US3051645A - Upgrading heavy hydrocarbon oils - Google Patents

Upgrading heavy hydrocarbon oils Download PDF

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US3051645A
US3051645A US30878A US3087860A US3051645A US 3051645 A US3051645 A US 3051645A US 30878 A US30878 A US 30878A US 3087860 A US3087860 A US 3087860A US 3051645 A US3051645 A US 3051645A
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magma
oil
oils
sulfur
temperature
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William B Wilson
George M Good
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Shell USA Inc
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Shell Oil Co
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Priority to GB18404/61A priority patent/GB940146A/en
Priority to DE19611470628 priority patent/DE1470628A1/de
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    • 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
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/067—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with molten alkaline material

Definitions

  • heteroatomic materials such as thiophenic compounds, pyrrolic compounds, and pyranylic materials can be removed by catalytic hydrogenation processes. Such processes, moreover, are also moderately effective in removing metallic contaminants from heavy feeds.
  • Catalytic hydrogenation is currently gaining rapidly in its extent of utilization. It is used Widely in the treatment of gasoline, kerosene, light fuel oils (furnace oils), lubricating oils and transformer oils.
  • catalytic hydrogenation is basically and inherently a costly process which involves costly catalyst and equipment, and its use is by necessity limited to those stocks which may be hydrogenated economically (l) by virtue of their low contaminants content or (2) by virtue of the fact 3,051,645 Patented Aug. 28, 1962 that they are extremely high value products which can thus bear expensive processing costs.
  • FIGURE 1 is a graphical comparison of the sulfur distribution in various residues treated in difierent manners
  • FIGURE 2 is a graphical correlation of the removal of nitrogen compounds from residues treated in accordance with the invention.
  • FIGURE 3 is a graphical correlation of the removal of vanadium compounds from residues treated in accordance with the invention.
  • FIGURE 4 is a schematic flow diagram illustrating a preferred method for practicing the process in a continuous manner.
  • the process of the invention involves reacting heavy hydrocarbon oils and residues under conditions of incipient cracking in the liquid phase with a magma mainly of an alkali metal hydroxide whereby at least two separable phases are formed, separating the thus formed phases and recovering a reaction product greatly improved with regard to content of metals and heteroatomic compounds, and improved with regard to other properties which are critical to the further employment and treating of the product by conventional refining processes, especially conversion processes.
  • the feed to the present process may be any higher boiling hydrocarbon oil at least about 50% by volume of which boils above about 450 F. Though even lighter hydrocarbons can in principle be processed, the present process is most advantageous for treatment of oils containing materials which cannot be distilled in commercial equipment without extensive cracking, e.g. residual materials and hydrocarbon oils containing asphaltenes, resins and the like.
  • the process finds its greatest utility in the treatment of stocks containing appreciable amounts of hetero atoms and/ or metals. It is, therefore, particularly useful for the treatment of reduced crudes, vacuum residues, cracked gas oils, residues and the like which cannot otherwise be deeply flashed without excessive carryover of metal contaminants.
  • the active agent used in the process of the present in vention is the magma which appears to function (1) as a reagent, (2) as catalyst, and (3) as a solvent. Though the function of the magma is not fully understood, it appears also to act to inhibit certain undesirable side reactions, especially free radical chain reactions, while simultaneously promoting other desirable reactions with the hydrocarbon feed.
  • the essential component of the magma is an alkali metal caustic which may be sodium hydroxide, potassium hydroxide or mixtures thereof. Both fused caustics, which contain essentially no water, may be used as well as aqueous caustic solutions. When aqueous solutions are used, however, the water content must not exceed about 50% by weight when using potassium or 25% by weight when using sodium. Because of excessive pressures produced by the presence of water at the reaction temperature of the process, it is preferred in any event to use a caustic magma containing no more than 30% by weight water, a water content of no more than being particularly preferred when sodium is used.
  • the temperature at which the operation is carried out is important. Qualitatively, the desired temperature is that of incipient cracking, i.e. Where thermal cracking would normally begin to take place, but below that temperature at which extensive thermal decomposition occurs.
  • the temperature of incipient cracking varies with the nature of the particular oil being processed. But in all cases for satisfactory operation of the process of the invention, the final temperature will be within about 375 to about 475 C. For most heavy oils and residues the preferred temperature of reaction is from about 400 C. to about 430 C.
