JPS5927987A - Petroleum and related substances treatment and separation - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to natural substances such as petroleum gas, crude oil, bitumen, oil extracted from oil sand or oil shale, tar extracted from cool sand, etc. All petroleum and/or related substances, including the petroleum portion as well as streams and products from the petroleum refining process, are brought into contact with the added anuphaltenes to extract the asphalt components and/or substances contained therein. Alternatively, the present invention relates to a new method for recovering oil (and/or gas) containing the above-mentioned various components at a reduced concentration by precipitating them together with non-hydrocarbon components, removing and separating these components. Asphalt or asphaltenes can also be recovered in various methods according to the method provided by the present invention.

The feedstock used in the cranking process etc. is today generally pickle or distillate from the capping process. However, if necessary, raw crude oil may be used as a feedstock for cracking, and in that case, the crude oil must be desalted beforehand. Like leftover pickles on the lid,
Heavy G crude oils usually contain significant bituminous components, which can lead to coke formation in many high-temperature processes and can also be a source of carbon deposits on catalyst surfaces used in cranking processes. It is well known that this can reduce the performance of these catalysts and shorten their service life. Crude oil (common) contains significant amounts of non-carbonized organic components, primarily substances containing sulfides, nitrides and oxides, as well as small amounts of soluble organometallic substances and asphaltenes. Contains inorganic salts that coexist with the resin in a colloidal suspension. These non-hydrocarbon components, etc.
When the oil cap comes out, it appears throughout the entire Buddha range,
Non-volatile oils tend to be concentrated, especially in asphaltenes and resins. Although little is known, these substances can cause serious corrosion problems, catalyst deactivation, reduced product quality,
This may cause damage to the health mtt8j.

In general, there is a substantial correlation between the non-hydrocarbon components in crude oil and the asphalt a content, and the higher the content of the asphalt components, the higher the content of the non-hydrocarbon components. For this reason, it has been deemed necessary to previously remove asphalt components from feedstocks used in cracking and other petroleum refining processes.

There are various methods for removing asphalt and non-hydrocarbon components to enhance the properties of feedstocks and petroleum or related materials. As conventional methods and methods, the following can be considered.

(1) Flush lid method (2) A empty lid method (3) Viscous braking method (4) Coking method (5) Solvent treatment method (6) Alkali treatment method (7) Gas treatment method (8) Oxidation treatment Method (5)) Absorption treatment method However, this method, like other conventional methods, has economic and operational disadvantages, requiring specialized equipment and/or extreme 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
They require special waste handling methods and can create difficult waste disposal problems.

In view of the above-mentioned facts, one of the main objects of the present invention is to develop a new method for simultaneously removing asphalt 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 most crude oils.

Another major objective of the present invention is to provide a new method for economically recovering asphaltone while refining petroleum and/or related substances. Since the recovery of asphaltenes by conventional methods is expensive, asphaltenes have not been recovered to a large extent to date. It is known that asphaltenes have many small-scale applications.

Other M (objectives) of the present invention include the following: 1) 4'iL in petroleum? To provide a new method for refining petroleum and/or related substances that uses only the constituent ingredients and does not require any other substances;
2) petroleum and/or oil that can be used in conjunction with many conventional methods;
Or a rabbit that provides a new method for purifying related substances, 3)
4) to provide a new method for refining petroleum and/or related substances that requires relatively low energy consumption; 5) provide a new method for refining petroleum and/or related substances that generate waste; 6) reduce equipment and operating conditions; Even if you don't change it,
These include providing new methods for refining petroleum and/or related substances that can readily handle feedstocks with a wide range of chemical compositions and physical properties.

According to the invention, petroleum (or related substance 1) is brought into contact with added asphaltenes (preferably of the same type as the asphaltenes contained in the feedstock to be treated) and By precipitating and separating the asphalt components and non-hydrocarbon components contained in this petroleum (or related substances), the asphalt components and non-hydrocarbon components contained in this petroleum (or related substances) can be separated. The remaining oil components can be recovered and purified in a quick and effective manner. Under the above conditions, the asphaltenes added to the feed will attract and combine with the resins and other gL aromatics contained in the feed, resulting in The inventor of the present invention has set out to break the yoke of relationship between the asphaltic material and other aromatic materials. Disruption of the above equilibrium relationship results in the precipitation of asphalt components and non-hydrocarbon components. Following this precipitation, an agglomerate of added asphaltenes and precipitating asphalt components is formed. The resulting agglomerate is easily separated from the remaining oil component, and since the recovered oil component has already been de-asphalted, it is suitable as a feedstock for subsequent 111 production operations. On the other hand, the separated precipitate (
The agglomerates) are treated as gb' and recovered as asphalt or asphaltene.

