CA1229317A - Treatment and separation of petroleums and related materials - Google Patents
Treatment and separation of petroleums and related materialsInfo
- Publication number
- CA1229317A CA1229317A CA000432293A CA432293A CA1229317A CA 1229317 A CA1229317 A CA 1229317A CA 000432293 A CA000432293 A CA 000432293A CA 432293 A CA432293 A CA 432293A CA 1229317 A CA1229317 A CA 1229317A
- Authority
- CA
- Canada
- Prior art keywords
- asphaltenes
- constituents
- petroleum
- added
- treating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/003—Solvent de-asphalting
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Herein are disclosed a method and apparatus whereby all petroleums and/or related materials, including natural materials (such as, petroleum gas, crude oils, bitumens, crude oils from oil sands and oil shales, tars from sands, etc.), fraction or fractions derived from said natural materials, and refinery streams and products, are refined and separated to remove their asphaltic constituents (asphaltenes, resins, etc.) and/or nonhydrocarbon con-stituents (metals, heteroatoms, etc.), by contacting said petroleums and/or said related materials with an added asphaltenes, precipitating said constituents together with said added asphaltenes, and then separating the mixture of the resultant precipitates and said added asphaltenes to recover an oil and/or gas) having a reduced concentra-tion of said constituents.
Said mixture can also be separated to remove its residual volatile constituents to produce asphalts; or it can be treated by a low molecular weight paraffinic solvent to recover asphaltenes, which would have numerous potential usages although they have not been available commercially.
Herein are disclosed a method and apparatus whereby all petroleums and/or related materials, including natural materials (such as, petroleum gas, crude oils, bitumens, crude oils from oil sands and oil shales, tars from sands, etc.), fraction or fractions derived from said natural materials, and refinery streams and products, are refined and separated to remove their asphaltic constituents (asphaltenes, resins, etc.) and/or nonhydrocarbon con-stituents (metals, heteroatoms, etc.), by contacting said petroleums and/or said related materials with an added asphaltenes, precipitating said constituents together with said added asphaltenes, and then separating the mixture of the resultant precipitates and said added asphaltenes to recover an oil and/or gas) having a reduced concentra-tion of said constituents.
Said mixture can also be separated to remove its residual volatile constituents to produce asphalts; or it can be treated by a low molecular weight paraffinic solvent to recover asphaltenes, which would have numerous potential usages although they have not been available commercially.
Description
~l.2~3~7 BACKGROUND OF TAO MENTION
Field of the Invention Thus invention relates to a process for repining and separating all petroleums and/or related materials, including natural materials Couch as, petroleum gas, crude oils, bitumens, oils from oil-sands or oil-shales, tars from tar-sands, etc.), petroleum fraction or fractions derived from said natural materials, and refinery streams and products and, more particularly is concerned with a novel method for removing and separating asphaltic constituents and/or nonhydrocar~on constituents by contacting said petroleums Andre said related materials with an added asphaltenes, precipitating said constituents together with said added asphaltenes, and recovering an oil (Andre gas) having a reduced concentration of said constituents. In Ayers processes according to the method provided by the present invention, an asphalt or asphaltenes can also be recovered.
Description of Prior Art Feed stocks for cracking processes are now usually the residue or heavy distillate from a distillation sequence However, as the occasion demands, whole cruxes may also serve as the cracking ~eedstocks and, when this is the case, the crude must be desalted prior to the cracking process. Like still residue, heavy crude petroleums usually contain substantial amounts of asphalt tic constituents, which are not only regarded as the coke-forming constituents in many thermal processes but also the source of carbon depositing on the catalyst for cracking process, thus limiting the service life of the catalyst and the capacity of the catalytic cracking unit.
Crude oils contain appreciable amounts o organic non-hydrocarbon constituents, mainly sulfur-, nitrogen, and oxygen-containing compounds r in smaller amounts, organ-metallic compounds in solution and inorganic salts in colloidal suspension with asp~altenes and resins. These constituents appear throughout the entire boiling range I, . , ~2;~3~7
Field of the Invention Thus invention relates to a process for repining and separating all petroleums and/or related materials, including natural materials Couch as, petroleum gas, crude oils, bitumens, oils from oil-sands or oil-shales, tars from tar-sands, etc.), petroleum fraction or fractions derived from said natural materials, and refinery streams and products and, more particularly is concerned with a novel method for removing and separating asphaltic constituents and/or nonhydrocar~on constituents by contacting said petroleums Andre said related materials with an added asphaltenes, precipitating said constituents together with said added asphaltenes, and recovering an oil (Andre gas) having a reduced concentration of said constituents. In Ayers processes according to the method provided by the present invention, an asphalt or asphaltenes can also be recovered.
Description of Prior Art Feed stocks for cracking processes are now usually the residue or heavy distillate from a distillation sequence However, as the occasion demands, whole cruxes may also serve as the cracking ~eedstocks and, when this is the case, the crude must be desalted prior to the cracking process. Like still residue, heavy crude petroleums usually contain substantial amounts of asphalt tic constituents, which are not only regarded as the coke-forming constituents in many thermal processes but also the source of carbon depositing on the catalyst for cracking process, thus limiting the service life of the catalyst and the capacity of the catalytic cracking unit.
Crude oils contain appreciable amounts o organic non-hydrocarbon constituents, mainly sulfur-, nitrogen, and oxygen-containing compounds r in smaller amounts, organ-metallic compounds in solution and inorganic salts in colloidal suspension with asp~altenes and resins. These constituents appear throughout the entire boiling range I, . , ~2;~3~7
2 --of the crude oil jut do tend to concentrate mainly in the nonvolatile fractions especially asph~ltenes and resins In minute amounts, these compounds can cause serious corrosion problems, catalyst deactivation, degrading of product quality, health hazard, etch In general, there is an approximate correlation between the content of the non hydrocarbon constituents and the content of the asphaltic constituents of a petroleum stock - the higher the asphaltic constituents content, the higher the non hydrocarbon constituents content. It is, therefore often deemed necessary that the asphaltic constituents be removed from feed stocks for cracking and other refining processes.
There are a number of methods which are directed at upgrading feed stocks and separating petroleums and related materials by removal of the asphaltic con-stituents and the non hydrocarbon constituents. These conventional methods and processes may be summarized as follows:
1. Flash distillation I Vacuum flashing
There are a number of methods which are directed at upgrading feed stocks and separating petroleums and related materials by removal of the asphaltic con-stituents and the non hydrocarbon constituents. These conventional methods and processes may be summarized as follows:
1. Flash distillation I Vacuum flashing
3. viscosity breaking
4. Coking I Solvent treatment 6. Caustic treatment 7. Gas trea~nent I Ox dative treatment I Adsorbent treatment 10. Acid treatment 11. Precipitation with reactive metal salts, etc.
The solvent treatment method is most effective in removing the asphaltic constituents, however it has been subject to considerable economic and operational dozed-vantages as all other conventional methods have, which often require special equipment Andre severe operating conditions Most of these conventional methods are not applicable to the treatment of crude petroleums because of the large volumes and the high treatment costs Some of these methods produce wastes which require special handling, and pose serious disposal problems.
Object of' the 'Inanition In view of the above, a principal object of the present invention is to provide a novel method for simultaneously removing both the asphaltic constituents and the non hydrocarbon constituents from petroleums I Andre related materials, which avoid the difficulties normally associated with conventional method. In par-titular, it is an object of this invention to provide a simple but effective method for economically refining and separating crude petroleums in large volumes.
Another primary object of the invention is to provide a novel method for refining petroleums and/or related materials and, at the same time, economically recovering asphaltenes, which have not been commercially produced to any significant extent due to the high recovery cost of the conventional methods. Asphaltenes have been known -to have numerous important potential usages Other important objects of the present invention are: 1) to provide a novel method for refining petrol-ems and/or related materials, which employs only petroleum fractions and no foreign substances; I to provide a novel method for refining petroleums and/or related materials which can be carried out in conjunction with many conventional methods, 3) to provide a novel method for relining petroleums and/or related materials which has relatively small energy requirements; 4) to provide a novel method for reunion petroleums Andre related materials which can be carried out without special, costly equipment or hazardous operating con dictions; I to provide a novel method for relining petrol Lucy Andre related materials which produces no waste stream; and 6) to provide a novel method for refining I i , I. ,;
.
~2~3~
petroleums Andre related laterals which can be easily applied to feed stocks having a wide range ox chemical composition and ox physical properties, with out requiring the major modification of its equipment and operating conditions.
Summary of the Invention In accordance with the present invention, a petroleum or related material is rapidly and effectively refined by the removal of the asphaltic constituents and the non hydrocarbon constituents from the former by contacting same with an added asphaltenes, preferably those derived prom the same feed stock being treated, and then precipitating and separating said asphaltic constituents and said non hydrocarbon constituents together with said added asphaltenes to recover the oil fractions remaining Under the above conditions, it has been found by the present inventor that the asphaltenes added to the fed stock will attract and associate with the resins and other heavy aromatics which are contained in said stock, and thus breaking the equilibria existing amount the asphaltic compounds and other heavy aromatic compounds. The breaking of said equilibria results in the precipitation of the asphaltic constituents and the non hydrocarbon constituents. The precipitation is followed by the agglomeration between the added asphalt ones and the precipitating asphalt constituents. The agglomerates, can be easily separated from the remaining oil fractions, which is a disaffiliated oil Andre gas) suited as feedstoc~s for further reining operations.
The precipitates separated can be further treated to recover asphalts Andre asphaltenes~ The asphaltenes recovered can ye partly recycled to the above contacting step The contacting of a petroleum stock with an added asphaltenes is normally carried out at temperatures not higher than the boiling point of said stock, and the precipitation ox the asp~altic constituents is usually achieved at temperatures near the room temperature.
~2~g3~7
The solvent treatment method is most effective in removing the asphaltic constituents, however it has been subject to considerable economic and operational dozed-vantages as all other conventional methods have, which often require special equipment Andre severe operating conditions Most of these conventional methods are not applicable to the treatment of crude petroleums because of the large volumes and the high treatment costs Some of these methods produce wastes which require special handling, and pose serious disposal problems.
Object of' the 'Inanition In view of the above, a principal object of the present invention is to provide a novel method for simultaneously removing both the asphaltic constituents and the non hydrocarbon constituents from petroleums I Andre related materials, which avoid the difficulties normally associated with conventional method. In par-titular, it is an object of this invention to provide a simple but effective method for economically refining and separating crude petroleums in large volumes.
