EP0202099A2 - Procédé de traitement de résidus lourds d'huile pétrolière - Google Patents
Procédé de traitement de résidus lourds d'huile pétrolière Download PDFInfo
- Publication number
- EP0202099A2 EP0202099A2 EP86303612A EP86303612A EP0202099A2 EP 0202099 A2 EP0202099 A2 EP 0202099A2 EP 86303612 A EP86303612 A EP 86303612A EP 86303612 A EP86303612 A EP 86303612A EP 0202099 A2 EP0202099 A2 EP 0202099A2
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- EP
- European Patent Office
- Prior art keywords
- solvent
- resid
- light
- vessel
- heavy
- 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.)
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- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000003208 petroleum Substances 0.000 title claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 67
- 239000012530 fluid Substances 0.000 claims abstract description 58
- 238000004227 thermal cracking Methods 0.000 claims abstract description 28
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 18
- 238000005336 cracking Methods 0.000 claims abstract description 6
- 239000012071 phase Substances 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 28
- 238000000926 separation method Methods 0.000 claims description 17
- 238000009835 boiling Methods 0.000 claims description 14
- 238000000605 extraction Methods 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004939 coking Methods 0.000 abstract description 6
- 238000000638 solvent extraction Methods 0.000 abstract description 6
- 230000003111 delayed effect Effects 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 10
- 239000000295 fuel oil Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000011084 recovery Methods 0.000 description 7
- 239000000571 coke Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
-
- 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
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one thermal cracking step
-
- 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
Definitions
- This invention relates to a process for the treatment of heavy petroleum oil resid streams. More particularly, this invention relates to a process for the treatment of heavy petroleum oil resid streams to obtain therefrom useful oil fractions substantially free of asphaltenes and heavy metals.
- thermal cracking processes include the visbreaking process, such as exemplified by U. S. 4,454,023, and the delayed coking process both of which have been extensively practiced for effecting the thermal cracking of heavy petroleum oil.
- Solvent extraction processes also have been proposed. However, the use of such processes by themselves alone provide for the recovery of only a limited amount of useful oil products. This is especially true when the feedstock contains a very high content of heavy metals. From the viewpoint of effectively utilizing both resources and energy, it is clear that further improvements in the treatment of heavy petroleum oils resids are needed.
- the present invention relates to a novel and improved process for treating heavy petroleum oil resid feed streams.
- the novel and improved process of the present invention comprises introducing a heavy petroleum oil feed stream, which has been preheated to a temperature in the range of from about 450°C to about 550 * C in a preheater, into an upper portion of an adiabatic thermal cracker.
- the preheated heavy petroleum oil feed stream is caused to flow downwardly through the thermal cracker in a plug-flow condition through the use of multi-stage horizontally positioned perforated plates which are spaced at intervals throughout the thermal cracker.
- the operating conditions employed within the thermal cracker include temperatures in the range of from about 390°C to about 450°C, pressures of at least atmospheric pressure and residence times in the range of from about 1 to about 5 hours.
- distillate vapors and gaseous products resulting from the thermal cracking of the heavy petroleum oil resid feed stream are removed by means of steam introduced into a lower portion of the thermal cracker, which steam flows upwardly in a countercurrent direction to the descending heavy petroleum oil resid feed stream undergoing thermal cracking.
- steam introduced into a lower portion of the thermal cracker, which steam flows upwardly in a countercurrent direction to the descending heavy petroleum oil resid feed stream undergoing thermal cracking.
- From 30 to 65 percent of the components in the heavy petroleum oil resid feed stream having boiling points above about 500°C convert to components having boiling points below about 500°C.
- From the lower portion of the thermal cracker there is withdrawn a cracked resid bottoms stream, which resembles a liquid pitch.
- This bottoms stream which contains an asphaltene fraction, heavy metals and useful oil components, then is mixed with a solvent and the mixture subjected to solvent extraction.
- the solvent extraction is carried out at temperatures and pressures at or near the critical point of the solvent and above the softening point of the asphaltene fraction. Under such conditions a mixture of the asphaltene fraction and heavy metals is rapidly and efficiently separated from the useful oil components in said bottom stream.
- the single Figure is a schematic flow diagram illustrating one embodiment of the process of the present invention.
- the novel process of the present invention is comprised of a series of steps, whereby the overall yield and quality of useful oil components therefrom are improved.
- the steps comprise subjecting a heavy petroleum oil resid feed stream, such as an atmospheric or vacuum distillation column bottom resid (i.e., an atmospheric or vacuum residue) to selective thermal cracking.