A part of the asphaltene thus recovered is recycled (recycled) to the above-mentioned contacting process. Contact between the petroleum feedstock and the added asphaltenes is typically carried out at a temperature below the rating of the feedstock, and the precipitation of the asphalt components is
It is usually eaten at a temperature close to room temperature. Therefore, for the purpose of heat conservation, a heat exchange between the contacting device and the precipitation (or precipitation) device can be carried out. The above-mentioned precipitate can be treated with a Nononorafuin solvent to recover high-quality asphaltene. The used solvent can be easily recovered and used again. Therefore, the hydraulic method requires 1 of the feedstock.
No chemicals are required other than the 1q component.

Asphaltene is a brown to black, finely powdered, non-crystalline substance, and is usually obtained by treating petroleum, residual oil, waste matter, etc. using light naphtha or a solvent in petroleum. . Naphtha in petroleum has a wide range of sizes, ranging from very ordinary paraffinic hook-like compounds to aromatic types. On the basis of solubility in different solvents, the constituents in petroleum and/or related substances can be distinguished as follows:

1) Carboids - Not soluble 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 tetratide and low molecular weight paraffins.

Most petroleum oils contain very little carboid and carpene, but in the Clara hemorrhoid process, some pickles contain
It may contain 2% or more in 1 part. Industrially, crude oil and raw materials are separated to obtain the two components of asphaltenes and maltenes, and the selective bath-resolving power of hydrocarbons and simple low molecular weight hydrocarbons is used. This is conveniently achieved using paraffins of low molecular weight that have sieving properties.Aromatic petroleum naphtha partially dissolves the asphaltenes in the high temperature layer; The use of pentane, heptane and In particular, n-pentane is known to change the properties of asphaltenes and precipitate them very effectively.N-pentane can be used as a diluent. The inventor of the present invention has discovered that it is possible to precipitate more asunartene contained in petroleum or related substances by using it. By diluting the crude oil with 3% of the asphaltenes in the crude oil and using silica gel as a precipitation aid in an amount equivalent to 10% of the crude oil, it was possible to precipitate 3% of the asphaltenes in the crude oil. It was possible.

On the other hand, even if the same crude oil is not diluted with n-pentane, the asphaltenes of the same type as asnoartene contained therein will be converted to Nt and the residual oil in the crude oil (less than 600
By adding and contacting the crude oil at a rate equivalent to half of the decrement (315.6°C or more), it is possible to precipitate almost 0 percent of the asphaltenes contained in the crude oil.

I think it would be useful to examine the effects of adding asphaltenes to petroleum or related substances. Hydrocarbons contained in petroleum or related substances and their series are closely related to each other, and the differences between these substances are mainly in molecular weight and hydrogen/carbon ratio. Asphaltene hydrocarbons are often hydrogen deficient and often exhibit unusual structures, with the exception of petroleum or
Of course, the hydrocarbon series (consisting of asphaldenes, resins and oils) is characterized by molecular weight and hydrofoil/carbon-y4'
In comparison, there are 91 parts of each other between adjacent series. Asphaldenes can be said to be the final condensate, with the exception of carboids and carbhenes, which are present in extremely small amounts in crude oil.

Highly aromatic properties are commonly expressed in asphaltenes and their series (tl, t). Just as the paraffin content in petroleum is important for separating resins from asphaltenes, the aroma content is important for separating resins from asphaltenes.
This is important in that the resin binds to the asphalt 7' rutin. The more fragrant the resin and mail, the better the solvation effect of asphaltene (depending on the resin), and the solvation effect of resin and oil is n+ at the asphaltene/maltene boundary.
This is one of the most important things in understanding the properties of +, and this interface characterizes the colloidal nature of crude oil and Ut blue matter. The same asphaltenes disperse in highly aromatic solvents and precipitate in low aromatic solvents. To put it more clearly, the colloidal stability of a petroleum or bituminous substance refers to the colloidal stability of the asquartene/bituminous substance.
The inventors have discovered that this can be easily changed by changing the resin ratio or by changing the type of asphaltene or resin therein. The degree of peptization of asphaltenes in crude oil is determined by the degree of aromaticity of resins and aromatic substances contained in the crude oil,
It is strongly influenced by metal components and elemental components other than carbon in the aromatic ring. Even if the resin has the same degree of aroma, if the content of metal components and elements other than carbon is large,
The M stickiness of asphaltene increases. Resin and asphaltenes are bonded in a kind of electron-throwing/receiving relationship, and the molecular structure similarities between asunartene 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 experimentally observing the stability of the newly formed asphaltenes/oil dispersion by placing asphaltenes extracted from one crude oil into a different crude oil. This was discovered by the inventor. In all cases, asphaltenes were readily dispersed in the crude oil from which they were extracted. However, as the amount of asphaltenes added to this crude oil is increased, an insolubility point in the crude oil is finally reached, at which point the asphaltenes and 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 asphaltenes can contain the maximum amount of asphaltenes that can be dispersed in the crude oil without causing precipitation. I believed that there was a thing called the /resin ratio. This ratio can be defined as the "asqualtene/resin peptization constant (or ratio)", and this constant is the optimal amount required to contact and separate a given crude oil. It is useful for defining asphaltenes. Incidentally, it can be said that asphaltenes with a high hydrogen/carbon ratio are more easily dispersed in petroleum than asphaltenes with a low hydrogen/carbon ratio. As the asphaltene/resin ratio in crude oil decreases, there is an axis in which the addition of asphaltenes with a high hydrogen/carbon ratio produces gels, while the addition of asphaltenes with a low hydrogen/carbon ratio causes erosion. Similarly, these facts can be explained by the aromatic intensity of asphaltenes and maltenes in petroleum. Based on the extensive experimental evidence obtained by this book, asphaltenes in unprocessed crude oil exist in monomolecular form and are decomposed by resin molecules. It is glued and dispersed by aromatic molecules. However, the asphaltenes in the bitumen are present in agglomerates, and the asphaltenes in the residue material (from the steaming) appear to be present in the form of large nodules.