Another primary object of the invention is to provide a novel method for refining petroleums and/or related materials and, at the same time, economically recovering asphaltenes, which have not been commercially produced to any significant extent due to the high recovery cost of the conventional methods. Asphaltenes have been known -to have numerous important potential usages Other important objects of the present invention are: 1) to provide a novel method for refining petrol-ems and/or related materials, which employs only petroleum fractions and no foreign substances; I to provide a novel method for refining petroleums and/or related materials which can be carried out in conjunction with many conventional methods, 3) to provide a novel method for relining petroleums and/or related materials which has relatively small energy requirements; 4) to provide a novel method for reunion petroleums Andre related materials which can be carried out without special, costly equipment or hazardous operating con dictions; I to provide a novel method for relining petrol Lucy Andre related materials which produces no waste stream; and 6) to provide a novel method for refining I i , I. ,;
.
~2~3~
petroleums Andre related laterals which can be easily applied to feed stocks having a wide range ox chemical composition and ox physical properties, with out requiring the major modification of its equipment and operating conditions.
Summary of the Invention In accordance with the present invention, a petroleum or related material is rapidly and effectively refined by the removal of the asphaltic constituents and the non hydrocarbon constituents from the former by contacting same with an added asphaltenes, preferably those derived prom the same feed stock being treated, and then precipitating and separating said asphaltic constituents and said non hydrocarbon constituents together with said added asphaltenes to recover the oil fractions remaining Under the above conditions, it has been found by the present inventor that the asphaltenes added to the fed stock will attract and associate with the resins and other heavy aromatics which are contained in said stock, and thus breaking the equilibria existing amount the asphaltic compounds and other heavy aromatic compounds. The breaking of said equilibria results in the precipitation of the asphaltic constituents and the non hydrocarbon constituents. The precipitation is followed by the agglomeration between the added asphalt ones and the precipitating asphalt constituents. The agglomerates, can be easily separated from the remaining oil fractions, which is a disaffiliated oil Andre gas) suited as feedstoc~s for further reining operations.
The precipitates separated can be further treated to recover asphalts Andre asphaltenes~ The asphaltenes recovered can ye partly recycled to the above contacting step The contacting of a petroleum stock with an added asphaltenes is normally carried out at temperatures not higher than the boiling point of said stock, and the precipitation ox the asp~altic constituents is usually achieved at temperatures near the room temperature.
~2~g3~7
- 5 Therefore, heat can be exchanged between the contacting apparatus and the precipitating (Rand separating appear-tusk in order to save heat Furthermore, said precipi-tales can ye treated by a paraffinic solvent to pro-cipitate high-quality asphaltenes. The solvent used can be recovered easily for recycling. Therefore, the method requires no chemical, but fractions derived from the feed stock.
Asphaltenes are the brown-to-black, pulverulent, amorphous materials that are derived by treatment of petroleums, residue, bituminous materials, etc. with a light petroleum naphtha or solvent. Petroleum naphthas range widely from the ordinary paraffinic straight-run to the highly aromatic types On the basis of the volubility in a variety of solvents, it has been possible to distinguish among the various constituents of petroleums Andre related materials as follows:
1) Carbides - Insoluble in carbon disulfide, carbon tetrachloride, and low molecular weight paraffins 2) Carbines - Soluble in carbon disulfide, but insoluble in both carbon tetrachloride and low molecular weight paraffins.
3) Asphaltenes - Soluble in both carbon disulfide and carbon tetrachloride, but insoluble in low molecular weight paraffins.
4) Militancy - Soluble in carbon disulfide, carbon tetrachloride, and low molecular weight paraffins Most petroleums contain practically no carbides and carbines, but residue from the cracking processes may contain 2% by weight or more In the industry, the separation of crude petroleums and bitumens into two fractions, asphaltenes and militancy, is conveniently brought about by means of low molecular weight paraffins, which are known to have selective solvency for hydra-carbons and simple low molecular weight hydrocarbon ~2~3:~7 derivatives. Petroleum naphthas of highly aromatic types may dissolve asphaltenes partly, or completely at high temperatures, and are therefore not recomb-ended for treating asphaltenes or diluting asphaltenes containing petroleum stocks in this invention, in order to preserve the original characteristics of the asphalt tones to be used for contacting. Pontoons, hotness and hexanes are recommended for the above purpose.
Especially, n-pentane is known to precipitate asphaltenes effectively without affecting their characteristics apple-viably. This inventor has found that more asphaltenes can be precipitated from asphaltenes containing petrol-ems or related materials by using n-pentane as a delineate.
However, it still takes ~40 volumes of n-pentane to dilute one volume of a crude oil in order to precipitate as much as 90% by weigh of the asphaltenes contained in said crude, my using 10% by weight of silica gel as the precipitant. The same crude oil can be contacted with the asphaltenes of the type identical to that con-twined in Swede crude oil, in the amount equal to one half of the residue (cut point: 600F), to precipitate nearly 100~ of the asphaltenes contained in said oil without dilution by n-pentane.
It should be instructive to discuss further the effect of the addition of asphaltenes into petroleums or related materials. The hydrocarbons and their series in petroleums and related materials are related closely, and they differ from each other mainly in molecular weight and HO ratio The close relations of the various hydrocarbon series comprising the asphaltenes, resins, and oils give rise to much overlapping of free-lions into neighboring series, both in molecular weight and HO ratio, although there is a large hydrogen deficiency on the asphaltene hydrocarbons in which the pronounced heterostructure appears. Excluding carbides and carbines which may be contained in crude petroleums only in negligible amounts, the asphaltenes are the final ,... .
I
condensation product High aromatic;`ty is generally prevalent in the asphaltenes and in the series t Indeed, the degree of aromaticity is of particular ;mportanee when the resins associate with the asphaltene particles, just as the degree of par affinity is important when the resins dissociate The higher the aromaticity of resins and of oils the wetter the solvency for asphaltenes, and the solvent power of resins and of oils it one of the most important facts in understanding the behavior of the asphaltene/~altene interface, which characterize the colloidal nature of crude petroleums and bitumens.
The same asphaltenes that disperse in a solvent of high aromaticity may precipitate readily in a solvent of low aromaticity~ Specifically, this inventor has found that the colloidal stability of a petroleum, or of bitumen, can be easily broken by changing the asphaltenes/resins ratio of sand petroleum or of sand bitumen, or changing the type of the asphaltenes or of the resins in same.
The degree of peptizat~on of the asphaltenes in a crude 2Q petroleum appears to ye affected strongly by the aroma-Taoist, the metal constituents and the heteroatomic constituents of the resins and the heavy aromatics in said crude. For resins of equal aromaticity, those having higher contents of metals and heteroatoms appear to have greater peptizatton power for asphaltenes. It appears that the resins associate with asphaltenes in the manurer of an electron~donor-acceptor relation, and furthermore, certain structural similarities between the asphaltene molecules and the resin molecules in the same crude could be playing an important role in deter-mining -the colloidal behavior of said crude. This fact has been experimentally observed by the inventor by introducing asphaltenes obtained from one crude owl into another crude oil of a different origin 9 and observing the stability of toe newly formed asphaltenes .
oil dispersion system In every instance, asphaltenes dispersed more readily in the crude oil from which whey . Jo ~lZ293~7 had been obtained, By increasing the amount of the asphaltene$ added a point of immiscibility is reached in the crude, at which the precipitation of asphaltenes and resins begins to take place in the crude. This finding has led the inventor to believe that for a given petroleum at a siren temperature, there is a asphaltenes/
resins ratio at which the maximum amount of asphaltenes can ye dispersed in said crude without precipitating out.
This ratio may be defined as the "asphaltenes/resins salvation constant, or ratio", the knowledge of which is useful in determining the optimum amount of asphaltenes required in contacting and separating a given petroleum.
Furthermore, asphaltenes having higher H/C ratios can disperse in oils easier than asphaltenes having low H/C ratios. As the asphaltenes~resins ratio decreases an addition of asphaltenes having high H/C ratios may induce the formation of a gel, but an addition of asphaltenes having low HO ratios would tend to precipi~
late Again, these facts can be explained in terms of 2Q the aromatic;ty of the asphaltenes and that of the militancy in the petroleum Extensive experimental evidences obtained by this inventor indicate that asphaltenes in untreated crude petroleums exist as single entities which are peptized by the resin molecules and dispersed by the heavy aromatic molecules in the crude. Asphaltenes in bitumens appear to exist as clusters, and those in residue usually exist as large agglomerations. There is an experimental evidence that in untreated crude petroleums, hydrogen bonding could be a preferential intermolecular force acting between the resin molecules and the asphaltene molecules. This may explain why asphaltenes in crude petroleums are more difficult to separate than those in residual Asphaltene molecules which haze lost their peptizing resin molecules will easily form clusters or agglomerates when they contact due to their polarizabilities. Since both toe asphaltene SLY
9 _ molecules and to resin molecules are very large, their diffusion rates in petroleums would be extremely small or negl~gi~le. Therefore, the conditions of agitation and m;~x~ng on the contacting operation provided by the present invention are extremely important The direct intimate contact between the resins and the asphaltenes is utmost important Individual asphaltene molecules peptized my many resin molecules through hydrogen-bonding form muzzles, whose structure is such that the bulk of the substances with the greater molecular weight and the most pronounced aromatic and polar nature are arranged closest to the center (asphaltene molecule). These sub-stances are again surrounded by lighter constituents of less aromatic and polar nature until a gradual -transit-lion to the intermiceller phase (oil is formed. Themetalic constituents and the heteroatomic constituents appear to concentrate inside the Michelle than outside.
Therefore, the separation of the asphaltenes and the resins from petroleums and/or related materials is the key to the removal of the non hydrocarbon constituents metals and heteroatomsl. The wreaking of the equal brim at the asphaltene/resin interface by exceeding the asphaltenes/resins salvation constant (or ratio) discussed above us the key to the simple and effective separation of petroleums Andre related materials, in accordance to the principle of the present invention.
In the following, the present invention will be discussed in detail by reference to the preferred, basic processes of the invention shown in the accompany in drawings FIGS. 1, 2 and 3, by reference to the examples given in TABLES l and I
Brief Description of -the Drawings The accompanying drawings illustrate the method and apparatus of the present invention.
FIG 1 is a schematic representation showing a preferred, basic process for roughening and partially separating petroleums and related materials, in accord-~Z293~
-- 10 7`
ante with the method provided by the invention.
FIG. 2 is a schematic representation of a preferred, basic process for refining and partially separating heavy crude petroleums, bitumens, residue, etc. in accordance to the method provided by the invention.
FIG. 3 is a schematic representation of another preferred, basic process for refining and partially separating heavy crude petroleums, bitumens, residue, etc., together Wylie the recovery of asphaltenes, in accordance Thea the method provided by the invention.
.. ... ...
Detailed Description of the Invention .. . . .. _ . .. . _ . .