  • the pressure is generally not an important factor in the process of the invention. However, it is desirable usually to suppress vaporization of the reactants in order to minimize reactor size. Consequently, superatmospheric pressures are preferred. Any higher pressures can be used if desired, but it is preferred to employ operating pressures of at least 200 p.s.i.g. but below about 1,500 p.s.i.g. Above this pressure the eco nomic advantage of lower reactor volume is offset by the higher cost of such high pressure equipment.
  • Contacting of the two phases may be carried out batchwise, as in an autoclave, or continuously. Continuous operation is preferred for commercial application of the process. Intimate contactingof the magma with the oil feed is very important in order to obtain the unique advantages which characterize this process. It is therefore necessary to impart a high shear rate and degree of turbulence to the materials as they are mixed. Moreover, it is also preferred to keep the mixed materials under a high degree of turbulence during the reaction period. When in-the-line mixing of the magma and feed is employed, it is preferred to use a mixing valve downstream of the injection point of the two components.
  • both the initial mixing and sustained turbulance of the system may be obtained by the use of one or more turbine mixers.
  • the required contact time of the oil with the magma varies widely, depending upon (1) the particular stock being processed and (2) the desired degree of improvement of the limiting function for which the process is employed. At the lower temperatures contact times up to an hour or more may be used, but at the higher tem peratures contact times may be as short as about one minute. Generally, however, the contact time should be from about 2 to about minutes.
  • the magma During the mixing and reaction of the magma with the feed, the magma, being essentially insoluble, remains as a separate phase immiscible with the liquid feed.
  • the phase may be highly dispersed as in the form of an emulsion.
  • the ratio of the two phases charged to'the reactor may vary widely, e.g. from as low as 0.025 to as high as 1.5 or even higher, basis weight ratio of caustic to feed.
  • a weight ratio of caustic to feed (caustic ratio) of at least about 0.1 is preferred, and a weight ratio of at least 0.25 is preferred for feeds containing particularly high contents of sulfur and metals. Even higher ratios, up to about 1.1 to 1 are still further preferred since even betterresults are obtained therewith.
  • caustic-to-feed ratios may be employed, no greater benefits have been observed above about 1.5 to 1.
  • the preferred range is from about 0.1 to 1.5 parts by weight caustic per part by weight of feed.
  • the ratio of caustic to feed should not be less than about 0.025 for each percentage by weight of sulfur combined in the feed.
  • magma will ordinarily contain sizeable amounts of materials other 7 than the caustic, for example water, carbonates, sulfides,
  • the magma is preferably reused at least in part.
  • the once-used magma consists of 12.2% K S, 28.5% K CO 34.0% KOH, 22.9% H 0, and 2.4% coke, metals and soluble carbonaceous compounds. If the magma and oil are contacted countercurrently, the magma near the inlet may contain a sizeably greater concentration of the hydroxide with lesser amounts of the carbonate and sulfides, and that at the outlet may contain correspondingly greater concentrations of the carbonate and sulfides and less of the hydroxide.
  • the magma When part of the magma is recirculated, it is preferably fortified by the addition of the hydroxide so that the hydroxide content of the magma to be used constitutes at least 50% by weight of the magma. Such fortification may be accomplished by regeneration of the hydroxide from the corresponding carbonates and sulfides, and/ or by the addition of higher strength caustic.
  • the sulfur compounds present in the oils treated by the process of the invention are refractory compounds, e.g. benzothiophenes, having no appreciable acidity. Accordingly, the sulfur therein is not removed as, for example, alkali metal mercaptide but as an alkali metal sulfide, which necessitates scission or cracking of the sulfur-containing molecules in the oil.
  • the desulfurization problem of heavy oils and residuals is the rapid removal of benzothiophenic and dibenzothiophenic sulfur, which comprise from 60 to of the sulfur compounds present.
  • Example I A quantity of a Los Angeles Basin-Ventura/Four Corners crude straight run residue (reduced crude) was divided into several parts which were treated as follows:
  • a most advantageous feature of the magma cracking of heavy oils and residues in contrast to conventional thermal treatment is that thermal reactions involving cracking the hydrogen-rich alkyl fragments into gas, gasoline, and gas oils which normally occur at the conditions used are inhibited. This is illustrated by the following example.
  • the process of the invention is applicable to a wide range of oils, crudes, and residues. Though the degree of sulfur removal that can be obtained by magmacracking under practical operating conditions varies somewhat with different feeds, it is observed that the heavier the feed the more amenable it is to deep desulfurization. This may be seen from the following example.
  • Example III Three residues produced from the commercial processing of Los Angeles Basin-Ventura crude were treated in accordance with the invention. Different severity treatment with regard to temperature and caustic magma concentration were employed, the more severe conditions being used for the lighter (higher API gravity) stocks and less severe conditions being used for the heavier stocks. The results were as follows:
  • the metals are concentrated in the heavy oil and residual portions of the crude, they are easily entrained in various distillation and flashing operations into the lighter fractions and, moreover, they are decomposed and volatilized under the temperature conditions normally necessary for separating, for example, heavy gas oil fractions from crude.
