components, etc., removing and separating these components. It is. Asphalt or asphaltenes can also be recovered in various methods according to the method provided by the present invention. The feedstocks used in processes such as cracking are today generally residues or heavy distillates from distillation processes. However, if necessary, raw crude oil may be used as a raw material for cracking, and in that case, the crude oil must be desalted beforehand. Like distillation residues, heavy crude oils usually contain significant bituminous components, leading to coke formation in many high-temperature processes, and carbon formation on the catalyst surfaces used in cracking processes. It is well known that these catalysts can become a source of deposits, reducing their performance and shortening their service life. Crude oil (common) contains significant amounts of non-hydrocarbon organic components, primarily substances including sulfides, nitrides and oxides, as well as coexisting with small amounts of soluble organometallic substances and asphaltenes and resins. Contains inorganic salts present in colloidal suspension. These non-hydrocarbon components, etc., are encountered throughout the boiling range of petroleum oil, but tend to be concentrated in the non-volatile fractions, particularly asphaltenes and resins. Even in very small amounts, these substances can cause serious corrosion problems, catalyst deactivation, reduced product quality, and health problems. Regarding general, non-hydrocarbon components in crude oil,
There is a substantial correlation between the asphalt component and the asphalt component, and the higher the content of the asphalt component, the higher the content of non-hydrocarbon components. For this reason, it is considered necessary to preliminarily remove asphalt components from feedstocks used in cracking and other petroleum refining processes. BACKGROUND OF THE INVENTION There are various methods for removing asphalt and non-hydrocarbon components to enhance the properties of feedstocks and petroleum or related materials. Conventional methods and processes can be considered as summarized below. (1) Flat distillation method (2) Vacuum distillation method (3) Viscous braking method (4) Coking method (5) Solvent treatment method (6) Alkali treatment method (7) Gas treatment method (8) Oxidation treatment method (9) ) Adsorption treatment method (10) Acid treatment method (11) Precipitation method using reactive metal salts etc. [Problem to be solved by the invention] Among the above methods, the solvent treatment method is the most effective for removing asphalt components. Although effective, this method, like other conventional methods, suffers from economic and operational disadvantages, requiring specialized equipment and/or aggressive operating conditions. Most conventional methods are not suitable for large-scale processing of crude oil due to their high cost. Moreover, some of these traditional methods produce waste and require special waste handling methods.
This can lead to difficult waste disposal problems. In view of the above-mentioned facts, one of the main objects of the present invention is to provide a new method for simultaneously removing asphaltic and non-hydrocarbon components from petroleum and related materials, avoiding the difficulties common in conventional methods. The goal is to provide the following. Among other things, one of the objects of the present invention is to provide a simple and effective method for economically refining and separating large amounts of crude oil. Another main object of the invention is to
Alternatively, a novel method may be provided for economically recovering asphaltenes while simultaneously purifying related substances. Since recovery of asphaltene by conventional methods is expensive, asphaltene has not been produced in large quantities to date. It is known that asphaltenes have many important uses. Other important objects of the invention include the following. (1) To provide a new method for refining petroleum and/or related substances that uses only the constituent components in petroleum and does not require any other substances, and (2) to be able to be used in conjunction with many conventional methods. (3) providing a new method for refining petroleum and/or related substances that requires relatively low energy consumption; (4) to provide a new method for refining petroleum and/or related substances that does not require specialized, expensive equipment or hazardous operating conditions; (5) to provide a new method for refining petroleum and/or related substances that does not produce waste; (6) provide a new method for purifying the relevant substances; (6) feedstocks with a wide range of chemical compositions and physical properties can be easily handled without significant changes in equipment and operating conditions; and to provide new methods for refining such petroleum and/or related substances. Means of Solving the Problem According to the invention, petroleum (or related substances) is brought into contact with added asphaltenes (preferably of the same type as the asphaltenes contained in the feedstock to be treated) to By precipitating the asphalt components and non-hydrocarbon components contained in the petroleum oil (or related substances) together with the added asphaltene and separating the precipitate,
Petroleum can be refined in a quick and effective manner by removing the asphalt and non-hydrocarbon components contained in the oil and recovering the remaining oil components.