- the selective thermal cracking is carried out under conditions whereby cracking of the heavy petroleum oil resid feed stream is confined to the decomposition of only those high molecular hydrocarbon constituents or components in the feedstock that are relatively easily decomposed.
- This selective thermal cracking step separation and recovery of the light hydrocarbons formed is accelerated by simultaneous steam stripping.
- Thermally-cracked heavy petroleum oil resid withdrawn from the bottom of the thermal cracker then is subjected to a highly efficient critical solvent extraction-separation treatment which comprises the second step of the process of the present invention. Through the use of this critical solvent extraction-separation step, substantially all of any remaining useful oil components remaining in the thermally-cracked heavy oil resid are recovered.
- the operating conditions employed in both the thermal cracking step and the critical solvent extraction-separation step are selected in accordance with the composition of the heavy petroleum oil resid feed stream such that the total yield of useful oil components recovered as well as the quality thereof is maximized.
- said yield and quality are much higher than can be obtained from more conventional processes such as the catalytic cracking, hydrocracking, visbreaking, delayed coking or solvent extraction processes.
- the resid or bottom stream recovered from the thermal cracking step of the present process is in a highly fluid state as is the heavy metals containing asphaltene fraction recovered in the solvent extraction-separation step. The highly fluid nature of these materials makes them more easily handled than those recovered from the more conventional processes mentioned above.
- the operating conditions employed in the thermal cracking will be conditions which promote the selective concentration of nickel, vanadium and other heavy metals present in the heavy petroleum oil resid feedstock into the asphaltene fraction of the thermally-cracked heavy oil resid stream withdrawn from the bottom of the thermal cracker.
- the degree of cracking carried out in the thermal cracking step of the process of the present invention is restricted such that about 65 percent by weight or more, and preferably about 60 percent by weight or more of the components in the heavy petroleum oil resid feed having atmospheric boiling points above about 500°c are not decomposed to components having atmospheric boiling points below about 500°C.
- the separation, recovery, transportation and the like, of the final resid or asphaltene fraction becomes extremely difficult requiring complex apparatus to accomplish these tasks.
- the degree of thermal cracking carried out in the first step of the process of the present invention is limited such that the thermally-cracked heavy oil residue recovered therefrom contains minimal amounts of coke.
- the final resid or asphaltene fraction extracted therefrom in the extraction step of the present invention will be in a highly fluid state at process temperatures. Such highly fluid state facilitates its separation, recovery and the like and simplifies the type of equipment employed and the arrangement thereof.
- Further teachings relating to the operating conditions, equipment and the like for carrying out this selective thermal cracking or first step in the process of the present invention can be found in U. S. Patent Nos. 4,435,276 and 4,443,328. The teachings of these U. S. patents are incorporated herein by reference in their entirety.
- the thermally-cracked heavy oil resid or bottoms stream withdrawn from the thermal cracker is subjected to a critical solvent extraction-separation which comprises the second step of the present invention.
- the thermally-cracked heavy oil resid is mixed with a critical solvent.
- This mixture then is subjected to temperatures higher than the softening point of the asphaltene fraction in the thermally-cracked resid and preferably to conditions of temperature and pressure within the proximity of the critical point of the solvent. Under these conditions, the asphaltene fraction is less soluble in the critical solvent than the useful oil components and a rapid separation of the asphaltene fraction from the mixture can be effected.
- a heavy petroleum oil resid feedstock such as an atmospheric or vacuum distillation bottoms resid
- conduit 1 a heavy petroleum oil resid feedstock
- preheater 2 the heavy petroleum oil resid feedstock is heated to temperatures in the range of from about 450 * C to above 550°C under pressures in the range of from about 1 to about 10 kg/cm 2 .
- preheater 2 In order to avoid coking of the feedstock it is passed through preheater 2 at a velocity in the range of from about 2 to about 20 m/sec.
- the preheated feedstock then is conveyed from preheater 2 through conduit 3 to an upper portion of upright cylindrical thermal cracker 4.
- Steam, and preferably superheated steam is introduced into a bottom portion of thermal cracker 4 through conduit 18 and steam distributing means 18'.
- This superheated steam flows upwardly and countercurrent to the downwardly flowing feedstock which is undergoing thermal reaction.
- the countercurrently flowing superheated steam facilitates the evaporation and removal of cracker light oil components from the downwardly flowing thermally reacting feedstock, thus eliminating the need of subjecting the thermally-cracked resid recovered from thermal cracker 4 to vacuum distillation.