  • the lighter gas oil fractions are likely to contain significant amounts of metals.
  • the excellent degree of removal of vanadium from residuals by the process of the invention is shown by the following example.
  • Example XIII A number of tests were performed in which a Los Angeles Basin-Ventura straight run residue was magma cracked in accordance with the invention. Several different operating severities were again employed, and the product therefrom was analyzed with respect to vanadium content. As in the previous example, the degree of vanadium removal'was correlated with sulfur removal, the results of which are shown in FIGURE 3 of the drawing. This correlation shows clearly that over of the vanadium is removed at even low severity operation (40% sulfur removal), whereas over 96% of the vanadium is removed at the minimum preferred level of desulfurization (60%). Of particular importance, however, is that even above 99% removal of vanadium is obtained at the 80% desulfurization level of severity, which is readily attained in the process.
  • the degree of metals removal obtainable with this process is such that some reduced crudes may be amenable to catalytic cracking in their entirety, whereas in the past only the solvent deasphalted raftinates or vacuum gas oils therefrom could be completely catalytically cracked economically. Moreover, the cracked products obtained therefrom will be g superior due to the low sulfur content of the resultin products.
  • FIGURE 4 of the drawing A preferred way in which the process is performed continuously is illustrated by FIGURE 4 of the drawing, a detailed description of which follows.
  • ' action zone 207 consists of one or more parallel reaction chambers appropriately lined to avoid corrosion from the caustic magma and so sized that the mixed magma and feed may have a residence time of about minutes therein.
  • Fresh or regenerated magma supplied to the process consists of 71% wt. potassium hydroxide aqueous solution.
  • the magma is maintained at a temperature well above its solidification temperature.
  • magma is supplied at a temperature of about 300 F. through line 35, oil-magma rag is added from line 23, and the mixture is passed to heat exchanger 209 wherein it exchanges heat with the hot reactor efiiuent.
  • the magma is heated further to about 630 F. after which it is passed by means of line 9 to line 7 wherein it is mixed with residue feed as described before.
  • the temperature to which the residue is heated is adjusted so that the combined mixture of hot magma and residue are at the appropriate reaction temperature, in this case 800 F.
  • the outlet temperature of the residue from furnace 203 is, of course, raised accordingly.
  • the reacted mixture of magma and magma-cracked residue is passed by means of line 11 to heat exchanger 209 wherein it exchanges heat with magma from line 35 and is cooled from approximately the reaction temperature (300 F.) to about 720 F.
  • the partially cooled reaction mixture is passed further through line 11 to heat exchanger 201 wherein it exchanges heat with incoming feed and is cooled further to about 405 F.
  • the mixture of magma and oil reaction product must not be cooled to the solidification temperature of the magma. Preferably it is cooled to a temperature at least 50 F. above the solidification temperature.
  • the cooled mixture of reacted magma and cracked residue is mixed with 48,000 lb./hr.
  • settling zone 211 the mixture of reacted magma, residue, and water is allowed to settle upon which two layers are formed with an intermediate interfacial emulsion or rag.
  • the upper layer in settling zone 21]. consists of a layer of reacted oil and small amounts of entrained magma and other impurities.
  • the lower layer consists of a layer of aqueous solution of unreacted magma containing impurities removed from the treated oil as well as sulfides and carbonates produced during the reaction step.
  • the interfacial rag is an emulsion of largely unreacted magma, oil product, and some impurities.
  • This emulsion is withdrawn at a rate of about 5,000 lb./hr. through line 23 and mixed with fresh magma to the process in line 35 prior to heat exchange and passage to reaction zone 207.
  • About 1,500 lb./hr. of gaseous products are formed during the reaction step and are collected in the upper part of settling zone 211 from which they are passed by means of line 21 to further treating recovery, or disposal.
  • the lower layer of used contarninated magma is drawn off through line 25 for regeneration, in which case it may be recycled to the process with fresh magma in line 35, for other caustic treating processes, or for waste disposal.
  • the upper layer contained in settling zone 2.11 is Withdrawn through line 27 wherein it is mixed with 42,000 lb./ hr. of Water from line 29, and the mixture of oil from the upper layer and water are passed together to a second settling zone 213, wherein the mixture is settled into two distinct phases with little or no interfacial emulsion between.
  • the water from settling zone 213 which has removed essentially the final trace amounts of magma from the reacted oil is Withdrawn through 33 and passed to line 19 wherein it is mixed with cooled reaction product and magma as described above.
  • magma treated oil product which comprises the upper layer in zone 213, is passed at a rate of 412,500 lb./hr. by means of line 31 to further processing such as catalytic cracking, vacuum distillation, catalytic hydrogenation, and the like.
  • magma-oil mixture may form an extensive emulsion, therefore various measures will be taken to overcome this.