The invention now will be described in detail, by reference to the several specific embodiments shown in the accompanying drawings, and to the results of export-mental runs As noted above, FIG. l illustrates, in block diagram, a preferred basic process for refining and separating petroleums and related materials in accordance to the method provided by the invention, which comprises:
I a contacting step, 2) a solid-liquid separating step, I an asphaltenes precipitation step, 4) an asphaltenes drying step and 5) a n-pentane recovering step. Refer ring to FIG. l, the contacting apparatus 1 may be a mixing tank, a fluidized-bed, etc. to provide the intimate contacting between the feed stock and the added asphaltenes and to facilitate the precipitation of the asphaltic con-stituents and the non hydrocarbon constituents, together with said added asphaltenes~ the solid rid separation apparatus 2 may be a filter, a centrifuge, a liquid-cyclone, etc. to effect the separation between the resultant precipitates and the oil constituents remain-in the asphaltene precipitating apparatus 3 may be a mixer-settler combination, a filtered etch to effect the dilution of said precipitant with n-pentane and the precipitation and the subsequent separation of asphaltenes from said nwpentane7 the asphaltene drying apparatus 4 may be a flash drum, a vacuum dryer, etc. to remove the I' .
33~L7 . 11 residual n-pentane from the precipitated asphaltenes for final wrecker of asphaltenes? and the n-pentane recovery apparatus 5 may be a flash still, an e~apora-ion, eta to recover the n~pentane for recycling and the res~ns-oil mixture for further processing. The contacting step 1 and the solid-liquid separation step 2 are the basic steps, which can be carried out, if desirable, in a single apparatus, such as a counter-current mixer-settler, a contact filter, a rotary filter using asphaltenes as the filter-aid, etc. In the contacting apparatus 1, the feed stock is brought to intimately contact with an added asphaltenes to effect the precipitation of the asphaltic constituents and the non hydrocarbon constituents together with said added asphaltenes, and in the solid-liquid separating apparatus 2, the mixture of solid masses precipitated is effectively separated from the liquid (oil) medium constituting the treated oil, which is suited as a feed stock for catalytic cracking and for many further refining operations. A part or whole, of said mixture can be flashed to remove the residual volatile con-stitu~nts and then stripped with steam to produce high-qual~ty asphalts. Said mixture of solid masses precipated is treated with n-pentane in -the asphaltene precipitation apparatus 3 to precipitate the asphaltenes, which are substantially free of resins, while the pro-cipitated asphaltenes are dried in the asphaltene drying apparatus 4 for removal of the residual n-pentane, the spent n-pentane separated from the asphaltenes is sent to the n-pentane recovery unit 5 for recovery and recycling. A part of the asphaltenes recovered is recycled to the contacting apparatus 1. The resins-oil mixture from toe n-pentane recovery unit 5 may be used as a eedstock for thermal cracking ox for resin recovery.
The method and apparatus for the contacting may Mary widely, as noted aye. The contacting apparatus 1 in FIG. 1 should be, in general, equipped with a means i;
.. . . ..
~Z~3~7' for agi-t~tin~ and mixing the masses in said apparatus.
Said means may include stirrer, aerator, vibrator, solid-state mixture, sonic generator, etc. The contacting apparatus 1 may be a fluidi~zed-bed of an added asphaltenes and the petroleum being treated. When a filter-bed (or packed-bed) is used to carry out both the contacting and the subsequent sold liquid separation in the same appear-tusk the periodical discharging of the resultant precipi~
tents accumulated will be necessary. however, a continue out filter using asphaltenes as the filter-aid can be employed to effect the continuous contaCtincJ and separating of feed stocks. In this case, a layer of the precipitates retained on the filter-cloth will junction like a filter-bed to effect the contacting, the precipitation, and the separation The continuous contacting combined with the continuous solid-liqu;`d separation can be as effective, if the fresh asphaltenes are continuously added to the feed stream Other solid-liquid contacting methods and apparatus, I and various flow arrangements (counter-current, co-current, cross-current, etc.) also can be employed, as may be obvious to those who are skilled in the art. Needless to say, there are numerous different methods and apparatus for solid-liquid separation which can be employed in -the I practice of this invention.
As noted above, FIG. 2 is a schematic representation of a preferred basic process for refining and separating heavy crude petroleums, bitumens, residue, etc., in accordance with the method provided by the invention;
said process including the recovery of the solvent and the asphalt. Referring to FIG 2, feed stocks are diluted by a petroleum fraction (or fractions having a boiling range not exceeding 6~0F, preferably, a liquid paraffinic solvent (or sealants and intimately contacted by an added asphaltenes in the contacting apparatus 1, which may be a mixer-settler, a fluidized-bed, etc. to effect the precipitation of the asphaltic constituents and the ~2zg3~7 nonhydrocarhon constituents, together with said added asphaltenes. The mixture of solid masses precipitated is then sent to the flashing (or drying apparatus I, where the residual volatile constituents (mainly the solvent added Gil said contacting apparatus) is removed from sand mixture, which is treated in the stripper 3 to produce asphalt. The disaffiliated oil is separated from the solvent by evaporation in the evaporator 4 and steam-stripped in the stripper 5. The solvent no-covered in each of the four steps are combined and recycled to the contacting apparatus 1 as shown. By the method of this invention using an added asphaltene as the solid contractor, there is no need to use pique-fled propane, or liquefied butane, to treat feed stocks at high temperatures and high pressures. The treated oil is suited as a feed stock for catalytic cracking and for many other refining operations.
As noted above, FIG. 3 illustrates another pro-furred embodiment of the basic process for rev nine and separating heavy crude petroleums, bitumens, residue, etc., in accordance with the method provided by the invention; said process including the recovery of the asphaltenes and the solvent, n-pentane. The process is basically identical to the one shown in FIG. 2, except that n-pentane is used as the solvent in order to prey cipitate the asphaltenes, and that the treated oil con-twining resins will not be suited as a feed stock for catalytic cracking, but may be used in thermal cracking.
Referring to FIG 3 the contacting apparatus 1 may be a mixer-settler, a fluidized~bed, etc., in which the ~eedstock is diluted with n~pentane and then intimately contacted with an added asphaltene to effect the prows citation of the asphaltenes contained and the nonhydro-carbon constituents, together with said added asphaltenes.
us The total asphaltenes precipitated are then separated from the oil fractions remaining, and then flashed and dried in the flashing apparatus 2 to produce high-2293~.7 quality asphaltenes k which can be recycled or recovered as a byproduct The oil fractions are separated in -the evaporator 3 and in the stripper 4 to remove the n-pontoon fox recycling The treated oil recovered will contain resins, and is suited as a feed stock for thermal cracking, or for resin wrecker. Needless to say, the bottoms from the n-pentane recovery unit 5 in FIG. 1 and/or from the n-pentane recovery unit 5 in FIG. 3 can be treated by a hydrocarbon solvent, preferably liquefied propane, liquefied butane, or isobutane.
As may be obvious from the above discussion, in treating heavy crude petroleums, bitumens, residue, etc.
the feed stock should be diluted with a suitable hydra-carbon solvent (or solvents) before the contacting with an added asphaltene~ The asphaltenes to be used for the contacting with feed stocks are preferably treated by n-pentane to dissolve the resins, while preserving the original characteristics of said asphaltenes.
The conditions of the contacting operation are very important-in achieving the objects of the operation.
Several important operational variables are summarized below.
1. Temperature - The temperature of contacting can affect the fluidity of the feed stock, the hydron bonding between the asphaltenes and the resins, the rates and the equilibria of the redistribution of various constituents near the asphaltene-resin interface and inside the asphaltene-resins m~celles. The tempera-lure in the contacting apparatus is normally maintained above 60F, but not exceeding the boiling point of the feed stock (or diluted feed stock It has been found adequate to heat crude petroleums at approximately 160F
for 10 to 30 minutes, and then cool it to room temperature, at which the precipitation of the asphaltic constituents takes place I,, ~Z~3~7 more readily. The agglomeration of fine precipitates is facilitated by gentle agile-lion for a period of several minute before the solid-liquid separation (filtration) may be attempted 2. Pressure When no liquefied gas solvent is employed the pressure will have no effect.
The method provided by the invention prefers a liquid hydrocarbon solvent for diluting lo feed stock as may be needed; and the contact-in is normally carried out at thy atoms-phonic pressure.
I Contacting time - The contacting time needed depends on the nature of feed stock, the con-tatting temperature, the dilution ratio, the amount of asphaltenes added relative to the amount of the asphaltic constituents in the feed stock. Heavier feed stocks, lower con-tatting temperatures, lower dilution ratios, and small amounts of asphaltenes added normally would require longer contacting time.
The method and apparatus of contacting also will affect the contacting time required, as may be obvious.
I Agitation - The intimate and uniform contact-in between the feed stock and the added asphaltenes can be achieved rapidly at a higher temperature, if isotropic turbulence is obtained. Once the asphaltene particles and the resin particles have achieved the intimate contacting, little or no agitation is required for the precipitation of the asphaltic constituents To facilitate the agglomeration of all the precipitates, gentle agitation is useful The above suggests that a combination of a slurry-pump, a solid-state mixer, and a vertically elongated, multi-,, .
3~7 stages tank equipped with a slow stirrer would be an ideal contacting apparatus. The feed stock the solvent (if used), and the asphaltenes are fed -together to the slurry pump which pumps the slurry formed through a solid-state mixer to achieve the uniform intimate contacting between the three before entering said tank, where the precipitation and the agglomeration can take place.
5. Slip velocity - If a packed-bed or a filter-bed of asphaltenes is used, slower slip velocities and longer residence time are important in order to effect the precipita-lion, the agglomeration, and the separation of the asphaltic constituents while the feed stock flows through said bed.
Asphaltenes are the brown-to-black, pulverulent, amorphous materials that are derived by treatment of petroleums, residue, bituminous materials, etc. with a light petroleum naphtha or solvent. Petroleum naphthas range widely from the ordinary paraffinic straight-run to the highly aromatic types On the basis of the volubility in a variety of solvents, it has been possible to distinguish among the various constituents of petroleums Andre related materials as follows:
1) Carbides - Insoluble in carbon disulfide, carbon tetrachloride, and low molecular weight paraffins 2) Carbines - Soluble in carbon disulfide, but insoluble in both carbon tetrachloride and low molecular weight paraffins.
3) Asphaltenes - Soluble in both carbon disulfide and carbon tetrachloride, but insoluble in low molecular weight paraffins.
4) Militancy - Soluble in carbon disulfide, carbon tetrachloride, and low molecular weight paraffins Most petroleums contain practically no carbides and carbines, but residue from the cracking processes may contain 2% by weight or more In the industry, the separation of crude petroleums and bitumens into two fractions, asphaltenes and militancy, is conveniently brought about by means of low molecular weight paraffins, which are known to have selective solvency for hydra-carbons and simple low molecular weight hydrocarbon ~2~3:~7 derivatives. Petroleum naphthas of highly aromatic types may dissolve asphaltenes partly, or completely at high temperatures, and are therefore not recomb-ended for treating asphaltenes or diluting asphaltenes containing petroleum stocks in this invention, in order to preserve the original characteristics of the asphalt tones to be used for contacting. Pontoons, hotness and hexanes are recommended for the above purpose.