- the amount of superheated steam introduced to thermal cracker 4 through conduit 18 and distributing means 18' to evaporate and remove cracked light oil components will be in the range of from about 5 percent to about 20 percent by weight of the feedstock stream undergoing thermal reaction in thermal cracker 4.
- thermal cracker 4 is operated at atmospheric pressure and at temperatures ranging from about 390 * C to about the temperature of the preheated feedstock introduced thereto.
- the residence time of the feedstock in thermal cracker 4 will be at least two times that for a visbreaking process or from about 1 to about 10 hours.
- the thermally reacting feedstock be made to descend downwardly through thermal cracker 4 in a substantially plug-flow manner and that it not be allowed to stagnate at or near the internal surfaces of thermal cracker 4. Failure to maintain plug-flow also can result in the formation of channels and vortexes in the descending column of thermally reacting feedstock. Such channels and vortexes, once formed, provide paths along which portions of the feedstock can quickly pass through, and out of, thermal cracker 4. The shorter residence time for these portions of the thermally reacting feedstock in thermal cracker 4 can lead to an undesirable lowering of the overall conversion of the feedstock to the more desirable useful oil products.
- thermal cracker 4 is equipped with multiple horizontal perforated partition plates 4a through 4j.
- Thermal cracker 4 also is equipped with a drive shaft 38 driven by motor 40.
- Drive shaft 38 is fitted with multiple horizontal scraper blades, two of which (38a and 38b) are designated on the Figure.
- the horizontal scraper blades attached to drive shaft 38 are located immediately adjacent to each of the multiple horizontal perforated partition plates 4a through 4h and extend outwardly from drive shaft 38 to near the internal surface of thermal cracker 4.
- the purpose of drive shaft 38 and the multiple horizontal scraper blades affixed thereto is to provide for the even distribution throughout the downwardly flowing thermally reacting feedstock of the meso-phase coke precursors produced as part of the thermal cracking reaction. By maintaining these meso-phase coke precursors evenly distributed throughout the descending reactions stream, agglomeration of these precursors and, therefore, the accumulation of coke within thermal cracker 4 substantially is prevented.
- This mixture then is discharged from the upper portion of thermal cracker 4, through conduit 19 and condenser 20 to separator 21.
- separator 21 the mixture is separated into a cracked gas stream, a condensed water stream and a cracked light oil stream which are removed from separator 21 through conduits 22, 23 and 34, respectively.
- a fluid, thermally-cracked resid stream is removed from the bottom portion of thermal cracker 4.
- This fluid bottoms resid stream is removed from thermal cracker 4 and conveyed by means of pump 5 and communicating conduit 6 directly to mixer 7.
- the fluid resid stream is mixed with a suitable solvent introduced into mixer 7 by way of conduit 33 in a volumetric ratio in the range of from about 1:8 to about 1:12.
- the mixture of thermally-cracked bottoms resid and solvent then is conveyed through conduit 8 to first separating column 9 wherein the mixture is maintained at elevated temperatures ranging up to and above the critical temperature of the solvent and elevated pressures of at least about the vapor pressure of the solvent at the temperature being maintained.
- first separating column 9 and under the operating temperature disclosed said mixture of thermally-cracked bottoms resid and solvent undergoes separation into a first fluid light phase comprising resinous components, useful oil components and solvent and a fluid-like first heavy phase containing asphaltenes and heavy metals.
- the first fluid light phase is withdrawn from the top of first separating column 9 via communicating conduit 10 and conveyed to second separating column 11 through heater 27. By means of heater 27, the first fluid light phase further is heated to a temperature greater than the temperature employed in first separating column 9.
- the fluid-like first heavy phase which comprises asphaltenes, heavy metals and some solvent is withdrawn from the bottom portion of first separating column 9 via conduit 12, containing pressure reducing valve 35, and introduced into separator 24. In separator 24 the pressure further is reduced to thereby effect vaporization of the solvent.
- the solvent is recovered from separator 24 through conduit 26. This recovered solvent then can be returned to mixer 7 through communicating condenser 30, pump 32, and conduit 33.
- the asphaltenes, upon vaporization and removal of the solvent in separator 24, are removed and recovered therefrom in a highly fluid state through conduit 25.
- the first light phase is withdrawn from first separating column 9 and conveyed into second separating column 11 after being heated in heater 27 to a temperature higher than the temperature employed in first separating column 9.
- the first light phase separates into a second fluid light phase comprising the useful oil components and solvent, and a fluid-like second heavy phase comprising the resinous components and some solvent.