There is also substantial evidence that hydrogen bonds appear to be the source of preferential intermolecular forces between resin and asphaltene molecules in unprocessed crude oil. This fact seems to explain why asphaltenes in crude oil are more difficult to separate than asphaltenes in residual materials.

Once peptized resin molecules are lost, asphaltene molecules collide with each other and easily form agglomerates or nodules due to their polarizability. Both asphaltene molecules and resin molecules are very large, so the diffusion rate in petroleum is extremely slow and is not enough for J17. Therefore, stirring and mixing are extremely important in the melting operation provided by the present invention. The most important thing is to bring the resin and asphaltene into close contact. Through hydrogen bonding, each asphaltene molecule formed by a large number of resin molecules forms a micelle, and the most aromatic and polar resin molecule with the highest molecular weight is located near the asphaltene molecule in the center of the micelle. in an arrayed state. These substances are successively surrounded by aromatic, low-polarity, small molecular weight components, and are finally in a state where they gradually transform into oil cake 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 substances is important in separating these non-hydrocarbon components (elements other than gold and carbon).
It is also the key to removing Breaking the equilibrium at the asphaltene/resin interface by exceeding the above asphaltene/resin peptizing constant (or ratio) means:
This is the key to a simple and effective method of separating petroleum or related substances based on the principles of the present invention.

Hereinafter, with reference to some examples of the basic process of the present invention illustrated in the accompanying drawings, FIGS. IJJ
will be explained in detail.

FIG. 1 schematically depicts one embodiment of the basic process for producing and partially separating petroleum or related substances according to the method provided by the present invention.

FIG. 2 shows heavy crude oil,
Figure 1 schematically depicts one embodiment of the basic process for purifying and partially refining bitumen, residual materials, etc.

FIG. 3 schematically depicts 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.

The present invention will now be described in Review #III in connection with some different embodiments shown in the accompanying drawings and in connection with an experimental testis.

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 forces:
It includes two processes. Namely, 1) contact process, 2) solidity
3) asphaltene precipitation process, 4) asphaltene drying process, and 5) n-pentane recovery process. As shown in the first panel, the contacting device 1 includes, for example, a warming (or stirred) tank, a fluidized bed, etc., to ensure close contact between the feedstock and the added asphaltenes and to The solid-liquid separator 2 for facilitating the precipitation of the asphalt components and non-hydrocarbon chain components together with the added asphaltenes is, for example, a filter, centrifuge, hydrocyclone, etc., to remove the precipitates from the remaining oil. Its purpose is to separate it from its components. The asphaltene precipitator 3 is provided to separate asphaltene from pentane by washing the above precipitate with n-pentane and reprecipitating it using, for example, a mixer/settler combination device or a filtration layer. The asphaltene drying device 4 is, for example, a flash drum, a Makabe dryer, etc., and is used to remove residual pentane from asphaltene once precipitated for the purpose of final recovery of asphaltene. The n-pentane recovery device 5 is used, for example, in a flash distiller, evaporator, etc., to recover pentane for recycle and to recover a mixed liquid of resin and oil to be used in the subsequent purification process. Contact process 1 and solid-liquid separation process 2
is the most basic process, and in some cases the same equipment,
For example, countercurrent mixer/settler combinations, contact filters,
It can also be carried out simultaneously in a rotary filter or the like using asphaltene as a filter aid. In contactor 1, the feedstock is brought into intimate contact with the added asphaltenes and the asphalt components and non-hydrocarbon chain components in the feedstock are co-precipitated with the added asphaltenes. In the same liquid separator 2, the precipitated solid mixture is effectively separated from the liquid phase consisting of the oil component, and the oil component thus separated can be used for catalytic cracking and other refining operations. It is suitable as a feedstock for