Especially, n-pentane is known to precipitate asphaltenes effectively without affecting their characteristics apple-viably. This inventor has found that more asphaltenes can be precipitated from asphaltenes containing petrol-ems or related materials by using n-pentane as a delineate.
However, it still takes ~40 volumes of n-pentane to dilute one volume of a crude oil in order to precipitate as much as 90% by weigh of the asphaltenes contained in said crude, my using 10% by weight of silica gel as the precipitant. The same crude oil can be contacted with the asphaltenes of the type identical to that con-twined in Swede crude oil, in the amount equal to one half of the residue (cut point: 600F), to precipitate nearly 100~ of the asphaltenes contained in said oil without dilution by n-pentane.
It should be instructive to discuss further the effect of the addition of asphaltenes into petroleums or related materials. The hydrocarbons and their series in petroleums and related materials are related closely, and they differ from each other mainly in molecular weight and HO ratio The close relations of the various hydrocarbon series comprising the asphaltenes, resins, and oils give rise to much overlapping of free-lions into neighboring series, both in molecular weight and HO ratio, although there is a large hydrogen deficiency on the asphaltene hydrocarbons in which the pronounced heterostructure appears. Excluding carbides and carbines which may be contained in crude petroleums only in negligible amounts, the asphaltenes are the final ,... .
I
condensation product High aromatic;`ty is generally prevalent in the asphaltenes and in the series t Indeed, the degree of aromaticity is of particular ;mportanee when the resins associate with the asphaltene particles, just as the degree of par affinity is important when the resins dissociate The higher the aromaticity of resins and of oils the wetter the solvency for asphaltenes, and the solvent power of resins and of oils it one of the most important facts in understanding the behavior of the asphaltene/~altene interface, which characterize the colloidal nature of crude petroleums and bitumens.
The same asphaltenes that disperse in a solvent of high aromaticity may precipitate readily in a solvent of low aromaticity~ Specifically, this inventor has found that the colloidal stability of a petroleum, or of bitumen, can be easily broken by changing the asphaltenes/resins ratio of sand petroleum or of sand bitumen, or changing the type of the asphaltenes or of the resins in same.
The degree of peptizat~on of the asphaltenes in a crude 2Q petroleum appears to ye affected strongly by the aroma-Taoist, the metal constituents and the heteroatomic constituents of the resins and the heavy aromatics in said crude. For resins of equal aromaticity, those having higher contents of metals and heteroatoms appear to have greater peptizatton power for asphaltenes. It appears that the resins associate with asphaltenes in the manurer of an electron~donor-acceptor relation, and furthermore, certain structural similarities between the asphaltene molecules and the resin molecules in the same crude could be playing an important role in deter-mining -the colloidal behavior of said crude. This fact has been experimentally observed by the inventor by introducing asphaltenes obtained from one crude owl into another crude oil of a different origin 9 and observing the stability of toe newly formed asphaltenes .
oil dispersion system In every instance, asphaltenes dispersed more readily in the crude oil from which whey . Jo ~lZ293~7 had been obtained, By increasing the amount of the asphaltene$ added a point of immiscibility is reached in the crude, at which the precipitation of asphaltenes and resins begins to take place in the crude. This finding has led the inventor to believe that for a given petroleum at a siren temperature, there is a asphaltenes/
resins ratio at which the maximum amount of asphaltenes can ye dispersed in said crude without precipitating out.
This ratio may be defined as the "asphaltenes/resins salvation constant, or ratio", the knowledge of which is useful in determining the optimum amount of asphaltenes required in contacting and separating a given petroleum.
Furthermore, asphaltenes having higher H/C ratios can disperse in oils easier than asphaltenes having low H/C ratios. As the asphaltenes~resins ratio decreases an addition of asphaltenes having high H/C ratios may induce the formation of a gel, but an addition of asphaltenes having low HO ratios would tend to precipi~
late Again, these facts can be explained in terms of 2Q the aromatic;ty of the asphaltenes and that of the militancy in the petroleum Extensive experimental evidences obtained by this inventor indicate that asphaltenes in untreated crude petroleums exist as single entities which are peptized by the resin molecules and dispersed by the heavy aromatic molecules in the crude. Asphaltenes in bitumens appear to exist as clusters, and those in residue usually exist as large agglomerations. There is an experimental evidence that in untreated crude petroleums, hydrogen bonding could be a preferential intermolecular force acting between the resin molecules and the asphaltene molecules. This may explain why asphaltenes in crude petroleums are more difficult to separate than those in residual Asphaltene molecules which haze lost their peptizing resin molecules will easily form clusters or agglomerates when they contact due to their polarizabilities. Since both toe asphaltene SLY
9 _ molecules and to resin molecules are very large, their diffusion rates in petroleums would be extremely small or negl~gi~le. Therefore, the conditions of agitation and m;~x~ng on the contacting operation provided by the present invention are extremely important The direct intimate contact between the resins and the asphaltenes is utmost important Individual asphaltene molecules peptized my many resin molecules through hydrogen-bonding form muzzles, whose structure is such that the bulk of the substances with the greater molecular weight and the most pronounced aromatic and polar nature are arranged closest to the center (asphaltene molecule). These sub-stances are again surrounded by lighter constituents of less aromatic and polar nature until a gradual -transit-lion to the intermiceller phase (oil is formed. Themetalic constituents and the heteroatomic constituents appear to concentrate inside the Michelle than outside.
Therefore, the separation of the asphaltenes and the resins from petroleums and/or related materials is the key to the removal of the non hydrocarbon constituents metals and heteroatomsl. The wreaking of the equal brim at the asphaltene/resin interface by exceeding the asphaltenes/resins salvation constant (or ratio) discussed above us the key to the simple and effective separation of petroleums Andre related materials, in accordance to the principle of the present invention.
In the following, the present invention will be discussed in detail by reference to the preferred, basic processes of the invention shown in the accompany in drawings FIGS. 1, 2 and 3, by reference to the examples given in TABLES l and I
Brief Description of -the Drawings The accompanying drawings illustrate the method and apparatus of the present invention.
FIG 1 is a schematic representation showing a preferred, basic process for roughening and partially separating petroleums and related materials, in accord-~Z293~
-- 10 7`
ante with the method provided by the invention.
FIG. 2 is a schematic representation of a preferred, basic process for refining and partially separating heavy crude petroleums, bitumens, residue, etc. in accordance to the method provided by the invention.
FIG. 3 is a schematic representation of another preferred, basic process for refining and partially separating heavy crude petroleums, bitumens, residue, etc., together Wylie the recovery of asphaltenes, in accordance Thea the method provided by the invention.
.. ... ...
Detailed Description of the Invention .. . . .. _ . .. . _ . .
The invention now will be described in detail, by reference to the several specific embodiments shown in the accompanying drawings, and to the results of export-mental runs As noted above, FIG. l illustrates, in block diagram, a preferred basic process for refining and separating petroleums and related materials in accordance to the method provided by the invention, which comprises:
I a contacting step, 2) a solid-liquid separating step, I an asphaltenes precipitation step, 4) an asphaltenes drying step and 5) a n-pentane recovering step. Refer ring to FIG. l, the contacting apparatus 1 may be a mixing tank, a fluidized-bed, etc. to provide the intimate contacting between the feed stock and the added asphaltenes and to facilitate the precipitation of the asphaltic con-stituents and the non hydrocarbon constituents, together with said added asphaltenes~ the solid rid separation apparatus 2 may be a filter, a centrifuge, a liquid-cyclone, etc. to effect the separation between the resultant precipitates and the oil constituents remain-in the asphaltene precipitating apparatus 3 may be a mixer-settler combination, a filtered etch to effect the dilution of said precipitant with n-pentane and the precipitation and the subsequent separation of asphaltenes from said nwpentane7 the asphaltene drying apparatus 4 may be a flash drum, a vacuum dryer, etc. to remove the I' .
33~L7 . 11 residual n-pentane from the precipitated asphaltenes for final wrecker of asphaltenes? and the n-pentane recovery apparatus 5 may be a flash still, an e~apora-ion, eta to recover the n~pentane for recycling and the res~ns-oil mixture for further processing. The contacting step 1 and the solid-liquid separation step 2 are the basic steps, which can be carried out, if desirable, in a single apparatus, such as a counter-current mixer-settler, a contact filter, a rotary filter using asphaltenes as the filter-aid, etc. In the contacting apparatus 1, the feed stock is brought to intimately contact with an added asphaltenes to effect the precipitation of the asphaltic constituents and the non hydrocarbon constituents together with said added asphaltenes, and in the solid-liquid separating apparatus 2, the mixture of solid masses precipitated is effectively separated from the liquid (oil) medium constituting the treated oil, which is suited as a feed stock for catalytic cracking and for many further refining operations. A part or whole, of said mixture can be flashed to remove the residual volatile con-stitu~nts and then stripped with steam to produce high-qual~ty asphalts. Said mixture of solid masses precipated is treated with n-pentane in -the asphaltene precipitation apparatus 3 to precipitate the asphaltenes, which are substantially free of resins, while the pro-cipitated asphaltenes are dried in the asphaltene drying apparatus 4 for removal of the residual n-pentane, the spent n-pentane separated from the asphaltenes is sent to the n-pentane recovery unit 5 for recovery and recycling. A part of the asphaltenes recovered is recycled to the contacting apparatus 1. The resins-oil mixture from toe n-pentane recovery unit 5 may be used as a eedstock for thermal cracking ox for resin recovery.
The method and apparatus for the contacting may Mary widely, as noted aye. The contacting apparatus 1 in FIG. 1 should be, in general, equipped with a means i;
.. . . ..
~Z~3~7' for agi-t~tin~ and mixing the masses in said apparatus.
Said means may include stirrer, aerator, vibrator, solid-state mixture, sonic generator, etc. The contacting apparatus 1 may be a fluidi~zed-bed of an added asphaltenes and the petroleum being treated. When a filter-bed (or packed-bed) is used to carry out both the contacting and the subsequent sold liquid separation in the same appear-tusk the periodical discharging of the resultant precipi~
tents accumulated will be necessary. however, a continue out filter using asphaltenes as the filter-aid can be employed to effect the continuous contaCtincJ and separating of feed stocks. In this case, a layer of the precipitates retained on the filter-cloth will junction like a filter-bed to effect the contacting, the precipitation, and the separation The continuous contacting combined with the continuous solid-liqu;`d separation can be as effective, if the fresh asphaltenes are continuously added to the feed stream Other solid-liquid contacting methods and apparatus, I and various flow arrangements (counter-current, co-current, cross-current, etc.) also can be employed, as may be obvious to those who are skilled in the art. Needless to say, there are numerous different methods and apparatus for solid-liquid separation which can be employed in -the I practice of this invention.