- the second fluid light phase is withdrawn from the top of second separating column 11 through a conduit 13 and introduced into third separating column 14 after being heated to above the critical temperature of the solvent in heater 28.
- the fluid-like second heavy phase comprising the resinous components is discharged in a fluid state from the bottom of second separating column 11 through conduit 15 for recovery, or for recycle to preheater 2 for mixing with fresh feedstock and further cracking in thermal cracker 4.
- third separating column 14 wherein the solvent is in a supercritical state the second light phase undergoes separation into a third light phase and a fluid-like third heavy phase comprising the desired product, i.e., a deasphalted oil.
- This product is withdrawn from the bottom of third separating column 14 through conduit 16 and recovered.
- the third light phase comprising the bulk of the original extraction solvent is withdrawn from the top of third separating column 14 through conduit 17 and recycled via communicating cooler 29 and pump 31 back to mixer 7.
- Make-up solvent can be supplied to mixer 7 by means of pump 36 through conduit 37 to replenish solvent lost in small amounts from the system in company with the asphaltenes, resins and useful oil components being separated and recovered in this portion of the process of the present invention.
- a feed oil comprising a mixed vacuum distillation column bottoms oil (vacuum resid) obtained from Middle and Near East crude oils and containing 83 ppm of nickel and 272 ppm of vanadium was preheated to 480°C and introduced into the upper portion of a thermal cracker having 10 spaced-apart horizontal, perforated, partition plates.
- the vacuum resid flowed downwardly through the thermal cracker under reaction conditions of atmospheric pressure and a cracker bottom temperature of 420 * C.
- the residence time of the thermally reacting vacuum resid within the thermal cracker was about 120 minutes.
- a vaporous, mixed effluent stream was removed from the top of the thermal cracker which was composed of steam and 4 percent by weight of cracked gaseous products and 51 percent by weight of thermally-cracked light oil vapors based on the weight of the original vacuum resid feed.
- a fluid effluent stream was recovered from the bottom of the thermal cracker.
- This fluid effluent stream comprised thermally-cracked resid representing the remaining 45 percent by weight of the initial vacuum resid feed.
- the thermally-cracked fluid resid had a softening point of 150°c when measured in accordance with the ring and ball test and an asphaltene content of 40 percent by weight.
- the thermally-cracked fluid resid then was fed from the bottom of the thermal cracker to a mixer where it was mixed with cyclohexane solvent in a ratio of resid to solvent of 1:10 by volume and thereafter introduced into the first of a series of three separating columns.
- the first separating column was maintained at a temperature of 282 * C and a pressure of 53.7 kg/cm 2 (52 atm.). Under these conditions, the mixture in the first separating column separated into an asphaltene-containing heavy fluid phase and a light fluid phase of a mixture of a resinous oil component, a lighter oil component and cyclohexane solvent.
- the asphaltene-containing heavy fluid phase containing about 30 percent of the cyclohexane solvent then was withdrawn from the lower portion of this first separating column and reduced in pressure to atmospheric pressure to flash and recover the solvent therefrom. About 98 percent of the cyclohexane solvent contained in this heavy fluid phase was recovered leaving an asphaltene-rich fluid product representing a yield of 45 percent by weight based on the weight of the thermally-cracked fluid resid feed to the first separating column.
- This asphaltene-rich fluid product contained 460 ppm of nickel and 1500 ppm of vanadium and had a softening point of 240 * C when measured in accordance with the ring and ball test.
- the light liquid phase comprising the mixture of a resinous oil component, a lighter oil component and the cyclohexane solvent was withdrawn from the upper portion of the first separating column and heated. Thereafter, the heated light liquid phase was introduced into a second separating column being operated at an internal temperature of 290°C and an internal pressure of 51.6 kgcm 2 (50 atm.). Under these conditions, the mixture separated into a second heavy fluid phase comprising the resinous oil component and a second light liquid phase comprising a mixture of the lighter oil component and the cyclohexane solvent.
- the second heavy fluid phase comprising the resinous oil components was discharged and recovered from the bottom of the second separating column in a yield of 10 percent by weight based on the thermally-cracked fluid resid feed to the first distilling column.
- the second light liquid phase was withdrawn from the upper portion of the second separating column, further heated and thereafter introduced into a third separating column.
- This third separating column was operated at an internal temperature of 316 * C and an internal pressure of 50.6 kg/cm 2 (49 atm.) to effect a separation of the lighter oil component from the cyclohexane solvent.