The precipitated mixture may be partially or completely flashed to remove residual volatile components and then steam stripped to produce a quality asphalt. Alternatively, this precipitated mixture can be treated with n-pentane in the asphaltene precipitation unit 3 to precipitate pure asphaltene containing almost no resin. On the other hand, in the asphaltene drying unit f4, the residual n-pentane is removed and the precipitated asphaltene is dried, but the n-hentane separated from this asphaltene is further sent to the pentane recovery unit 5 and recovered. , recirculated. A portion of the asphaltene thus recovered is circulated to the contactor (#, 1). The mixture of resin and oil collected in the asphaltene recovery unit 45 can be used as a feedstock for thermal cracking or resin recovery. .

Methods and devices for contacting vary widely as described above. The contacting device 1 shown in FIG. 1 should normally be provided with means for mixing and agitating the substances within the device. These means include, for example, stirrers, air stirring equipment, vibrators, stationary mixers, sonic generators, and the like. It is also conceivable to use a single contactor in the form of a fluidized bed between the added asphaltenes and the oil to be treated. When a filtration bed (or packed bed) is used to perform both contact and subsequent solid-liquid separation (in the same device), it is necessary to periodically discharge accumulated precipitates 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 a filter aid. In this case, the membrane layer of precipitate left on the fence cloth serves as a filter aid and performs the functions of contact, settling, and separation. Thus, continuous contacting combined with continuous same-liquid separation can be effectively carried out by continuously adding fresh asphaltenes into the feedstock.

It will be obvious to those skilled in the art that other solid-liquid contact methods and equipment, as well as tin h flow combinations (e.g., countercurrent, cocurrent, crosscurrent, etc.), can be used. It is. , B, there are many different types of liquids and devices that can be used to carry out the present invention.

As mentioned above, FIG. 2 shows the 1. Figure 1 schematically depicts the separation edge, the solvent (used) and the basic steps for recovering asphaltenes.

According to FIG. 2, the feedstock has first been diluted with a petroleum fraction with a boiling point below 315.6°C, in particular a paraffinic solvent, and the asphaltene added in the contactor 1. The asphalt components and non-hydrocarbon components in the feedstock are brought into intimate contact with the asphaltenes 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 homogeneous mixture η is sent to a flaging (or drying) device 2, where the remaining volatile components (mainly the diluent added in the contacting device) are removed from this mixture and then The solid mixture is treated with a stripper 3 to form asphalt. On the other hand, the oil from which the asphaldo component has been removed is sent to an evaporator 4, where it is separated from the diluent by evaporation, and further stripped with steam by a stripper 5. The solvent (diluent) recovered in each of the above four stages is combined and circulated to the contacting device 1.

The process of the present invention using added asphaltenes as an isotropic 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 cranking and many other refining operations.

As mentioned above, the third step 1 is to grind and separate A1° crude oil, pipe production, residual pickle bonds, etc. according to the method provided by the present invention,
This is a schematic illustration of one of the basic steps for recovering asphaltene and the solvent pentane. The process is fundamentally similar to that shown in Figure 2, except that asphaltenes are precipitated using pentane as a solvent (f@pluent), and the treated petroleum is used as a resin. This makes it unsuitable as a feedstock for catalytic cranking, but it differs in that it can be used for thermal cracking. According to FIG. 3, contact device 1
A mixer/settler combination, fluidized bed, etc. are used.
In this apparatus the feedstock is diluted with pentane and brought into contact with the added asphaltenes so that the asphalt and non-hydrocarbon components contained therein are precipitated together with the added asphaltenes. All of the precipitated asphaltenes are separated from the oil component and sent to the Floodjung unit 2 where they are flashed, dried and dried to produce good quality asphaltenes, a portion of which is recycled to the contact unit 1 or recovered as a by-product. be done. 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 heat cranking. 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. It is also possible.

・As is already clear from the above explanation, heavy crude oil, bitumen,
When treating residual materials, etc., the feedstock should be forcefully diluted with a suitable hydrocarbon solvent before contacting with the added asphaltenes. The added asphaltene used for contacting the feedstock should preferably be one that has been first treated with pentane (in a manner that does not change its original properties) and the resin contained therein has been washed and dissolved. Conditions for contact operation are extremely important in achieving the purpose of operation. Various important operational variables (conditions) are described below.