As noted above, FIG. 2 is a schematic representation of a preferred basic process for refining and separating heavy crude petroleums, bitumens, residue, etc., in accordance with the method provided by the invention;
said process including the recovery of the solvent and the asphalt. Referring to FIG 2, feed stocks are diluted by a petroleum fraction (or fractions having a boiling range not exceeding 6~0F, preferably, a liquid paraffinic solvent (or sealants and intimately contacted by an added asphaltenes in the contacting apparatus 1, which may be a mixer-settler, a fluidized-bed, etc. to effect the precipitation of the asphaltic constituents and the ~2zg3~7 nonhydrocarhon constituents, together with said added asphaltenes. The mixture of solid masses precipitated is then sent to the flashing (or drying apparatus I, where the residual volatile constituents (mainly the solvent added Gil said contacting apparatus) is removed from sand mixture, which is treated in the stripper 3 to produce asphalt. The disaffiliated oil is separated from the solvent by evaporation in the evaporator 4 and steam-stripped in the stripper 5. The solvent no-covered in each of the four steps are combined and recycled to the contacting apparatus 1 as shown. By the method of this invention using an added asphaltene as the solid contractor, there is no need to use pique-fled propane, or liquefied butane, to treat feed stocks at high temperatures and high pressures. The treated oil is suited as a feed stock for catalytic cracking and for many other refining operations.
As noted above, FIG. 3 illustrates another pro-furred embodiment of the basic process for rev nine and separating heavy crude petroleums, bitumens, residue, etc., in accordance with the method provided by the invention; said process including the recovery of the asphaltenes and the solvent, n-pentane. The process is basically identical to the one shown in FIG. 2, except that n-pentane is used as the solvent in order to prey cipitate the asphaltenes, and that the treated oil con-twining resins will not be suited as a feed stock for catalytic cracking, but may be used in thermal cracking.
Referring to FIG 3 the contacting apparatus 1 may be a mixer-settler, a fluidized~bed, etc., in which the ~eedstock is diluted with n~pentane and then intimately contacted with an added asphaltene to effect the prows citation of the asphaltenes contained and the nonhydro-carbon constituents, together with said added asphaltenes.
us The total asphaltenes precipitated are then separated from the oil fractions remaining, and then flashed and dried in the flashing apparatus 2 to produce high-2293~.7 quality asphaltenes k which can be recycled or recovered as a byproduct The oil fractions are separated in -the evaporator 3 and in the stripper 4 to remove the n-pontoon fox recycling The treated oil recovered will contain resins, and is suited as a feed stock for thermal cracking, or for resin wrecker. Needless to say, the bottoms from the n-pentane recovery unit 5 in FIG. 1 and/or from the n-pentane recovery unit 5 in FIG. 3 can be treated by a hydrocarbon solvent, preferably liquefied propane, liquefied butane, or isobutane.
As may be obvious from the above discussion, in treating heavy crude petroleums, bitumens, residue, etc.
the feed stock should be diluted with a suitable hydra-carbon solvent (or solvents) before the contacting with an added asphaltene~ The asphaltenes to be used for the contacting with feed stocks are preferably treated by n-pentane to dissolve the resins, while preserving the original characteristics of said asphaltenes.
The conditions of the contacting operation are very important-in achieving the objects of the operation.
Several important operational variables are summarized below.
1. Temperature - The temperature of contacting can affect the fluidity of the feed stock, the hydron bonding between the asphaltenes and the resins, the rates and the equilibria of the redistribution of various constituents near the asphaltene-resin interface and inside the asphaltene-resins m~celles. The tempera-lure in the contacting apparatus is normally maintained above 60F, but not exceeding the boiling point of the feed stock (or diluted feed stock It has been found adequate to heat crude petroleums at approximately 160F
for 10 to 30 minutes, and then cool it to room temperature, at which the precipitation of the asphaltic constituents takes place I,, ~Z~3~7 more readily. The agglomeration of fine precipitates is facilitated by gentle agile-lion for a period of several minute before the solid-liquid separation (filtration) may be attempted 2. Pressure When no liquefied gas solvent is employed the pressure will have no effect.
The method provided by the invention prefers a liquid hydrocarbon solvent for diluting lo feed stock as may be needed; and the contact-in is normally carried out at thy atoms-phonic pressure.
I Contacting time - The contacting time needed depends on the nature of feed stock, the con-tatting temperature, the dilution ratio, the amount of asphaltenes added relative to the amount of the asphaltic constituents in the feed stock. Heavier feed stocks, lower con-tatting temperatures, lower dilution ratios, and small amounts of asphaltenes added normally would require longer contacting time.
The method and apparatus of contacting also will affect the contacting time required, as may be obvious.
I Agitation - The intimate and uniform contact-in between the feed stock and the added asphaltenes can be achieved rapidly at a higher temperature, if isotropic turbulence is obtained. Once the asphaltene particles and the resin particles have achieved the intimate contacting, little or no agitation is required for the precipitation of the asphaltic constituents To facilitate the agglomeration of all the precipitates, gentle agitation is useful The above suggests that a combination of a slurry-pump, a solid-state mixer, and a vertically elongated, multi-,, .
3~7 stages tank equipped with a slow stirrer would be an ideal contacting apparatus. The feed stock the solvent (if used), and the asphaltenes are fed -together to the slurry pump which pumps the slurry formed through a solid-state mixer to achieve the uniform intimate contacting between the three before entering said tank, where the precipitation and the agglomeration can take place.
5. Slip velocity - If a packed-bed or a filter-bed of asphaltenes is used, slower slip velocities and longer residence time are important in order to effect the precipita-lion, the agglomeration, and the separation of the asphaltic constituents while the feed stock flows through said bed.
6. Viscosity - The viscosity of the ~eedstock should be adjusted by heating or dilution with a petroleum fraction (or fractions) to facilitate the intimate contacting between the asphalkenes and the resins and the precipitation of the asphaltic constituents.
For ordinary crude petroleums, the dilution would not be required if the contacting is carried out at its boiling point, or about 160F.
For ordinary crude petroleums, the dilution would not be required if the contacting is carried out at its boiling point, or about 160F.
7. Asphaltenas - As noted above the type and the cleanness (free from resins and other heavy aromatics) of the asphaltenes to be used for the contacting operation are extremely important. Preferably, they are identical, in type, to those contained in the feed stock, or similar types having high aromaticity and lo HO ratio, and haze been treated by n pontoon/ for the reasons already described avow The n~pentane precipitated asphalt tones are reasonably free from resins and ~.2Z93~
other heavy aromatics, and extremely effective as the solid contractor to be used in the method provided my the invention The amount of asphaltenes required depends mostly on the asphaltenes-resins salvation constant of the feed stock, as already discussed above. The asphaLtenes-resins solution constant (or ratio) normally decreased as more paraffinic solvent is added to the feed stock. While the solvent molecules dissolve the resin molecules and attempt to remove them away from thy pep-tired asphaltene molecule, the effect of an added asphaltene is to use the molecules of the added asphaltenes to make hydrogen bonding with these resin molecules and to break the existing hydrogen bonds that they make with the peptized asphaltene molecule.
It is important to note that the asphaltenes to be used for contacting should not be treated by a solvent which can dissolve said asphaltenes, or change their characteristics, especially their surface properties and chemical structure. For example, cycle-paraffins, aromatics, cyclohexane, pardon, nitrobenzene, ethylene dichlorides chloroform, carbon disulfide, carbon tetrachloride, etc., which can attack asphaltenes, should not be used in diluting feed stocks or treating asphaltenes Steam stripping, at a high temperature, ox asphaltenes should be done with a great care so that the asphaltenes would not be badly oxidized or changed.
other heavy aromatics, and extremely effective as the solid contractor to be used in the method provided my the invention The amount of asphaltenes required depends mostly on the asphaltenes-resins salvation constant of the feed stock, as already discussed above. The asphaLtenes-resins solution constant (or ratio) normally decreased as more paraffinic solvent is added to the feed stock. While the solvent molecules dissolve the resin molecules and attempt to remove them away from thy pep-tired asphaltene molecule, the effect of an added asphaltene is to use the molecules of the added asphaltenes to make hydrogen bonding with these resin molecules and to break the existing hydrogen bonds that they make with the peptized asphaltene molecule.
It is important to note that the asphaltenes to be used for contacting should not be treated by a solvent which can dissolve said asphaltenes, or change their characteristics, especially their surface properties and chemical structure. For example, cycle-paraffins, aromatics, cyclohexane, pardon, nitrobenzene, ethylene dichlorides chloroform, carbon disulfide, carbon tetrachloride, etc., which can attack asphaltenes, should not be used in diluting feed stocks or treating asphaltenes Steam stripping, at a high temperature, ox asphaltenes should be done with a great care so that the asphaltenes would not be badly oxidized or changed.
8. Solvent As already discussed above, hydra-carbon solvents having lo aromaticity, low polarity, and it HO ratio are on general suited for use in diluting feed stocks.
Although low molecular weight paraffinic I
solvents are preferred, in Yost cases a petroleum fraction (or fractions containing little ox no aromatics and having a boiling range below 400F is adequate as a delineate for most feed socks Petroleum fractions having a bowling range as high as nearly 600F may also be used if they are mixed with fractions having low boiling ranges, and if the contacting is carried out at a temperature above 160F.
There are a wide variety of solid-liquid swooper-lion methods and apparatus, which can be applied to the solid-liquid separation operation following the contact-in operation in accordance with the method of the invention. A few examples are: filtration (both batch and continuous, centrifugation, liquid cyclone, settling, etch The conditions for the separation will depend on the nature of the feed stock and of the precipitates to be separated. Filtration and centrifugation are usually very effective liquid cyclone is not as effective; and simple settling is too inefficient if the feed stock is not diluted considerably Thus, the simply method provided by the invention can simultaneously remove the asphaltic, metallic, and heteroatomic constituents rapidly from petroleums and/or related materials It may include the recovery of asphalts and of asphaltenes, without any operational difficulties. The method can be modified through the use of various additives, if desirable, thus enhancing its effects and broadening its applicability. For example, various solid sorbentsl, such as inorganic metallic oxides (silica gel, alumina zealot, etc.), clay minerals fullers earth, molecular sieves, etch and organic solid sorbents, such as activated carbons, charcoals, lignite coals etch can be used together with asphaltenesr if desirable, as the contractors. In the solid-liquid separation operation, filter-aids, ,. .