Under the above conditions, asphaltenes added to the feedstock will attract and combine with the resins and other heavy aromatics contained in the feedstock, resulting in The inventors have discovered that the equilibrium relationship between asphaltic substances and other heavily aromatic substances is broken. Disruption of the above equilibrium relationships results in precipitation of asphalt and non-hydrocarbon components. Following this precipitation, an agglomerate of added asphaltene and precipitated asphalt components is formed. The agglomerates thus formed are
It is easily separated from the remaining oil component, and since the recovered oil component has already been de-asphalted,
Suitable as feedstock for subsequent purification operations. On the other hand, the separated precipitate (agglomerate) is further processed and recovered as asphalt or asphaltene. A portion of the asphaltene thus recovered is recycled to the contacting process described above. Contact between the petroleum feedstock and the added asphaltene is typically carried out at a temperature below the boiling point of the feedstock, and precipitation of the asphalt component is usually carried out at temperatures near ambient temperature. Heat exchange can therefore take place between the contacting device and the precipitation (or separation) device for heat saving purposes. Incidentally, the above precipitate can be treated with a paraffin-based solvent to precipitate and recover high-quality asphaltene. The used solvent can be easily recovered and used again. Therefore, the process does not require any chemicals other than the feedstock components. Asphaltenes are brown to black, finely powdered, non-crystalline substances, usually obtained by processing petroleum, residues, bituminous materials, etc. using light naphtha or solvents in petroleum. Naphthas in petroleum range from very common paraffinic chain compounds to highly aromatic types. Based on their solubility in different solvents, the constituents in petroleum and/or related substances can be distinguished as follows: (1) Carboids - Insoluble in carbon disulfide, carbon tetrachloride and low molecular weight paraffins. (2) Carbenes - Soluble in carbon disulfide, but not in carbon tetrachloride and low molecular weight paraffins. (3) Asphaltene - Soluble in carbon disulfide and carbon tetrachloride, but not in low molecular weight paraffins. (4) Maltene - Soluble in carbon disulfide, carbon tetrachloride and low molecular weight paraffins. Although most petroleum oils contain very little carboids and carbenes, some residues from the cracking process may contain 2 percent or more by weight. In industry, the separation of crude oil and bituminous materials to obtain the binary components of asphaltenes and maltenes is a process that involves the separation of crude oil and bituminous materials to obtain the binary components of asphaltenes and maltenes. This is conveniently achieved using . Highly aromatic petroleum naphtha is
Since asphaltenes are partially dissolved at high temperatures, their use for the purification of asphaltenes or the dilution of petroleum containing asphaltenes is not recommended in the present invention. The reason for this is to preserve the original properties of the added asphaltenes used in the contacting operation. Pentane, heptane and hexane are particularly suitable for this purpose. In particular, it is known that n-pentane can effectively precipitate asphaltenes without changing their properties. The inventors have discovered that by using n-pentane as a diluent, it is possible to precipitate more of the asphaltenes contained in petroleum or related substances. Even so, the capacity of n is more than 40 times that of crude oil.
- By diluting the crude oil with pentane and using silica gel in an amount equivalent to 10 percent of the weight of the crude oil as a precipitation aid, it was possible to precipitate 90 percent of the asphaltenes in the crude oil. On the other hand, even if the same crude oil is not diluted with n-pentane, the same type of asphaltenes as the asphaltenes contained in the crude oil can be converted into residual oil (distillation of 600〓 (315.6℃) or higher) in the crude oil. Most of the asphaltenes contained in crude oil can be removed by adding only half of the amount of
100% can be precipitated. I think it would be useful to consider the effects of adding asphaltene to petroleum or related substances. Hydrocarbons and their series contained in petroleum or related substances are closely related to each other, and these substances differ mainly in molecular weight and hydrogen/carbon ratio. With the exception of asphaltene hydrocarbons, which are often hydrogen deficient and often exhibit anomalous structures, the hydrocarbon series (consisting of asphaltenes, resins and oils) in petroleum or related materials vary in molecular weight and hydrogen/carbon ratio. There is partial overlap between adjacent series. Except for carboids and carbenes, which are contained in extremely small amounts in crude oil,
Asphaltene can be said to be the final condensate. A high degree of aromaticity is generally exhibited in common with asphaltenes and their series. Just as the paraffin content in petroleum is important in separating resins from asphaltenes, aroma content is important in binding resins with asphaltenes. The higher the aromaticity of the resin and oil, the better the solvation effect of asphaltene (depending on the resin), and the solvation effect of resin and oil is one of the most important things in understanding the properties of the asphaltene/maltene interface. This interface characterizes the colloidal nature of crude oil and bituminous materials. Even if the same asphaltene is dispersed in a highly aromatic solvent, it will precipitate in a low aromatic solvent. Specifically, the colloidal stability of a petroleum or bituminous material can be easily altered by changing the asphaltene/resin ratio or by changing the type of asphaltene or resin in it. The inventor of the present application has discovered that this is possible. The degree of peptization of asphaltenes in crude oil is strongly influenced by the aromaticity of resins and heavy aromatic substances contained in the crude oil, metal components, and elemental components other than carbon in the aromatic rings. Ru. Even if the resin has the same level of aromatic properties, the degree of peptization of asphaltene increases if the content of metal components and elemental components other than carbon is large. The resin and asphaltene are bonded together in a type of electron transfer relationship, and the certain molecular structural similarities between asphaltene molecules and resin molecules play an important role in determining the colloidal properties of crude oil. It seems to be working. The above facts were discovered by the present invention by introducing asphaltene extracted from one crude oil into another different crude oil and experimentally observing the stability of the newly formed asphaltene/oil dispersion. This was discovered by someone. In all cases, asphaltenes were readily dispersed in the crude oil from which they were extracted. However, as the amount of asphaltenes added to the crude oil increases, an insolubility point in the crude oil is finally reached, at which point the asphaltenes and the resin begin to precipitate together. Based on this discovery, the inventor of the present application has determined that, for a given crude oil, at a given temperature, the asphaltene/resin ratio can contain the maximum amount of asphaltene that can be dispersed in the crude oil without precipitation. I believed that there was such a thing. This ratio can be defined as the "asphaltene/resin peptization constant (or ratio)", and this constant is the optimum amount of asphaltene required to contact and separate a given crude oil. It is useful for determining the It can be said that asphaltene with a high hydrogen/carbon ratio is more easily dispersed in petroleum than asphaltene with a low hydrogen/carbon ratio. As the asphaltene/resin ratio in the crude oil decreases, addition of asphaltenes with high hydrogen/carbon ratios tends to produce gels, whereas addition of asphaltenes with low hydrogen/carbon ratios tends to cause precipitation. Similarly, these facts can be explained by the aromatic intensity of asphaltenes and maltenes in petroleum. Extensive experimental evidence obtained by the inventors shows that asphaltenes in unprocessed crude oil exist in monomolecular form and are peptized and deagglomerated by resin molecules. Dispersed by aromatic molecules. However, the asphaltenes in the bitumen are present in agglomerated form, and the asphaltenes in the residue (of distillation) appear to be present in the form of large nodules. There is also experimental evidence that hydrogen bonds appear to be the dominant source of intermolecular forces between resin molecules and asphaltene molecules in unprocessed crude oil. This fact may explain why asphaltenes in crude oil are more difficult to separate than asphaltenes in residual materials.