  • demulsifying agents such as those which are well known in the art of crude desalting, may be added either to the water in line 29 or 33 or to the magma-oil mixture; or electrostatic precipitation means may be used in the settling zone; or combinations of these techniques may be used.
  • electrostatic precipitation means may be used in the settling zone; or combinations of these techniques may be used.
  • other separation techniques may be used for separating the oil and magma layers and the emulsion, among which is the use of centrifugal action either with or without diluents added to increase the density difference between the phases.
  • the process of the invention is further advantageous in that valuable by-product vanadium metal or vanadium pentoxide may be recovered from the magma.
  • the recovery of vanadium from this source is particularly advantageous since (1) the vanadium pentoxide may be recovered in higher purity than in conventional ore recovery processes and (2) the vanadium or vanadium compounds produced according to the invention are especially low in radioactivity as recovered without extensive and costly refining.
  • Vanadium pentoxide which is the principal per-cursor for vanadium metal, is produced from various primary ores such as Patronite, Bravoite, Sulvanite, Davidite, Roscoelite, and Montroselite.
  • the ore is usually roasted with common salt forming largely sodium vanadate which is leached in successive stages with water and dilute sulfuric acid, after which it is precipitated with concentrated sulfuric acid thus forming vanadium pentoxide.
  • the V 0 produced in this manner without further excessive refining steps is normally about purity, the major impurities being calcium and sodium salts.
  • the major impurities being calcium and sodium salts.
  • V 0 may be extracted simply and directly from the caustic magma produced in accordance with the invention in purities of nearly
  • the extraction of vanadium pentoxide from the caustic magma is illustrated by the following example.
  • Example XIV The once-used potassium hydroxide magma which was employed in the treatment of Ba mangoro straight run residue in Example VIII was treated as follows:
  • magma Upon separation of the magma from the treated oil in Example VIII, 290 grams of the magma were analyzed and found to contain 0.264 gram of vanadium. The magma was washed with carbon tetrachloride to facilitate handling at normal temperatures and diluted with water. The diluted magma was filtered to remove the iron and nickel compounds which are insoluble in the diluted magma. The filtrate was then weakly acidified (pH 5-6) by the addition of acetic acid which resulted in decomposition of the carbonates and sulfides contained in the diluted magma and the consequent evolution of carbon dioxide and hydrogen sulfide gases.
  • the acidified dilute magma was again filtered upon which an initial portion of vanadium was removed as a potassium vanadate precipitate.
  • the potassium vanadate thus removed by filtration contained 0.076 gram of vanadium.
  • To the weakly acid filtrate was then added an aqueous solution of tannic acid which formed an insoluble complex phase.
  • the complex phase was separated from the bulk of the filtrate and ignited to decompose the complex, care being taken that the temperature during ignition did not exceed about 600 C.
  • the product from the ignition was found to be about 88% pure V containing 0.188 gram of vanadium.
  • vanadium obtained from petroleum in accordance with the invention is much lower in radioactivity than that which is normally obtainable.
  • low radioactivity vanadium may be produced in this manner without extensive rerefining as is now required in the purification of orederived vanadium metal.
  • Such low radioactivity is of particular advantage when the metal is used for sensitive instruments which require a low radioactivity background.
  • Process for upgrading heavy hydrocarbon oils containing contaminants selected from the group consisting of metals and heteroatomic compounds of sulfur and nitrogen which comprises the steps (1) intimately contacting the oil in the liquid phase with a magma consisting essentially of the carbonate, sulfide and hydroxide of a metal selected from the group consisting of sodium, potassium, and mixtures thereof and no more than about 30% by weight water, basis the metal hydroxide content of the magma, the ,weight ratio of metal hydroxide in the magma to hydrocarbon oil being from 0.1 to 1.5, the magma comprising at least 50% by weight of said hydroxide, at a temperature between about 375 and 450 C., and a pressure of at least 200 p.s.i.g..f0r at least one 12 minute at the high end of the contacting temperature range to at least about 1 hour at the low end of said range thus forming a reaction mixture of magma and reacted oil product, (2) cooling the reaction mixture to.
  • a magma consisting essentially of the carbonate
  • Process for upgreading heavy hydrocarbon oils containing contaminants selected from the group consisting of metals and heteroatomic compounds of sulfur and nitrogen which comprises contacting the heavy hydrocarbon oil in the liquid phase at a temperature between about 375 and 475 C., and a pressure of at least 200 p.s.i.g. and a contact time of from about one minute to about two hours, with a magma consisting essentially of sodium carbonate, sulfide and hydroxide and water, the weight ratio of water to sodium hydroxide in the magma being not more than 0.43 to 1 and the weight ratio of metal hydroxide to hydrocarbon oil being from 0.1 to 1.5, and separating from the contacted mixture an oil phase having substantially reduced content of contaminants.
  • a magma consisting essentially of sodium carbonate, sulfide and hydroxide and water