(1) Temperature - The temperature during contact depends on the fluidity of the feedstock, the hydrogen bonding between asphaltene molecules and resin molecules, and the redistribution of various components near the interface between asphaltene and resin and inside the micelles. Affects speed and equilibrium relationships, etc. The temperature within the contacting device is typically 60'F (15,6°
C) maintained above but not above the boiling point of the feedstock (or diluted feedstock). Generally speaking, one batch of crude oil is heated to about 60°F (71.1°C).
If the material is heated for 0 to 30 minutes and allowed to cool to room temperature, the asphalt components will quickly precipitate. Small precipitates may be formed into large agglomerates by slow stirring, and then separated (e.g., by filtration).

(2) Pressure - Pressure has no effect unless liquefied scum is used as a solvent. The method provided by the present invention utilizes a liquid hydrocarbon solvent to optionally dilute the feedstock. Therefore, the contacting operation is usually carried out under atmospheric pressure.

(3) Contact time - The required contact time depends on the quality of the feedstock,
It depends on the contact temperature, degree of dilution, amount of asphaltene added to the amount of asphalt component contained in the raw material, etc. In situ loading using heavy feedstocks, low contact temperatures, low dilutions, and low asphaltene loadings generally require long contact times. It is clear that the contacting method and equipment (eg, presence or absence of agitation, mixing conditions, etc.), as well as the contacting time required, will influence the required contact time.

(4) Agitation - Intimate and uniform contact between the feedstock and added asphalt components depends on agitation at high temperatures.
This can be quickly achieved by creating a stirred state (isotropic turbulence). Once the asphaltene and resin molecules are in complete intimate contact, precipitation of the asphalt component (in the yA material) requires little further agitation.

However, the small precipitated particles thus generated tend to grow into large agglomerates by slow and continuous stirring.

Inferring from these facts, an apparatus such as a series combination of a number of mixing vessels equipped with a slurry pump, a stationary mixer, and a low-speed agitator is ideal for contact operation. In this case, the feedstock, solvent (if necessary) and added asphaltene are fed into 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, and precipitation and agglomeration of the precipitated particles occur in the mixing vessel.

(5) Differential velocity (between the same and liquid phase) - When using packed or filtered beds with added asphaltenes, using a small differential velocity and long residence time means that the feedstock flows through the bed. During this time, the asphalt components in it are precipitated,
It is important in causing the effects of agglomeration and separation.

(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. For Futsu crude oil, no dilution is necessary if it is brought into contact at the boiling point or at temperatures around 160"F (71.1°C).

(Additional Asphaltenes) - As mentioned above, the type and purity (free of contamination from resins and other heavy aromatic substances) of the addition asphaltenes used in the contacting operation are extremely important. Preferably &' +≦Additional asphaltenes are of the same type as those contained in the feedstock, yet have high aromaticity and hydrogen/returning elements, and are uniformly treated with bentane to produce resins and other heavy It is preferable that it is not contaminated with aromatic substances. Once treated with pentane, asphaltenes are free of contamination with resins and other heavy aromatic substances and are therefore highly effective as solid contact agents for use in the method provided by the present invention. The required amount of added asphaltenes is most influenced by the asqualtene/resin peptization constant, as discussed above. This asphaltene/resin peptization constant (or ratio) is generally determined by the feedstock. The larger the size of the paraffinic solvent added for dilution, the smaller it will become.The reason is that the solvent molecules (paraffin) dissolve the resin molecules by separating them from the asphaltene molecules that peptize the resin molecules. It has a sweet effect, but on the other hand, as a result of the effect of added asphaltene (
This may create new hydrogen bonds between asphaltene molecules (dispersed) and resin molecules, or break the hydrogen bonds between asphaltef molecules and resin molecules as shown in Solution II.

It is important that the added asphaltenes for contacting should not be treated with strong solvents that would dissolve them or change their molecular properties, especially the molecular surface properties and the molecular structure. For example, black paraffin, aromatic (1
44@; 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 asphaltenes for addition. In addition, when steam stripping asphaltenes for addition at high temperatures, care should be taken not to oxidize or alter the quality of the asphaltenes.

(8) Solvents - As already mentioned above, among hydrocarbon solvents, those with low aromaticity and low polarity are generally suitable for diluting the feedstock. If possible, a paraffinic solvent with a low molecular weight is most suitable; however, in most cases, the content of aromatic substances is minimal and the boiling point range is 400"F (2
Parts of petroleum that do not exceed temperatures (0.4,4°C) are suitable for use in diluting most feedstocks. Even if the oil fraction has a boiling point range close to 600"F (315,6°C), if mixed with the lower boiling point fraction,
It can be used for contact operations at temperatures below 0 (71,1"C) or higher.