Once the peptized resin molecules are lost, asphaltene molecules easily form agglomerates or nodules when they collide with each other due to their polarizability. Both asphaltene molecules and resin molecules are very large, so their diffusion rate in petroleum is extremely slow and insignificant. Therefore, stirring and mixing are extremely important in the contact operation provided by the present invention.
It is most important to bring the resin and asphaltene into direct and intimate contact. Through hydrogen bonding, each asphaltene molecule peptized by a large number of resin molecules forms a micelle, and the most aromatic and polar resin molecules with large molecular weights are arranged near the asphaltene molecule in the center of the micelle. is in a state of These substances are in turn surrounded by aromatic and less polar components of small molecular weight, and are finally in a state where they are gradually transferred to the oil phase between the micelles. Metal components and elements other than carbon in petroleum appear to be concentrated on the inside of the micelles rather than on the outside. Therefore, separating asphaltenes and resins from petroleum or related materials is also key to the removal of these non-hydrocarbon components (elements other than metals and carbon). Asphaltene/resin peptization constant (or ratio) above
Breaking the equilibrium at the asphaltene/resin interface by exceeding . Hereinafter, the present invention will be described with reference to some examples of the basic process of the present invention shown in the accompanying drawings, FIGS. The invention will be explained in detail. FIG. 1 schematically depicts one embodiment of the basic process for refining and partially separating petroleum or related substances according to the method provided by the present invention. FIG. 2 schematically depicts one embodiment of the basic process for refining and partially separating heavy crude oil, bitumen, residual materials, etc. according to the method provided by the present invention. FIG. 3 schematically illustrates one embodiment of the basic process for purifying and partially separating heavy crude oil, bitumen, residual materials, etc. and recovering asphaltenes according to the method provided by the present invention. It is something that The invention will now be described in detail in conjunction with some different embodiments and experimental results illustrated in the accompanying drawings. As mentioned above, FIG. 1 schematically depicts one embodiment of the basic process for refining and partially separating petroleum or related substances according to the method provided by the present invention, which includes the following five steps. It includes two processes. That is, (1) contact process, (2) solid-liquid separation process, (3) asphaltene precipitation process, (4) asphaltene drying process, and (5) n-pentane recovery process. As shown in FIG. 1, the contacting device 1 is, for example, a mixing (or stirred) tank, a fluidized bed, etc., which ensures intimate contact between the feedstock and the added asphaltenes and removes the asphaltenes in the feedstock. A solid-liquid separator 2 for facilitating the precipitation of components and non-hydrocarbon components together with added asphaltene includes, for example, a filter, a centrifuge, a hydrocyclone, etc., to separate the precipitate from the remaining oil components. It exists to perform a certain function.
The asphaltene precipitation device 3 is, for example, a mixer/
The purpose of this system is to wash the above precipitate with n-pentane and reprecipitate it using a settler combination device, a filtration layer, etc., and to separate asphaltene from pentane. The asphaltene drying device 4 is, for example, a flash drum,
This is a vacuum dryer or the like to remove residual pentane from asphaltene that has been precipitated for the purpose of final recovery of asphaltene. The n-pentane recovery device 5 is provided to recover pentane for reflux (recycling) using, for example, a flash distiller or evaporator, and to recover a mixed liquid of resin and oil to be used in the subsequent refining process. Contact step 1 and solid-liquid separation step 2 are the most basic steps, and in some cases they may be performed using the same equipment, such as a countercurrent mixer/settler combination, a contactor, and a rotary filtration process using asphaltene as a super-aid. They can also be carried out simultaneously in a container. In contactor 1, the feedstock is brought into intimate contact with the added asphaltenes and the asphalt and non-hydrocarbon components in the feed are precipitated with the added asphaltenes. In the solid-liquid separator 2, the precipitated solid mixed substance is
It is effectively separated from the liquid phase consisting of the oil component, and the oil component thus separated is suitable as a feedstock for use in catalytic cracking and other refining operations. The precipitated mixture may be partially or completely flashed to remove residual volatile components and then steam stripped to produce high quality asphalt. Alternatively, this precipitated mixture can be treated with n-pentane in the asphaltene precipitation device 3 to precipitate pure asphaltene containing almost no resin. On the other hand, in the asphaltene drying device 4, the residual n-pentane is removed and the precipitated asphaltene is dried, but the n-pentane separated from this asphaltene is further sent to the pentane recovery device 5 and recovered. , recirculated. A portion of the asphaltene thus recovered is recycled to the contacting device 1. The resin and oil mixture obtained by the pentane recovery device 5 can be used as a feedstock for heat cracking or resin recovery. Methods and devices for contacting vary widely as described above. Contact device 1 shown in FIG.