Jo ~ZZ~93~7 such as diato~ceous earth, gypsum, etc. can be used to facilitate the filtration of the precipitated asphaltic constituents Polyvalent electrolytes which promote the precipitation metallic halides which react with heavy aromatics to form halides of the aromatics for easier separation of resins and asphaltenes~ or acids which react with asphaltenes and precipitate same from petrol-ems also can be considered as additives. It should be kept In mind that any foreign substances introduced to a feed stock could become a source of the contamination of the treated owls and of the products of the subsequent refining processes. Furthermore, the complete separation of these additives from the solid hydrocarbon constituents (asphaltenes and resins) is usually extremely difficult and costly. Therefore, the use of non hydrocarbon sub-stances is not preferred in the method provided by the invention .
The method of this invention may also be carried out in conjunction with the conventional method, or methods, in order to complement said conventional method.
However, for the reason described above, this approach must be considered carefully in order to avoid the possible operational difficulties and the contamination problems In order to illustrate specifically the practice and the benefits of the present invention, the methods descried in detail in connection with the accompanying Figs 1 through 3 were followed in numerous experimental runs conducted The results of some typical experimental runs are shown in Tables 1 and 2; the former reporting the results of experiments involving the treatment of eleven (111 different crude petroleums; and the latter reporting the results of experiments ;:nvol~ing the treatment of four I different residual Referring to TABLE 1, for each crude oil treated and for each property measured, the first value listed is that obtained before the treatment and the second - SLY
value listed is that obtained after the treatment. The properties determined are: the specific gravity at 60F, the sulfur content by weigh-t percent I the nitrogen content by weight percent (%1, the atmospheric residue at cut point of 7Q0F, and the asphaltenes recovered by weight percent to Because of the inevitable loss of asphaltenes during the recovering process conducted in the laboratory, the percent of the asphaltenes recovered reported in TABLE 1 is smaller than the true value, and the reproducibility of the data is probably about + 10%.
In carrying out each run, the crude in the amount of 2000 milliliters was added with the n-pentane precipitated asphaltenes (previously recovered from the same crude stock) in the amount equal to one half (1/2) of its atmospheric residue (cut point: 700F), and then boiled at about 160F for approximately 10 minutes. The slurry was then allowed to cool to room temperature (about 70F) prior to the filtration of said slurry through No. 4 Whitman filter paper to separate the entire precipitates.
Said precipitates separated were then treated with n-pentane (10 volumes) to precipitate only the asphaltenes, which were dried in vacuum at about 190F prior to the weighing. The net amount of the asphaltenes produced, which is the difference between the total asphaltenes recovered and the asphaltenes added, was converted to weight percent and reported in TABLE 1. Control runs were made for each crude oil without adding the asphalt tones, by following the some procedure No asphaltenes could be separated in all of the control runs made.
As may be seen in TABLE 1, the contacting of these crude oils with the added asphaltenes has resulted in the reduction in specific gravity as much as nearly 6 percent (:%), in sulfur content over 8G percent (%~, in nitrogen content over 80 percent (%~, in ash content o'er 85 percent (%~, and in residue content nearly 95 percent ~%~. The weight of the asphaltenes separated varied 11.2 to 35~5 percent (%~, depending on the crude 12Z93~7 . 21 TABLE 1. Treatment of Various Crude Petroleums Specific Sulfur Nitrogen Ash Residue Asphal~enes Gut- -Cbnbent Content Content Content Recovered Cruxes ( - ) - (Wattage White) (Wt.%} (Whatnot I?
California Owe 0.51 0.398 0.0009 33.8 0 0.856 0.08 0.071 0.0001 1.4 20.6 . .............
_ .
California Owe 1.84 0.555 0.0035 41.9 0 LEA. 0.859 0.31 0.104 0.0Q04 2.8 29.1 .
Colorado 0.850 0.56 0.073 0.0004 26.5 0 RUB. 0.838 0.12 0.012 0.0000 1.2 17.5 - .
Ill mows 0.847 0.21 0.138 0.0005 28.3 0 L 0.831 0.03 0.033 0.0000 1.6 15.0 -Kansas Owe 0.76 0.19 0.0021 43.6 0 R 0.851 0.11 0.03 0.0002 2.7 27.3 : .. .
Louisiana 0.846 0.21 0.040 0.0008 20.6 0 L 0.830 0.02 0.000 0.0000 1.1 11.2 . . . .. ..
Oklahoma Owe 1.68 0.4820.0022 55.9 0 G 0.864 0.29 0.0800.0003 2.6 35.5 Oklahoma 0~893 1.34 0.2430.0020 48.9 0 S 00848 0.24 0.0360.0003 3.1 30.7 ... . . .. ..... ...
Texas 0.871 0.15 0.0200.0003 23.0 0 B 0.845 0.02 0.0000.0000 1.3 16.4 ..... . ...
. _ _ Texas 0.863 2.12 0.000.0005 27.0 0 C 0.841 0.36 0.0Q00.00Q0 1.5 15~8 . . .. . . . .... .. ..... . ... .... . ... ... ... ..
. _ _ .
North 0.846 0~44 Q.21 0.0001 39.9 0 ; yea 0.835 0.04 Q~02 0.0000 2.5 17.3 .. .. .. ... ... . .. . . - - -_ . .
Jo ~l2Z~3~f oil treated. These results represent that the separation of asphaltenes is over go percent I in most cases, considering the fact that the reduction in residue us over 95 percent C~2 in most cases In TABLE 2, the results of experimental runs involving the treatment of four I different still residue from four (4) different crude owls are reported. Except North Sea residue, which was a vacuum still residue with 1070F.cut point, the other three residue were atoms-phonic still residue with 700F. cut point. Each residue was treated in the three different ways: 1) contacting with the asphaltenes; 2) contacting with silica gel;
and 3) contacting with a mixture of asphaltenes and silica gel. In carrying out each run, the residue in the amount of 200 milliliters was first diluted with 1200 milliliters of aromatic-free gasoline (boiling range: 180 to 400QF.), and then boiled with one of the solid contractors at approximately 160F~ for about 20 minutes. The amounts of the three solid contractors employed were: I asphaltenes ~60 grams), 2) silica gel (120 grams); and 3) asphaltenes-silica gel mixture in 1:1 ratio (100 grooms After boiling, the slurry was allowed -to cool to room temperature (about 70F~), and then filtered through No. 4 Whitman filter paper to separate the entire precipitates. Said precipitates separated were then treated by n-pentane (10 volumes) to precipitate only top asphaltenes, which were dried in vacuum at about 190F~ prior to the weighing. The net amount of the asphaltenes produced which is the difference between the total weight of the recovered solids and the solid contractor added was converted to weight percent and reported on TABLE 2. Control runs were jade for each residue without adding a solid con-tractor, by following the above procedure No asphaltenes could be separated on all ox the control runs made.
The data given in TABLE 2 are the average values oboe twined from several runs made for each residue. As Jo I
I
TABLE I Recovery of ~sphaltenes from Various Residue.
........ ...
Solid Contacbors Residue 1 ~haltenes Silica Gel Asphaltenes~l ice None . , , Gel ._ _ . . _ Texas 38.0% 11~2~ 21.3% 0%
, _ _ Oklahoma 41.2% 14.3% 22.5% o%
North 73~1% Z0~1% 41.1% 0%
. _ Monangas 71.4% 27~5% 42.0% I
. _ , .
may be seen from TALE 2, in every instance the result of contacting by 60 grams of the asphaltenes is better than that by 120 grams of the silica gel or that by 100 grams of the asphaltenes-silica gel mixture. The results indicate also that the ability of the asphaltenes to disaffiliate these residue is approximately 5 to 6 times that of the silica gel used. The weight percent (based on the residue) of the asphaltene separated in each case is over 30 percent to), which may account for the near complete separation of the asphaltenes contained in the residue. It was extremely difficult to separate the asphaltenes precipitated from the silica gel added Therefore, it is not preferable to mix another solid con-tractor with the asphaltenes in treating petroleums and/
or related materials by the method provided by the invention.
In addition to those crude petroleums and residue listed in Tables 1 and 2, many other crude petroleums, bitumens, and residue haze been repined and separated successfully, using various asphaltene doses, solvents, and dilution ratios under various experimental Canada lions, all in accordance to the method provided my the invention Other experimental runs have been made, using different methods of sold liquid contacting and ..
~22~93~L~
of solid-liquid separation In all cases, substantially similar beneficial results were obtained.
It is obvious from the above illustrations and discussion that petroleums and/or related materials can be refined by removing the asphaltic, metallic, and heteroatomic constituents by contacting same with an added asphaltenes to effect the precipitation of said constituents, and then separating the resultant precipi-tales to recover the treated oil Andre gas containing lo a substantially reduced concentration of said constituents, in accordance with the method provided by the invention.
In carrying out said method, the fluidity of the feed-stock to be treated should be adjusted, if necessary, by heating or solvent dilution in order to facilitate the contacting and the precipitation. Said added asphaltenes are preferably the type identical to that contained in the feed stock to be treated, or one having a lower H/C
ratio, and substantially free from resins and other heavy aromatics. The optimum dose of said asphaltenes to be added depends mainly on the nature of the feed-stock to be treated. The method, apparatus, and opera-tying conditions for said contacting and for said separation of precipitates may vary widely as already described above in detail. Furthermore, both said contacting and said separation of precipitates can be carried out in a single apparatus, such as a mixer-settler, a filter-bed of asphaltenes, a continuous filter (using asphaltenes as the filter aid), etc., if desirable.
The method provided by the invention may also be carried out in conjunction with one of many conventional methods, if the circumstance permits. Said method may also be modified by the use of various additives intended to affect the efficiency of said method although the possible contamination, by said additives; of the treated streams and the products from the subsequent operations must be carefully considered.
The solvent (or solvents to ye used on diluting . -I,,, 3~7 heavy feed stocks and in precipitating the asphaltenes to be used for said contacting must be compatible with said feed stocks and asphaltenes~ For diluting a petroleum fraction or fractions having a boiling range not exceeding 600F is preferable. For precipitating the asphaltenes to be used as the contractor, n-pentane is preferred, for the reason already described above.
It is obvious to those who are skilled in the art that the recycling of the treated oil can be practiced in the method provided by the invention, in order to increase the final separation efficiency. In the alterna-live, several units of the contacting and solid-liquid separating apparatus can be connected in series and/or parallel, in order to increase the capacity Andre the separation efficiency of the process.
It should be understood that the present invention applies to the refining and separation of all petroleums and all petroleum-related materials, and, to the recovery of asphalts and/or asphaltenes from said petroleums Andre said materials, by contacting same with an added asphaltenes, preferably the type identical to that contained in said petrolelDms and/or said materials to be treated, or one having lower HO ratio, to effect the precipitation of the asphaltic, metallic, and heteroatomic constituents, and then separating the resultant precipitates from the treated oil (and/or gas) containing a reduced concentration of said constituents.