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  • Engineering & Computer Science (AREA)
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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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GB18404/61A GB940146A (en) 1960-05-23 1961-05-19 Process for upgrading heavy hydrocarbon oils
DE19611470628 DE1470628A1 (de) 1960-05-23 1961-05-20 Verfahren zur Befreiung von Kohlenwasserstoffoelen von Verunreinigungen

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Cited By (17)

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US3129165A (en) * 1960-05-09 1964-04-14 Shell Oil Co Refining of steam-cracked gasolines with molten salt
US3354081A (en) * 1965-09-01 1967-11-21 Exxon Research Engineering Co Process for desulfurization employing k2s
US3440164A (en) * 1965-09-03 1969-04-22 Exxon Research Engineering Co Process for desulfurizing vacuum distilled fractions
US4224139A (en) * 1979-04-16 1980-09-23 Phillips Petroleum Company Treatment of sulfur-containing lubricating oil to increase resistance to oxidation
US20030229583A1 (en) * 2001-02-15 2003-12-11 Sandra Cotten Methods of coordinating products and service demonstrations
US20050167323A1 (en) * 2003-12-19 2005-08-04 Wellington Scott L. Systems and methods of producing a crude product
US20060006556A1 (en) * 2004-07-08 2006-01-12 Chen Hung Y Gas supply device by gasifying burnable liquid
US7534342B2 (en) 2003-12-19 2009-05-19 Shell Oil Company Systems, methods, and catalysts for producing a crude product
US7678264B2 (en) 2005-04-11 2010-03-16 Shell Oil Company Systems, methods, and catalysts for producing a crude product
US20100155298A1 (en) * 2008-12-18 2010-06-24 Raterman Michael F Process for producing a high stability desulfurized heavy oils stream
US7745369B2 (en) 2003-12-19 2010-06-29 Shell Oil Company Method and catalyst for producing a crude product with minimal hydrogen uptake
US7749374B2 (en) 2006-10-06 2010-07-06 Shell Oil Company Methods for producing a crude product
US7918992B2 (en) 2005-04-11 2011-04-05 Shell Oil Company Systems, methods, and catalysts for producing a crude product
US20110147273A1 (en) * 2009-12-18 2011-06-23 Exxonmobil Research And Engineering Company Desulfurization process using alkali metal reagent
US20110147271A1 (en) * 2009-12-18 2011-06-23 Exxonmobil Research And Engineering Company Process for producing a high stability desulfurized heavy oils stream
US20110147274A1 (en) * 2009-12-18 2011-06-23 Exxonmobil Research And Engineering Company Regeneration of alkali metal reagent
US8894845B2 (en) 2011-12-07 2014-11-25 Exxonmobil Research And Engineering Company Alkali metal hydroprocessing of heavy oils with enhanced removal of coke products

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Cited By (61)

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Publication number Priority date Publication date Assignee Title
US3129165A (en) * 1960-05-09 1964-04-14 Shell Oil Co Refining of steam-cracked gasolines with molten salt
US3354081A (en) * 1965-09-01 1967-11-21 Exxon Research Engineering Co Process for desulfurization employing k2s
US3440164A (en) * 1965-09-03 1969-04-22 Exxon Research Engineering Co Process for desulfurizing vacuum distilled fractions
US4224139A (en) * 1979-04-16 1980-09-23 Phillips Petroleum Company Treatment of sulfur-containing lubricating oil to increase resistance to oxidation
US20030229583A1 (en) * 2001-02-15 2003-12-11 Sandra Cotten Methods of coordinating products and service demonstrations
US7807046B2 (en) 2003-12-19 2010-10-05 Shell Oil Company Systems, methods, and catalysts for producing a crude product
US7416653B2 (en) 2003-12-19 2008-08-26 Shell Oil Company Systems and methods of producing a crude product
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GB940146A (en) 1963-10-23
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