The apparatus should normally be equipped with means for mixing and agitating the materials within the apparatus. These means include, for example, an agitator, an air agitator, a vibrator,
There are fixed mixers, sonic generators, etc. It is also conceivable that the contacting device 1 takes the form of a fluidized bed of added asphaltenes and the oil to be treated. If a superbed (or packed bed) is used to carry out both contact and subsequent solid-liquid separation (in the same device), it is necessary to periodically discharge accumulated precipitate from the device. However, it is also possible to carry out both contacting and separation of the feedstocks (in the same equipment) continuously by means of a continuous filter using asphaltenes as filter aid. In this case, the film thickness of the precipitate left on the filter cloth acts as a filter aid and performs various functions of contact, precipitation, and separation. Thus, continuous contacting combined with continuous solid-liquid separation can be effectively carried out by continuously adding fresh asphaltenes into the feedstock. Other solid-liquid contact methods and devices and various flow combinations (e.g., countercurrent, cocurrent, crosscurrent, etc.)
It is obvious to those knowledgeable in this field that it can also be used. Needless to say,
There are a wide variety of solid-liquid separation methods and apparatus that can be used to carry out the present invention. As mentioned above, Figure 2 schematically illustrates the basic steps for recovering the solvent (used) and asphaltenes after purification and separation of heavy crude oil, bitumen, residue, etc. according to the method provided by the present invention. This is what is shown. According to FIG. 2, the feedstock is first diluted with a petroleum fraction with a boiling point below 315.6°C, especially a paraffinic solvent, and then intimately mixed with the added asphaltenes in the contactor 1. The asphalt and non-hydrocarbon components in the feed are brought into contact to cause them to precipitate with the added asphaltenes. The contacting device 1 may be a mixer/settler combination, a fluidized bed, etc. as described above. The precipitated solid mixture is flashed (or dried)
The remaining volatile components (mainly the diluent added in the contactor) are removed from the mixed material, after which the solid mixture is further treated with a stripper 3 to strip the asphalt. Become.
On the other hand, the oil from which the asphalt component has been removed is transferred to the evaporator 4.
The diluent is separated from the diluent by evaporation and further stripped with steam in a stripper 5. The solvent (diluent) recovered in each of the four stages described above is combined and recycled to contactor 1. The method of the present invention using added asphaltenes as a solid contact agent eliminates the need to use liquefied propane or butane to process the feedstock at high temperatures and pressures. The crude oil thus treated is suitable for use as a feedstock for catalytic cracking and many other refining operations. As mentioned above, FIG. 3 depicts one basic process concept for refining and separating heavy crude oil, bitumen, residual materials, etc. and recovering asphaltenes and solvent pentane according to the method provided by the present invention. This is an illustration. The process is fundamentally similar to that shown in Figure 2, except that pentane is used as a solvent (diluent) to precipitate the asphaltenes, and the treated oil still contains resin. However, it is different in that it can be used for thermal cracking. According to Figure 3,
The contacting device 1 is a mixer/settler combination, fluidized bed, etc., in which the feedstock is diluted with pentane and brought into contact with the added asphaltene to decarbonize the asphalt components contained therein. The hydrogen components are allowed to precipitate together with the added asphaltenes. All of the precipitated asphaltenes are separated from the oil component and sent to the flashing device 2 where they are flashed and dried to produce good quality asphaltenes, a portion of which is recycled to the contacting device 1 or recovered as a by-product. Ru. Incidentally, after the oil component is separated in the evaporator 3, a stripper 4 further collects pentane for recirculation. The oil component thus treated, which still contains resin, is suitable as a feedstock for hot cracking. Of course, the first
The bottoms coming out of the pentane recovery device 5 shown in the figure or the pentane recovery device 5 shown in FIG. can also be considered. As already clear from the above explanation, heavy crude oil,
When processing bitumen, residual materials, etc., the feedstock should first be diluted with a suitable hydrocarbon solvent before contacting with the added asphaltenes. The added asphaltene used for contacting the feedstock should preferably be first treated with pentane (in a manner that does not alter its original properties) to wash and dissolve the resin contained therein. Conditions for contact operation are extremely important in achieving the purpose of operation. Various important operating variables (conditions) are described below. (1) Temperature - The contact temperature is determined by the fluidity of the feedstock, the hydrogen bonding between asphaltene and resin molecules, and the redistribution of components near the interface between asphaltene and resin and within the micelles. Affects speed and equilibrium relationships, etc. The temperature within the contactor is normally maintained above 60°C (15.6°C), but not above the boiling point of the feedstock (or diluted feedstock). Generally speaking, crude oil is heated to about 160°C (71.1°C).