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 patch and continuous), centrifugation, liquid Zyclone, sedimentation, etc. The conditions of the solid-free separation operation depend on the nature of the feedstock and/or the nature of the precipitated material to be separated. Filtration and centrifugation are generally effective, but liquid Zyclone is less effective, and simple natural sedimentation appears to be very inefficient unless the feedstock is highly diluted. .

Thus, in the simple method provided by the present invention,
Asphalt components, metal components, and synonymous components of elements other than carbon can be quickly removed from petroleum or related substances at the same time. This method can include the recovery of asphalt and asphaltenes without any operational difficulties. Moreover, this method can be applied in a wider range and be more effective by using various additives and changing the method slightly according to F9F's wishes. for example,
Various additives, such as inorganic metal oxides (silica gel, alumina, theolite, etc.), clay minerals, white clay, molecular sieves, organic solid adsorbents, viscous carbon, charcoal, lignite, etc., can also be used with asphaltene additives. It can also be used as a contact agent. In the same liquid separation operation, filter aids, such as diatomaceous earth and gypsum, facilitate the filtration of precipitated asphalt components. Multivalent electrolytes that promote precipitation, metal halogen compounds that react with aromatic substances to form halogen compounds, or acids that react with asphaltone and precipitate it from petroleum may also be used as additives. It is possible to share it. However, it should be noted that even foreign substances (other than petroleum constituents), if added to the feedstock, can cause contamination of the treated oil and the products of subsequent refining processes. be. Moreover, these foreign additives can be combined with solid hydrocarbon components (
Separating JiGH from 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 may outperform 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 in conjunction with illustrated figures 1.2 and 3 will be further illustrated with the results of a number of experimental examples.

The results of some representative experimental examples are shown in Tables 1 and 2, with the former reporting the results of experiments involving 11 different crude oils, and the back right reporting the results of experiments involving 11 different types of crude oil. The results of experiments in which different types of pickles (from petroleum distillation) were treated are reported.

With reference to Table 1, for each crude oil treated and each physical property measured, the first listed value is before treatment and the second listed value is before treatment. This is after processing.

The measured physical properties are: specific gravity at 15,6"C, sulfur content at 1%, nitrogen content at 1%, atmospheric pressure at 700°C (371,1°C). Weight percent of lid residue and net N short percent of recovered asphaltene.Experiment Ii conducted within ¥
-<1 Due to the loss of asphaltene in the recovery process, the percentage of asphaltene recovery reported in Table 1 is less than the actual value, yet the reproduction of the data is probably on the order of plus or minus 10 percent. be. To conduct each series of experiments, asphaltenes produced by pentane treatment and precipitation were first added to 2000 ml of crude oil at 700°F (371,1
Add fresh water equivalent to half of the total temperature (in 71.1°C) and allow to rise at a temperature of 160'F (71.1°C) for about 10 minutes. This slurry (mixture of crude oil and added asphaltenes) is cooled down to room temperature (approximately below 70°C (21,1°C)), filtered using No. 4 Whatman filter paper, and precipitated. The entire material was separated (from the oil component).

The precipitate thus separated is pentane (10
After drying in vacuo at a temperature of about 190° C. (87.8° C.), its weight was measured. The net amount of asphaltenes produced is the difference between the total N of asphaltenes recovered and the it of asphaltenes added, which is further converted to weight percent (relative to the amount of crude oil used) and
? This is reported in Table S1. In a series of control experiments, the crude oil in each building was treated in the same manner without the addition of asphaltenes. In all control series of experiments, it was not possible to separate asphaltenes (from the crude oil).

As shown in Table 1, by contacting these crude oils with added asphaltenes, the specific gravity of the crude oil is close to 6%, the sulfur content is over 80%, and the nitrogen content is over (capital)%. , the ash content was more than 85 percent, and the residue content in the oil was reduced by nearly 95·ξ-cent. The amount of asphaltenes separated ranged from 11.2 to 35.5 percent of the amount of crude oil processed, depending on the crude oil. Considering that pickle shoulder content was reduced by more than 95 percentage points in most cases, the above results correspond to asphaltene separation rates in excess of 95 percentage points.

Table 2 reports the results of an example experiment involving the treatment of residual materials from four different crude oils. North Sea (No.
rth Sea) 1070 lower (576
, 5°C), all of the samples were leftovers in the air lid at temperatures below 700°C (371, 1°C). Each of the above residues was processed in three different ways: Namely, there are three methods: 1) contact using added asphaltene, 2) contact using silica gel, and 3) contact using a mixture of asphaltene and silica gel. 6
To carry out a series of experiments, a point range of 180' (82,2°C
) -400"F (204,4°C)) and after addition of one of the solid contact agents listed above,
1° C.) for about an additional minute. The amounts of each of the solid contact agents used are as follows. Namely: 1) asphaltenes stamped Durum, 2) 120 grams of silica gel, and 3) 1:1 mixture of asphaltenes and silica gel.
00 grams. After boiling, wait until the slurry drops to room temperature (approximately below 70°C (21,1°C)) and then add it to the fourth
The whole precipitate was separated by filtration using a No. No. Whatman filter paper.