Therefore, the intimate contacting between the feed stock to be treated and said added asphaltenes, and the come plate precipitation and subsequent separation of said constituents precipitated together with said added asphaltenes are the keys to the method provided my this invention I'
Although low molecular weight paraffinic I
solvents are preferred, in Yost cases a petroleum fraction (or fractions containing little ox no aromatics and having a boiling range below 400F is adequate as a delineate for most feed socks Petroleum fractions having a bowling range as high as nearly 600F may also be used if they are mixed with fractions having low boiling ranges, and if the contacting is carried out at a temperature above 160F.
There are a wide variety of solid-liquid swooper-lion methods and apparatus, which can be applied to the solid-liquid separation operation following the contact-in operation in accordance with the method of the invention. A few examples are: filtration (both batch and continuous, centrifugation, liquid cyclone, settling, etch The conditions for the separation will depend on the nature of the feed stock and of the precipitates to be separated. Filtration and centrifugation are usually very effective liquid cyclone is not as effective; and simple settling is too inefficient if the feed stock is not diluted considerably Thus, the simply method provided by the invention can simultaneously remove the asphaltic, metallic, and heteroatomic constituents rapidly from petroleums and/or related materials It may include the recovery of asphalts and of asphaltenes, without any operational difficulties. The method can be modified through the use of various additives, if desirable, thus enhancing its effects and broadening its applicability. For example, various solid sorbentsl, such as inorganic metallic oxides (silica gel, alumina zealot, etc.), clay minerals fullers earth, molecular sieves, etch and organic solid sorbents, such as activated carbons, charcoals, lignite coals etch can be used together with asphaltenesr if desirable, as the contractors. In the solid-liquid separation operation, filter-aids, ,. .
Jo ~ZZ~93~7 such as diato~ceous earth, gypsum, etc. can be used to facilitate the filtration of the precipitated asphaltic constituents Polyvalent electrolytes which promote the precipitation metallic halides which react with heavy aromatics to form halides of the aromatics for easier separation of resins and asphaltenes~ or acids which react with asphaltenes and precipitate same from petrol-ems also can be considered as additives. It should be kept In mind that any foreign substances introduced to a feed stock could become a source of the contamination of the treated owls and of the products of the subsequent refining processes. Furthermore, the complete separation of these additives from the solid hydrocarbon constituents (asphaltenes and resins) is usually extremely difficult and costly. Therefore, the use of non hydrocarbon sub-stances is not preferred in the method provided by the invention .
The method of this invention may also be carried out in conjunction with the conventional method, or methods, in order to complement said conventional method.
However, for the reason described above, this approach must be considered carefully in order to avoid the possible operational difficulties and the contamination problems In order to illustrate specifically the practice and the benefits of the present invention, the methods descried in detail in connection with the accompanying Figs 1 through 3 were followed in numerous experimental runs conducted The results of some typical experimental runs are shown in Tables 1 and 2; the former reporting the results of experiments involving the treatment of eleven (111 different crude petroleums; and the latter reporting the results of experiments ;:nvol~ing the treatment of four I different residual Referring to TABLE 1, for each crude oil treated and for each property measured, the first value listed is that obtained before the treatment and the second - SLY
value listed is that obtained after the treatment. The properties determined are: the specific gravity at 60F, the sulfur content by weigh-t percent I the nitrogen content by weight percent (%1, the atmospheric residue at cut point of 7Q0F, and the asphaltenes recovered by weight percent to Because of the inevitable loss of asphaltenes during the recovering process conducted in the laboratory, the percent of the asphaltenes recovered reported in TABLE 1 is smaller than the true value, and the reproducibility of the data is probably about + 10%.
In carrying out each run, the crude in the amount of 2000 milliliters was added with the n-pentane precipitated asphaltenes (previously recovered from the same crude stock) in the amount equal to one half (1/2) of its atmospheric residue (cut point: 700F), and then boiled at about 160F for approximately 10 minutes. The slurry was then allowed to cool to room temperature (about 70F) prior to the filtration of said slurry through No. 4 Whitman filter paper to separate the entire precipitates.
Said precipitates separated were then treated with n-pentane (10 volumes) to precipitate only the asphaltenes, which were dried in vacuum at about 190F prior to the weighing. The net amount of the asphaltenes produced, which is the difference between the total asphaltenes recovered and the asphaltenes added, was converted to weight percent and reported in TABLE 1. Control runs were made for each crude oil without adding the asphalt tones, by following the some procedure No asphaltenes could be separated in all of the control runs made.
As may be seen in TABLE 1, the contacting of these crude oils with the added asphaltenes has resulted in the reduction in specific gravity as much as nearly 6 percent (:%), in sulfur content over 8G percent (%~, in nitrogen content over 80 percent (%~, in ash content o'er 85 percent (%~, and in residue content nearly 95 percent ~%~. The weight of the asphaltenes separated varied 11.2 to 35~5 percent (%~, depending on the crude 12Z93~7 . 21 TABLE 1. Treatment of Various Crude Petroleums Specific Sulfur Nitrogen Ash Residue Asphal~enes Gut- -Cbnbent Content Content Content Recovered Cruxes ( - ) - (Wattage White) (Wt.%} (Whatnot I?
California Owe 0.51 0.398 0.0009 33.8 0 0.856 0.08 0.071 0.0001 1.4 20.6 . .............
_ .
California Owe 1.84 0.555 0.0035 41.9 0 LEA. 0.859 0.31 0.104 0.0Q04 2.8 29.1 .
Colorado 0.850 0.56 0.073 0.0004 26.5 0 RUB. 0.838 0.12 0.012 0.0000 1.2 17.5 - .
Ill mows 0.847 0.21 0.138 0.0005 28.3 0 L 0.831 0.03 0.033 0.0000 1.6 15.0 -Kansas Owe 0.76 0.19 0.0021 43.6 0 R 0.851 0.11 0.03 0.0002 2.7 27.3 : .. .
Louisiana 0.846 0.21 0.040 0.0008 20.6 0 L 0.830 0.02 0.000 0.0000 1.1 11.2 . . . .. ..
Oklahoma Owe 1.68 0.4820.0022 55.9 0 G 0.864 0.29 0.0800.0003 2.6 35.5 Oklahoma 0~893 1.34 0.2430.0020 48.9 0 S 00848 0.24 0.0360.0003 3.1 30.7 ... . . .. ..... ...
Texas 0.871 0.15 0.0200.0003 23.0 0 B 0.845 0.02 0.0000.0000 1.3 16.4 ..... . ...
. _ _ Texas 0.863 2.12 0.000.0005 27.0 0 C 0.841 0.36 0.0Q00.00Q0 1.5 15~8 . . .. . . . .... .. ..... . ... .... . ... ... ... ..
. _ _ .
North 0.846 0~44 Q.21 0.0001 39.9 0 ; yea 0.835 0.04 Q~02 0.0000 2.5 17.3 .. .. .. ... ... . .. . . - - -_ . .
Jo ~l2Z~3~f oil treated. These results represent that the separation of asphaltenes is over go percent I in most cases, considering the fact that the reduction in residue us over 95 percent C~2 in most cases In TABLE 2, the results of experimental runs involving the treatment of four I different still residue from four (4) different crude owls are reported. Except North Sea residue, which was a vacuum still residue with 1070F.cut point, the other three residue were atoms-phonic still residue with 700F. cut point. Each residue was treated in the three different ways: 1) contacting with the asphaltenes; 2) contacting with silica gel;
and 3) contacting with a mixture of asphaltenes and silica gel. In carrying out each run, the residue in the amount of 200 milliliters was first diluted with 1200 milliliters of aromatic-free gasoline (boiling range: 180 to 400QF.), and then boiled with one of the solid contractors at approximately 160F~ for about 20 minutes. The amounts of the three solid contractors employed were: I asphaltenes ~60 grams), 2) silica gel (120 grams); and 3) asphaltenes-silica gel mixture in 1:1 ratio (100 grooms After boiling, the slurry was allowed -to cool to room temperature (about 70F~), and then filtered through No. 4 Whitman filter paper to separate the entire precipitates. Said precipitates separated were then treated by n-pentane (10 volumes) to precipitate only top asphaltenes, which were dried in vacuum at about 190F~ prior to the weighing. The net amount of the asphaltenes produced which is the difference between the total weight of the recovered solids and the solid contractor added was converted to weight percent and reported on TABLE 2. Control runs were jade for each residue without adding a solid con-tractor, by following the above procedure No asphaltenes could be separated on all ox the control runs made.
The data given in TABLE 2 are the average values oboe twined from several runs made for each residue. As Jo I
I
TABLE I Recovery of ~sphaltenes from Various Residue.
........ ...
Solid Contacbors Residue 1 ~haltenes Silica Gel Asphaltenes~l ice None . , , Gel ._ _ . . _ Texas 38.0% 11~2~ 21.3% 0%
, _ _ Oklahoma 41.2% 14.3% 22.5% o%
North 73~1% Z0~1% 41.1% 0%
. _ Monangas 71.4% 27~5% 42.0% I
. _ , .
may be seen from TALE 2, in every instance the result of contacting by 60 grams of the asphaltenes is better than that by 120 grams of the silica gel or that by 100 grams of the asphaltenes-silica gel mixture. The results indicate also that the ability of the asphaltenes to disaffiliate these residue is approximately 5 to 6 times that of the silica gel used. The weight percent (based on the residue) of the asphaltene separated in each case is over 30 percent to), which may account for the near complete separation of the asphaltenes contained in the residue. It was extremely difficult to separate the asphaltenes precipitated from the silica gel added Therefore, it is not preferable to mix another solid con-tractor with the asphaltenes in treating petroleums and/
or related materials by the method provided by the invention.
In addition to those crude petroleums and residue listed in Tables 1 and 2, many other crude petroleums, bitumens, and residue haze been repined and separated successfully, using various asphaltene doses, solvents, and dilution ratios under various experimental Canada lions, all in accordance to the method provided my the invention Other experimental runs have been made, using different methods of sold liquid contacting and ..
~22~93~L~
of solid-liquid separation In all cases, substantially similar beneficial results were obtained.
It is obvious from the above illustrations and discussion that petroleums and/or related materials can be refined by removing the asphaltic, metallic, and heteroatomic constituents by contacting same with an added asphaltenes to effect the precipitation of said constituents, and then separating the resultant precipi-tales to recover the treated oil Andre gas containing lo a substantially reduced concentration of said constituents, in accordance with the method provided by the invention.
In carrying out said method, the fluidity of the feed-stock to be treated should be adjusted, if necessary, by heating or solvent dilution in order to facilitate the contacting and the precipitation. Said added asphaltenes are preferably the type identical to that contained in the feed stock to be treated, or one having a lower H/C
ratio, and substantially free from resins and other heavy aromatics. The optimum dose of said asphaltenes to be added depends mainly on the nature of the feed-stock to be treated. The method, apparatus, and opera-tying conditions for said contacting and for said separation of precipitates may vary widely as already described above in detail. Furthermore, both said contacting and said separation of precipitates can be carried out in a single apparatus, such as a mixer-settler, a filter-bed of asphaltenes, a continuous filter (using asphaltenes as the filter aid), etc., if desirable.