If the mixture is heated for 10 to 30 minutes and then allowed to cool to room temperature, the asphalt components will precipitate quickly. Small precipitates may be formed into large agglomerates by gentle stirring, followed by solid-liquid separation (eg, by filtration). (2) Pressure - Pressure has no effect unless liquefied gas is used as a solvent. The method provided by the present invention utilizes a liquid hydrocarbon solvent and optionally dilutes the feedstock. Therefore,
The contacting operation is usually carried out under atmospheric pressure. (3) Contact time - The required contact time is determined by the nature of the feedstock, the contact temperature, the degree of dilution, the amount of asphaltene added relative to the amount of asphalt component contained in the feedstock, etc. Heavy feedstocks, low contact temperatures, low dilutions, and low asphaltene loadings generally require longer contact times. Of course, the contact method and equipment (for example, whether or not to stir, mixing conditions, etc.)
It is clear that this will have an effect on the contact time required. (4) Stirring - Intimate and uniform contact between the feedstock and the added asphaltenes can be quickly achieved at high temperatures by creating a homogeneous agitation condition (isotropic turbulence) through stirring. Once the asphaltene and resin molecules are in complete intimate contact, precipitation of the asphalt component (in the feedstock) requires little further agitation. However, the small precipitated particles thus generated tend to grow into large agglomerates by slow stirring and continued stirring. Inferring from these facts, a system consisting of a slurry pump, a stationary mixer, and a number of mixing tanks in series with a low-speed agitator is ideal for contact operations. In this case, the feedstock, solvent (if necessary) and added asphaltenes are fed to the slurry pump simultaneously, and the resulting slurry is uniformly mixed through a stationary mixer before entering the multiple mixing tank mentioned above. Close contact between the three is obtained, which results in precipitation and agglomeration of the precipitated particles in the mixing tank. (5) Differential Velocity (Between Solid-Liquid Phase) - When using packed beds or overbeds with added asphaltenes, using a small differential velocity and long residence time means that the feedstock flows through the bed. This is important for causing precipitation, agglomeration, and separation of the asphalt components during the process. (6) Viscosity - The viscosity of the feedstock should be adjusted by heating or dilution with petroleum fractions and promote contact between asphaltene and resin molecules and precipitation of asphalt components. If it is ordinary crude oil, the boiling point or 160〓 (71.1℃)
No dilution is necessary if contact is made at temperatures of about 100 ml. (7) Asphaltene (for addition) - as mentioned above,
The type and purity (free of contamination from resins and other heavy aromatics) of the added asphaltenes used in the contacting operation are critical. Preferably, the additive asphaltenes are of the same type as those contained in the feedstock, but have high aromaticity and hydrogen/carbon ratio, and are uniformly treated with pentane to produce resins and other heavy aromatics. It is best if it is not contaminated with substances. Asphaltene, once treated with pentane, is free of resin and other heavy aromatic contamination and is therefore highly effective as a solid contact agent for use in the methods provided by the present invention. The required amount of added asphaltene is most influenced by the asphaltene/resin peptization constant, as discussed above. This asphaltene/resin peptization constant (or ratio) generally decreases as the amount of diluting paraffinic solvent added to the feedstock increases. The reason for this is that the solvent molecules (paraffin) dissolve the resin molecules and thus separate them from the peptized asphaltene molecules. ) It may create new hydrogen bonds between asphaltene molecules and resin molecules, or break the hydrogen bonds between peptized asphaltene molecules and resin molecules. It is important that the asphaltene added for contacting should not be treated with strong solvents that would dissolve it or change its molecular substance, especially its molecular surface properties and molecular structure. For example, cycloparaffin, aromatic cyclohexane, pyridine, nitrobenzene, methylene dichloride, chloroform,
Carbon disulfide, carbon tetrachloride, etc. strongly attack asphaltene molecules and should not be used to dilute the feedstock or treat asphaltene for addition. In addition, when steam stripping asphaltene for addition at high temperatures, care should be taken not to oxidize or alter the quality of the asphaltene. (8) Solvents - As already mentioned above, hydrocarbon solvents that are less aromatic and less polar are generally suitable for diluting the feedstock. If possible, a paraffinic solvent with a low molecular weight is most suitable, but in most cases a petroleum distillate with an extremely low content of aromatic substances and whose boiling point does not exceed 400〓 (204.4℃) is used. Once hot, it is suitable for use in diluting most feedstocks. Even if the boiling point range of petroleum distillates is close to 600〓 (315.6℃), if mixed with lower boiling point distillates, the boiling point range will be 160〓
It can be used for contact operations at temperatures above (71.1℃). There are a wide variety of methods and apparatuses that can be applied to the solid-liquid separation operation following the contacting operation according to the method of the invention.