The separated precipitate was further treated with pentane (10 times the amount of the precipitate), and the precipitated asphaltene was approximately 190%. (8
It was dried in vacuo at a temperature of 7.8°C). The net amount of asphaltenes recovered is the difference between the total amount of congener material recovered and one part of the added asphaltenes, which is further converted to one percent and reported in Table 2. . In a series of control experiments, various pickles were treated in the same manner without the addition of a solid contact agent. However, in all control series of experiments, it was not possible to separate asphaltenes. The data in Table 2 are averages of the results of several identical experiments performed on each residue. As can be seen from Table 2, in all cases the contact result with ω grams of asphaltenes is 120
gram of silica gel or a mixture of 100 grams of asphaltenes and silica gel.

These results also show that asphaltenes have a 5 to 6 times stronger ability to separate asphalt components from the residual material than silica gel. The amount of asphaltenes separated exceeded 30% (based on the residual pickle -1iK), which corresponds to almost complete separation of the asphaltenes contained in the residual pickle. By the way, when silica gel was used as a contact agent, it was extremely difficult to separate it from the silica gel to which asphaltene was 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 residue materials listed in Tables 1 and 2, a wide variety of crude oils, bitumen and residue materials, all according to the method provided by the present invention, were prepared with different asphaltene vinegar loadings,
A precise separation could be achieved using different solvents or dilutions. Various other experiments were also conducted using different solid-liquid contact and solid-liquid separation methods. In all cases, we were able to obtain roughly similar good results.

As is clear from the above examples and explanations, petroleum and/or petroleum-related components can be obtained by contacting the asphaltene added therein according to the method provided by the present invention. and elemental components other than carbon are precipitated with added asphaltenes, these components are separated, and the oil (or gas) component is recovered with substantially reduced concentrations of these components. Depending on the process, it can be purified.

In carrying out the process, the feedstock to be treated should, if necessary, be heated or diluted with a solvent to adjust its fluidity and to facilitate the contacting and precipitation described above. The additive asphaltone described above is preferably of the same type as that to be incorporated into the feedstock to be treated, yet has a low hydrogen/carbon ratio and is largely free of resins and other aromatic materials. It is better to use one that does not contain any substances. As already detailed above, the methods, equipment and operating conditions for contacting and precipitate separation described above can vary widely. The above contact and precipitate separation may be carried out in the same device, for example, a mixer/settler combination, a filtration layer using asphaltene, a continuous filtration device (using asphaltene as the permeation medium), etc. If you try to implement both at the same time, you can do it.

The method provided by the present invention may be implemented in combination with conventional methods, if circumstances permit.

In order to adjust 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 due to these additives and the materials produced in the subsequent purification operation. 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 dilution purposes, the oil portion has a boiling point of 600'F (31
5.6°C) or less. It is clear that pentane is suitable for the purpose of precipitation (purification) of catalytic asphaltenes for the reasons already mentioned above.

It will be obvious to those skilled in the art that in order to improve the final separation efficiency, the dedusted petroleum can be recycled and processed again in the process of the invention. It should be noted that several contacting or solid-liquid separators can be connected in series or in parallel for the purpose of increasing the capacity or efficiency of the 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 petroleum oil and/or petroleum oil as described above is used in order to precipitate and separate the copper components, metal components and elemental copper components other than carbon, and recover the oil (or gas) component in which the concentration of these essential components is substantially reduced. It achieves its purpose by contacting the relevant substances with added asphaltones, especially those of the same type as the asphaltenes contained in the raw materials mentioned above, but with a low swimming/carbon ratio. I just want you to understand. Therefore, due to the close contact between the feed and the added asphaltenes, and the complete precipitation of the above components,
The integrity of the resulting precipitate is the key to implementing the method provided by the present invention.