The method provided by the invention may also be carried out in conjunction with one of many conventional methods, if the circumstance permits. Said method may also be modified by the use of various additives intended to affect the efficiency of said method although the possible contamination, by said additives; of the treated streams and the products from the subsequent operations must be carefully considered.
The solvent (or solvents to ye used on diluting . -I,,, 3~7 heavy feed stocks and in precipitating the asphaltenes to be used for said contacting must be compatible with said feed stocks and asphaltenes~ For diluting a petroleum fraction or fractions having a boiling range not exceeding 600F is preferable. For precipitating the asphaltenes to be used as the contractor, n-pentane is preferred, for the reason already described above.
It is obvious to those who are skilled in the art that the recycling of the treated oil can be practiced in the method provided by the invention, in order to increase the final separation efficiency. In the alterna-live, several units of the contacting and solid-liquid separating apparatus can be connected in series and/or parallel, in order to increase the capacity Andre the separation efficiency of the process.
It should be understood that the present invention applies to the refining and separation of all petroleums and all petroleum-related materials, and, to the recovery of asphalts and/or asphaltenes from said petroleums Andre said materials, by contacting same with an added asphaltenes, preferably the type identical to that contained in said petrolelDms and/or said materials to be treated, or one having lower HO ratio, to effect the precipitation of the asphaltic, metallic, and heteroatomic constituents, and then separating the resultant precipitates from the treated oil (and/or gas) containing a reduced concentration of said constituents.
Therefore, the intimate contacting between the feed stock to be treated and said added asphaltenes, and the come plate precipitation and subsequent separation of said constituents precipitated together with said added asphaltenes are the keys to the method provided my this invention I'
Claims (22)
1. Method for treating a petroleum and/or related material containing asphaltic constituents (asphaltenes, resins, etc.) and/or nonhydrocarbon constituents (metals, heteroatoms, etc.) which are capable of being attracted by an added asphaltenes in a finely divided form, said method comprising:
A) intimately contacting said petroleum and/or said material, in a contacting apparatus capable of holding same for a predetermined period of time, with said added asphaltenes thereby to attract and precipitate said constituents together with said added asphaltenes;
and (B) separating from the mixture of said con-stituents precipitated with said added asphaltenes, an oil (and/or gas) having a reduced concentration of said constituents.
A) intimately contacting said petroleum and/or said material, in a contacting apparatus capable of holding same for a predetermined period of time, with said added asphaltenes thereby to attract and precipitate said constituents together with said added asphaltenes;
and (B) separating from the mixture of said con-stituents precipitated with said added asphaltenes, an oil (and/or gas) having a reduced concentration of said constituents.
2. Method according to claim 1, wherein said added asphaltenes are those which have been recovered from a feedstock (or feedstocks) of the type identical to said petroleum and/or said material to be treated.
3. Method according to claim 1, wherein said petroleum and/or said material is added and diluted with an organic solvent, preferably a petroleum fraction (or fractions) having a boiling range not higher than 600°F.
in order to facilitate the contacting with said added asphaltenes and the precipitation of said constituents.
in order to facilitate the contacting with said added asphaltenes and the precipitation of said constituents.
4. Method according to claim 1, wherein a pre-cipitating agent, such as a polyvalent electrolyte, is added to said contacting apparatus to promote the precipitation of said constituents.
5. Method according to claim 1, wherein a reactive metal salt, such as a metal halide, is added to said contacting apparatus to induce a chemical reaction between said salt and said constituents to produce a new substance capable of precipitation, thereby facili-tating the separation of said constituents from said petroleum and/or said material.
6. Method according to claim 1, wherein said added asphaltenes have been treated and precipitated by n-pentane, and are substantially free from resins and other heavy aromatics.
7. Method according to claim 1, wherein said contacting apparatus is equipped with a means for agi-tating and mixing said petroleum and/or said material to facilitate the intimate contacting with said added asphaltenes.
8. Method according to claim 1, wherein said contacting apparatus consists of a fluidized-bed of said petroleum and/or said material, and said added asphaltenes.
9. Method according to claim 1, wherein said contacting apparatus consists of a fixed bed of said added asphaltenes capable of collecting and retaining said constituents when said petroleum and/or said material flow through said bed and contact intimately with said added asphaltenes.
10. Method according to claim 1, wherein said separating in Step B is accomplished by a filtration method.
11. Method according to claim 1, wherein said separation in Step B is accomplished by a sedimentation method.
12. Method according to claim 1, wherein said contacting apparatus consists of a combined mixer-settler, capable of intimately contacting said petroleum and/or said material with said added asphaltenes and precipitating said substances, and then settling same with said added asphaltenes.
13. Method according to claim 1, wherein said contacting apparatus consists of a continuous filter using said added asphaltenes as a filter-aid, capable of continuously filtering said petroleum and/or said material at a predetermined rate allowing the precipi-tation and the separation of said constituents together with said added asphaltenes.
14. Process for treating a petroleum and/or related material containing asphaltic constituents and/or nonhydrocarbon constituents, wherein the method according to claim 1 is carried out in conjunction with the conventional solvent treating method.
15. Process for treating a petroleum and/or related material containing asphaltic constituents and/or nonhydrocarbon constituents, wherein the method according to claim 1 is carried out in conjunction with the conventional acid treating method.
16. Process for treating a petroleum and/or related material containing asphaltic constituents and/or nonhydrocarbon constituents, wherein the method according to claim 1 is carried out in conjunction with the conventional caustic treating method.
17. Process for treating a petroleum and/or related material containing asphaltic constituents and/or nonhydrocarbon constituents wherein the method according to claim 1 is carried out in conjunction with the conventional adsorbent treating method.
18. Process for treating a petroleum and/or related material containing asphaltic constituents and/or nonhydrocarbon constituents, wherein the method according to claim 1 is first carried out, and then followed by the two steps comprising:
(A) treating said mixture separated in Step B of claim 1, with n-pentane in order to precipi-tate and recover asphaltenes; and (B) separating and recovering said n-pentane used in the above step A of this claim, following said recovering of asphaltenes.
(A) treating said mixture separated in Step B of claim 1, with n-pentane in order to precipi-tate and recover asphaltenes; and (B) separating and recovering said n-pentane used in the above step A of this claim, following said recovering of asphaltenes.
19. Process for treating a petroleum and/or related material containing asphaltic constituents and/or nonhydrocarbon constituents, which are capable of being attracted by an added asphaltenes in a finely divided form, said process comprising:
(A) diluting said petroleum and/or said material by adding a petroleum fraction (or fractions), preferably a low molecular weight paraffin (or paraffins) to improve the fluidity of same;
(B) intimately contacting said petroleum and/or said material having an improved fluidity, in a contacting apparatus capable of holding same for a predetermined period of time, with said added asphaltenes thereby to attract and then precipitate said constituents together with said added asphaltenes;
(C) separating from the mixture of said constituents precipitated with said added asphaltenes, an oil (and/or gas) containing a reduced concentration of said constituents;
(D) separating and recovering said petroleum fraction (or fractions) from said oil (and/or gas); and (E) removing the volatile constituents from said mixture already separated by the above step C, to recover an asphalt.
(A) diluting said petroleum and/or said material by adding a petroleum fraction (or fractions), preferably a low molecular weight paraffin (or paraffins) to improve the fluidity of same;
(B) intimately contacting said petroleum and/or said material having an improved fluidity, in a contacting apparatus capable of holding same for a predetermined period of time, with said added asphaltenes thereby to attract and then precipitate said constituents together with said added asphaltenes;
(C) separating from the mixture of said constituents precipitated with said added asphaltenes, an oil (and/or gas) containing a reduced concentration of said constituents;
(D) separating and recovering said petroleum fraction (or fractions) from said oil (and/or gas); and (E) removing the volatile constituents from said mixture already separated by the above step C, to recover an asphalt.
20. Process according to claim 19, wherein in steps A and D said petroleum fraction being n-pentane;
and as a consequence, asphaltenes are recovered instead of an asphalt in step E.
and as a consequence, asphaltenes are recovered instead of an asphalt in step E.
21. Process for treating a petroleum and/or related material containing asphaltic constituents and/or nonhydrocarbon constituents, wherein the process according to claim 18 is first carried out, and then followed by:
treating the oils containing resins, which is left after said recovering of n-pentane in step A of claim 18, by a hydrocarbon solvent, such as liquefied propane, butane, or isobutane to separate and recover said resins.
treating the oils containing resins, which is left after said recovering of n-pentane in step A of claim 18, by a hydrocarbon solvent, such as liquefied propane, butane, or isobutane to separate and recover said resins.
22. Process for treating a petroleum and/or related material containing asphaltic constituents and/or nonhydrocarbon constituents, wherein the process according to claim 20 is first carried out, and then followed by:
treating the oils containing resins, which is left after said recovering of n-pentane in step D
of claim 20, by a hydrocarbon solvent, such as liquefied propane, butane, or isobutane to separate and recover said resins.
treating the oils containing resins, which is left after said recovering of n-pentane in step D
of claim 20, by a hydrocarbon solvent, such as liquefied propane, butane, or isobutane to separate and recover said resins.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US39985382A | 1982-07-19 | 1982-07-19 | |
| US399,853 | 1982-07-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1229317A true CA1229317A (en) | 1987-11-17 |
Family
ID=23581237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000432293A Expired CA1229317A (en) | 1982-07-19 | 1983-07-12 | Treatment and separation of petroleums and related materials |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5927987A (en) |
| CA (1) | CA1229317A (en) |
| GB (1) | GB2124250A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10570341B2 (en) | 2015-04-28 | 2020-02-25 | Siemens Aktiengesellschaft | Apparatus and process for separating asphaltenes from an oil-containing fuel |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB341560A (en) * | 1929-10-22 | 1931-01-22 | Layos Von Szeszich | Improvements relating to the hydrogenation of carbonaceous bodies in the presence of catalysts |
| GB688711A (en) * | 1949-07-20 | 1953-03-11 | Bataafsche Petroleum | Improvements in the de-asphaltising of hydrocarbon oils |
-
1983
- 1983-07-12 CA CA000432293A patent/CA1229317A/en not_active Expired
- 1983-07-15 GB GB08319151A patent/GB2124250A/en not_active Withdrawn
- 1983-07-18 JP JP12957883A patent/JPS5927987A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10570341B2 (en) | 2015-04-28 | 2020-02-25 | Siemens Aktiengesellschaft | Apparatus and process for separating asphaltenes from an oil-containing fuel |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0117518B2 (en) | 1989-03-30 |
| GB8319151D0 (en) | 1983-08-17 |
| GB2124250A (en) | 1984-02-15 |
| JPS5927987A (en) | 1984-02-14 |
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