Examples include filtration (both batch and continuous), centrifugation, hydrocyclone, sedimentation, etc. The conditions for the solid-liquid separation operation depend on the nature of the feedstock and/or the precipitated material to be separated. Although filtration and centrifugation are generally effective,
Hydrocyclones are not very effective
Incidentally, mere natural sedimentation appears to be very inefficient unless the feedstock is considerably diluted. Thus, the simple method provided by the present invention allows for simultaneous and rapid removal of its asphalt components, metal components and non-carbon elemental components from petroleum or related substances. This process can include the recovery of asphalt and asphaltenes without any operational difficulties. Moreover, this method can be carried out in a slightly different manner by using various additives as desired, thereby widening its range of application and improving its effectiveness. For example, various additives such as inorganic metal oxides (silica gel, alumina, zeolite, etc.), clay minerals,
White clay, molecular sieves, etc., organic solid adsorbents, activated carbon, charcoal,
Lignite etc. can also be used as a contact agent together with the additive asphaltene. In solid-liquid separation operations,
A filter aid, such as diatomaceous earth, gypsum, etc., facilitates the filtering of precipitated asphalt components. Since asphaltene has a surface charge as mentioned above, it can be used with any polyelectrolyte, e.g.
When AlCl ₃ is added, its surface charge is canceled and it aggregates to form large particles and precipitate. It is well known that polycharged electrolyte substances are used as precipitation promoters in this manner. It is also well known that metal halide compounds such as Cucl ₂ and FeCl ₃ react with heavy aromatic substances to form complex compounds. Therefore, it is also known that such a metal halide compound can be reacted with a heavy aromatic substance such as asphaltene to form a complex compound and precipitate it. In this way, not only the above-mentioned polyvalent electrolytes and metal halide compounds, but also any acid that reacts with asphaltene and precipitates it from petroleum can be added as a precipitation promoter. However, it should be noted that any foreign matter (other than petroleum constituents) added to the feedstock may cause contamination of the treated oil and the products of subsequent refining processes. Moreover, separating these foreign additives from the solid hydrocarbon components (asphaltenes and resins) is generally extremely difficult and very costly. Therefore, the use of non-hydrocarbon materials is not particularly preferred in the method provided by the present invention. It is also conceivable that the method of the present invention supplements conventional methods by being carried out in parallel with them. However, for the reasons mentioned above, such processing methods should be carefully considered to avoid operational difficulties and contamination problems. In order to clearly illustrate the implementation of the invention and its advantages, the methods described above will now be further illustrated with the results of a number of experimental examples in connection with the accompanying figures 1, 2 and 3. The results of some representative experimental examples are shown in Tables 1 and 2.
The former reports the results of experiments involving 11 different crude oils, and the latter reports 4
The results of experiments in which different types of residues (petroleum distillates) were treated are reported.

[Table] In relation to Table 1, for each type of crude oil treated and each physical property measured, the first listed value is before treatment, and the second listed value is before treatment. Certain numbers are after processing. The measured physical properties were specific gravity at 60〓 (15.6℃), sulfur content weight percent, nitrogen content weight percent, atmospheric distillation residue weight percent at 700〓 (371.1℃), and recovered Net weight percent of asphaltenes. Due to losses of asphaltene in the recovery process performed in the laboratory, the percentage of asphaltene recovery reported in Table 1 is lower than the actual value, and the reproducibility of the data is probably plus or minus 10 percent. It is the rank. In carrying out each series of experiments, firstly, asphaltenes produced by treatment and precipitation with pentane were added to 2000 milliliters of crude oil, equivalent to half of the atmospheric distillation residue (at 700㎓ (371.1℃)). Add just the right amount and boil at 160℃ (71.1℃) for about 10 minutes. This slurry (mixture of crude oil and added asphaltenes)
was allowed to cool to room temperature (approximately 70 °C (21.1 °C)) and then passed through No. 4 Whattmann filter paper, and the entire precipitated material was separated (from the oil component). The precipitate thus separated was treated with pentane (10 times the amount of the precipitate) to precipitate only asphaltene, and then dried in vacuum at a temperature of about 190°C (87.8°C), and its weight was measured. Ivy. The net amount of asphaltene produced is the difference between the total weight of asphaltene recovered and the weight of asphaltene added, which is further converted to a weight percentage (relative to the amount of crude oil used) and shown in Table 1. has been reported. In a series of control experiments, various crude oils were treated in the same manner without the addition of asphaltene. In all control series of experiments, it was not possible to separate asphaltenes (from the crude oil). As can be seen from Table 1, by contacting these crude oils with added asphaltenes, the specific gravity of the crude oils is close to 6%, the sulfur content is over 80%, the nitrogen content is over 80%, and the ash content is More than 85 percent, and the residue content in the oil was reduced by nearly 95 percent. The amount of asphaltenes separated is the amount of crude oil processed.
It ranged from 11.2 to 35.5 percent, depending on the crude oil. Considering that the residue content was reduced by more than 95 percent in most cases, the above results correspond to asphaltene separation rates of more than 95 percent.