[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 shows that heavy crude oil,
1 schematically depicts one embodiment of the basic process for purifying and partially separating bitumen, residue a, etc.; FIG. FIG. 3 shows that heavy crude oil,
This diagram schematically shows one embodiment of a basic process for purifying and partially separating bitumen, residue, etc., and recovering asphaltenes. Fig. 1 1... Contact device 2... Solid-liquid separation device 3... Asphaltene precipitation device 4... Asunartene drying device 5... Pentane recovery noodle making Fig. 2 1... Contact device 2.・Frudge-Jung device 3... Stripper 4... Evaporation and 5... Stripper Figure 3 1... Contact device 2... Fludge-Jung device 3... Evaporator 4... Stritz/ξ Applicant George Chaco Ie 1 Patent Attorney Tosasai Yotabe f- Patent Attorney Sasai Katsube〆-1Fi
g, 2 η−+ Rntan voice circulation de

Claims (1)

[Scope of Claims] (1) Asphalt components (asphaltenes, resins, etc.) and/or non-hydrocarbon components (metals, atoms other than carbon) that are attracted by the added asphaltone in a subdivided form. (4) in a contacting device capable of containing the above-mentioned petroleum and/or related substances for a predetermined period of time; (B) attracting and co-precipitating the components with the added asphaltenes in intimate contact with the added asphaltenes; From the mixture, oil containing the above components in reduced concentrations (
and/or gas). (2) A process according to claim 1, in which the petroleum and/or related substances to be treated are brought into contact with the added asphaltenes directly, without dilution. (3) The method of claim 1, wherein the added asphaltenes are of the same type as the asphaltenes contained in the petroleum and/or related materials to be treated. (4) If the petroleum and/or related substances to be treated are treated with organic solvents, especially distillates of petroleum (boiling range 600°F (3
2. The method according to claim 1, wherein the asphaltenes are diluted at temperatures not exceeding 6[deg.] C.) and then contacted with the added asphaltenes. 5. A method according to claim 1, characterized in that the precipitation is carried out using a precipitation promoter, such as a polyelectrolyte material. (6) using reactive general groups, e.g. metal halides;
2. A process according to claim 1, characterized by forming a compound with a non-hydrocarbon component, precipitation and separation. Claim 1, wherein the added asphaltenes are substantially free of resins and other heavy aromatic substances, which have been treated and precipitated with pentane before their use.
The method described in. (8) Claim 1, wherein the contact device is provided with steps for stirring and mixing to facilitate close contact.
The method described in. (9) The method according to claim 1, wherein the contacting device is a fluidized bed of petroleum and/or related substances to be treated and asphaltenes to be added. 00) The contacting device is a packed bed of asphaltenes to be added, such that when the petroleum and/or related substances are passed through it, it adsorbs the non-hydrocarbon components mentioned above.
A method according to claim 1. 01) Process according to claim 1, characterized in that the separation in stage B is by a filtration method. 02 (by sedimentation method (depending on gravity or centrifugal force),
2. Process according to claim 1, characterized by separation in step B. <+:J,) The method according to claim 1, wherein the contacting device is a mixer/settler combination capable of carrying out contacting and separation simultaneously in the same device. 04) The contacting device is a continuous r-filter using added asphaltenes as a p-filtering agent, and by continuously filtering the oil and/or related substances, contacting, precipitation and separation are carried out in the same device. The method according to claim 1, which is carried out. (1', +l) The method according to claim 1, in which a conventional solvent treatment method is also used. (16) Claim 1, in which a conventional acid treatment method is also used.
The method described in. Q7) Using the conventional alkaline treatment method, 4? The method according to claim 1. 0 (To) The method according to claim 1, which also uses a conventional adsorption treatment method. In carrying out the method described in Scope 1 of the Patent nt', the method further comprises: (g) treating the mixture separated in step B with pentane to precipitate and recover asphaltenes; and (B) asphaltenes. After precipitation and recovery, the pentane used in step A above is separated and recovered. (20) +1 (In the process of treating petroleum and/or related substances containing asphalt components and/or non-hydrocarbon components, as may be induced by added asphaltenes, in 8-part form, ( 4) In order to improve the fluidity of the above-mentioned petroleum and/or related substances, the above-mentioned petroleum with improved fluidity is diluted with petroleum oil, preferably paraffin (or paraffins) with a low molecular weight. The above components are brought into contact with the added asphaltenes in a contact chamber capable of containing the petroleum and/or related substances for a predetermined period of time. (
C) separating an oil (and/or gas) containing a reduced concentration of the above components from the mixture of the added asphaltenes and the components precipitated therewith;
(D) separating and recovering the petroleum portion from the oil (and/or gas); (E) removing volatile components from the mixture already separated in step C; A method consisting of recovering asphalt. (21j) The process according to scope 2 of the patent application, wherein the petroleum fraction used in steps A and 3 is pentane, and therefore in step E, instead of asphalt, asphaltene is featured. (22j nfJ) In carrying out the process described in paragraph 19, it is further provided that the resin-containing oil remaining after recovering the pentane in step A thereof is treated with a hydrocarbon solvent, such as liquefied propane, butane or palmobutane. , and separating and recovering the resin. (23) In carrying out the process described in item 21 above, furthermore, at that stage, the remaining pentane after recovering the , a process comprising treating an oil containing resin with a hydrocarbon solvent, such as liquefied propane, butane or isobutane, and separating and recovering said resin.