Table 2 reports the results of an example experiment involving the treatment of residual materials from four different crude oils. 1070 extracted from North Sea crude oil
Except for the vacuum distillation residue at (576.5°C), all are atmospheric distillation residues at 700°C (371.1°C). Each of the above residues was treated in three different ways: Namely, (1) contact by added asphaltene, (2) contact by silica gel, and
(3) Three methods of contact using a mixture of asphaltene and silica gel. To carry out each series of experiments, first mix 200 ml of residual oil with 1200 ml of aromatic-free gasoline (boiling point range 180° (82.2°C) - 400° (204.4°C)).
After adding one of the solid contact agents mentioned above, the mixture was boiled at a temperature of about 160°C (71.1°C) for about 20 minutes. The amounts of each of the solid contact agents used are as follows. (1) 60 grams of asphaltenes, (2) 120 grams of silica gel, and (3) 100 grams of a 1:1 mixture of asphaltenes and silica gel. After boiling, the slurry will be at room temperature (approximately 70〓(21.1
℃)) and then filtered through No. 4 Whattmann filter paper to separate all the precipitate. The separated precipitate is further divided into pentane (10% of the precipitate
The precipitated asphaltenes were treated with
Dry in vacuum at a temperature of 190㎓ (87.8℃). The net amount of asphaltenes recovered is the difference between the total weight of solid material recovered and the weight of added asphaltenes, which is further converted to weight percent and reported in Table 2. A series of control experiments were carried out in which various residues were treated without the addition of solid contact agents.
The rest was processed in the same way. However, in all control series of experiments, it was not possible to separate asphaltenes. The data in Table 2 are the average values of the results of several identical experiments performed on each residue. As can be seen from Table 2, in all cases the results of contacting with 60 grams of asphaltene were better than those of contacting with 120 grams of silica gel or 100 grams of a mixture of asphaltene and silica gel. These results also indicate that asphaltene has a 5 to 6 times stronger ability to separate asphalt components from the above-mentioned residual materials than licagel. The amount of asphaltene separated is more than 30 percent by weight (relative to the weight of the residue);
This corresponds to an almost complete separation of the asphaltenes contained in the residue. By the way, when silica gel is used as a contact agent, it is extremely difficult to separate it from the silica gel to which asphaltene is added.
Therefore, when treating petroleum or related substances by the method provided by the present invention, it is not preferable to mix the added asphaltenes with other solid contact agents. In addition to the crude oils and residual materials listed in Tables 1 and 2, various crude oils, bitumens and residual materials are
All could be purified and separated using different asphaltene loadings, different solvents or dilutions according to the method provided by the present invention. different hardness
Various other experiments were also conducted using liquid contact and solid-liquid separation methods. Roughly similar good results were obtained in all cases. As is clear from the above examples and explanations, petroleum and/or petroleum-related substances can be brought into contact with added asphaltene in accordance with the method provided by the present invention. components and elements other than carbon with the added asphaltenes, separating these components, and recovering an oil (or gas) component with substantially reduced concentrations of these components. Depending on the situation, it can be purified.
In carrying out the process, the feedstock to be treated should be heated or diluted with a solvent, if necessary, to adjust its fluidity and to facilitate the contacting and precipitation described above. The additive asphaltenes described above are preferably of the same type as contained in the feedstock to be treated, yet have a low hydrogen/carbon ratio and are mostly free of resins and other heavy aromatics. It's better not to. As already detailed above, the methods, equipment and operating conditions for the contacting and precipitate separation described above can vary widely. The above contact and precipitate separation may be carried out using the same equipment, such as a mixer/settler combination, an overlayer using asphaltene,
It is possible to carry out the process simultaneously in a continuous filter (using asphaltene as a super-aid) or the like. The method provided by the present invention may be implemented in combination with conventional methods, if circumstances permit.
In order to moderate the effect of this method, it is possible to use other additives for asphaltene, but in this case, it is possible to prevent contamination of the treated materials and the materials produced in the subsequent purification operations due to these additives. Particular attention should be paid to possibilities. It has already been mentioned above that the solvent used for diluting the heavy feedstock and precipitating the asphaltenes for addition (for purification) must be compatible with the feedstock and the asphaltenes. For the purpose of dilution, petroleum distillate with a boiling point of 600〓
(315.6℃) or lower. The suitability of pentane for the purpose of precipitation (purification) of catalytic asphaltenes is already clear for the reasons mentioned above. It will be clear to those skilled in the art that the oil once treated can be recycled and treated again in the process of the invention in order to improve the final separation efficiency. It is also possible to connect several contact or solid-liquid separation devices in series or in parallel in order to increase the capacity or efficiency of the separation process. In summary, the present invention aims to refine and separate all petroleum and/or petroleum-related substances and to recover asphaltenes from these raw materials. The above-mentioned petroleum and/or petroleum-related substances are separated by precipitation to recover oil (or gas) components in which the concentrations of these components are substantially reduced. It is understood that this purpose is achieved by contacting the asphaltenes with added asphaltenes, especially those of the same type as the asphaltenes contained in the raw materials mentioned above, but with a lower hydrogen/carbon ratio. I want to have it. Therefore, following intimate contact between the feedstock and the added asphaltenes and complete precipitation of the above-mentioned components, complete separation of the resulting precipitate is an important consideration in carrying out the process provided by the present invention. That's the key.

[Brief explanation of drawings]

FIG. 1 schematically depicts one embodiment of the basic process for refining and partially separating petroleum and/or related substances according to the method provided by the present invention. FIG. 2 schematically depicts one embodiment of the basic process for purifying and partially separating heavy crude oil, bitumen, residual materials, etc. according to the method provided by the present invention. FIG. 3 schematically illustrates one embodiment of the basic process for refining and partially separating heavy crude oil, bitumen, residual materials, etc. and recovering asphaltenes by the method provided by the present invention. This is what is shown. FIG. 1, 1... Contact device, 2... Solid-liquid separation device, 3... Asphaltene precipitation device, 4... Asphaltene drying device, 5... Pentane recovery device,
Fig. 2, 1... contact device, 2... flashing device, 3... stripper, 4... evaporator, 5...
Stripper, FIG. 3, 1... Contact device, 2... Flashing device, 3... Evaporator, 4... Stripper.

Claims (1)

[Scope of Claims] 1. Asphaltene is added to petroleum containing an asphalt component and/or a non-hydrocarbon component, or petroleum fraction is brought into close contact with asphaltene and an asphaltene to which an asphalt component and/or a non-hydrocarbon component is added. A method for treating petroleum or petroleum fractions, which comprises adhesion bonding, precipitating the adhesively bonded components with asphaltene added thereto, and separating said precipitate from the petroleum or petroleum fraction. 2. Process according to claim 1, in which the petroleum or petroleum fraction to be treated is brought into contact directly, undiluted, with the added asphaltenes. 3. Process according to claim 1, in which the added asphaltenes are the same as the asphaltenes contained in the petroleum and petroleum fractions to be treated. 4. If the petroleum or petroleum fraction to be treated is an organic solvent, in particular a petroleum fraction (boiling point range 600〓 (315.6°C)
claim 1, wherein the asphaltenes are diluted with a mixture of asphaltenes (not more than
The method described in. 5. The method of claim 1, wherein the precipitation is promoted using a precipitation promoter, such as a polyelectrolyte material. 6. Process according to claim 1, in which a reactive metal salt, such as a metal halide, is used to form a compound with the asphalt component and/or the non-hydrocarbon component to facilitate precipitation and separation. 7. If the asphaltene to be added is used before its use,
2. The method of claim 1, which is substantially free of pentane treated and precipitated resins and other heavy aromatic materials. 8. A method as claimed in claim 1, comprising means for stirring and mixing in the contacting device to facilitate intimate contact. 9. Process according to claim 1, wherein the contacting device is a fluidized bed of the petroleum or petroleum fraction to be treated and the asphaltenes to be added. 10. Process according to claim 1, in which the contacting device is a packed bed of asphaltenes to be added, through which the petroleum or petroleum fraction to be treated is made to flow. 11. The method of claim 1, wherein the separation of the precipitate from the petroleum or petroleum fraction is achieved by a filtration method. 12. The method of claim 1, wherein the separation of the sediment from the petroleum or petroleum distillate is achieved by sedimentation methods (by gravity or by centrifugal force). 13. The method of claim 1, wherein the contacting device is a mixer/settler combination, allowing contacting and separation to be carried out simultaneously in the same device. 14. The contacting device is a continuous filter using added asphaltene as a filtering aid, and the contacting, precipitation and separation are carried out in the same device by continuously filtering the petroleum or petroleum fraction. , Claim 1
The method described in. 15 Asphaltene is added to petroleum or petroleum fraction containing an asphalt component and/or a non-hydrocarbon component, and the asphaltene is brought into close contact with the asphaltene and the asphalt component and/or a non-hydrocarbon component is adhesively bonded to the asphaltene. The method consists of precipitating the above components and added asphaltene, separating the above precipitate from petroleum or petroleum fraction, treating the separated precipitate with pentane to precipitate and recover asphaltene, and separating and recovering the used pentane. A method for treating petroleum or petroleum distillates. 16. The method according to claim 15, wherein the resin-containing oil remaining after separating and recovering pentane is treated with a hydrocarbon solvent to separate and recover the resin. 17 Petroleum or petroleum fractions containing asphalt components and/or non-hydrocarbon components are diluted with petroleum fractions such as low molecular weight paraffin to increase fluidity, and asphaltenes are added to the diluted product and brought into close contact to form asphalts. component and/or non-hydrocarbon component with the added asphaltene, precipitating the adhesively bonded component and the added asphaltene, separating the precipitate from a diluted petroleum or petroleum fraction, A method for treating petroleum or petroleum fractions, which comprises separating and recovering the petroleum fraction used for dilution from the precipitate, and recovering asphalt or asphaltene by removing volatile components from the precipitate. 18. The method according to claim 17, wherein the petroleum fraction used for diluting low molecular weight paraffin or the like is pentane, and asphaltene is recovered from the precipitate. 19 Claim 18: The resin-containing oil remaining after recovering the pentane used for dilution is treated with a hydrocarbon solvent to separate and recover the resin.
The method described in section.