- the lighter oil component was discharged from the bottom portion of the third separating column while the cyclohexane solvent was withdrawn from the upper portion of the column.
- the withdrawn cyclohexane solvent then was cooled and thereafter recycled to the mixer for reuse.
- the lighter oil component recovered in the third separating column represented a yield of 45 percent by weight based on the thermally-cracked fluid resid feed to the first distilling column and had an asphaltene content of 0.5 percent by weight, a nickel content of 10 ppm and a vanadium content of 20 ppm.
- the combined yield of the thermally-cracked light oils recovered directly from the thermal cracker and the lighter oil components extracted and separated by the solvent was 71.25 percent by weight and the extent of removal of heavy metals present in the initial thermally-cracked fluid resid feed was 98.3 percent.
- the amount of cyclohexane solvent consumed during the extraction and separation steps was 0.05 percent by weight based on the weight of the resid feed to the thermal cracker.
- the same vacuum resid feed oil as used in the above Example was preheated to 450 . C and fed to the same thermal cracker as used in the above Example. Within the thermal cracker the vacuum resid feed oil was subjected to thermal decomposition under the conditions of 14.8 atm. pressure, 430°C and a residence time of 10 minutes without steam stripping. Under these conditions, which are similar to those employed in conventional visbreaking processes, only 20 percent by weight of the components having boiling points above 500°C was converted to the components having boiling points below 500°C.
- a thermally-cracked fluid resid was withdrawn from the bottom of the thermal cracker and combined in a mixer with pentane in a ratio of solvent to resid of 10:1 by volume and the resulting mixture then introduced into a first separating column operated at an internal temperature of 177°C and an internal pressure of 43.4 kg/cm 2 (42 atm.). Under these conditions, the mixture in the first separating column separated into an asphaltene-containing heavy fluid phase and a light liquid phase of a mixture of a resinous oil component, a lighter oil component and pentane solvent.
- the asphaltene-containing heavy fluid phase containing some pentane solvent was discharged from the bottom of the first separating column and reduced in pressure to atmospheric pressure whereby the solvent pentane was vaporized through flashing for the separation and recovery thereof.
- An asphaltene-rich fluid product was recovered in a yield of 50 percent by weight based on the weight of the thermally-cracked fluid resid feed to the first separating column.
- This asphaltene-rich fluid product contained 111 ppm nickel and 363 ppm of vanadium.
- the light liquid phase comprising the mixture of a resinous oil component, a lighter oil component and the pentane solvent was discharged from the upper portion of the first separating column and introduced into a second separating column operated at an internal temperature of 200 * C and an internal pressure of 47.5 kg/cm 2 (46 atm.).
- the second separating column Within the second separating column the light liquid phase was separated into a second heavy fluid phase of the resinous oil components which was discharged from the bottom of the second separating column and recovered in a yield of 10 percent by weight based on the weight of thermally-cracked fluid resid feed introduced into the first distilling column.
- the second light liquid phase was withdrawn from the upper portion of the second separating column, heated and thereafter introduced into a third separating column operated at an internal temperature of 227 . C and an internal pressure of 45.4 kg/cm 2 (44 atm.).
- the third separating column the lighter oil component was separated from the solvent.
- the lighter oil component was discharged from the bottom of the third distilling column while the solvent was discharged from the upper portion thereof, cooled and thereafter circulated to the mixer for reuse.
- the lighter oil component recovered in the third separating column was obtained in a yield of 40 percent by weight based on the weight of thermally-cracked fluid resid feed to the first distilling column and had an asphaltene content of 0.1 percent by weight or less, a nickel content of 42 ppm and a vanadium content of 136 ppm.
- the combined yield of the thermally-cracked light oils recovered directly from the thermal cracker and the lighter oil component extracted and separated by the solvent was only 52 percent by weight. This yield is substantially lower than the 71.25 percent yield of the previous Example.
- the extent of removal of heavy metals present in the initial thermally-cracked fluid resid feed in this Example was only 80 percent compared to 98.3 percent in the previous Example.
- the amount of the pentane solvent consumed in this Example was 0.5 percent by weight based on the weight of the thermal cracker vacuum resid feed compared to only 0.05 percent in the previous Example.
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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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60101161A JPS61261391A (ja) | 1985-05-13 | 1985-05-13 | 熱分解改質油の製法 |
JP101161/85 | 1985-05-13 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0202099A2 true EP0202099A2 (fr) | 1986-11-20 |
EP0202099A3 EP0202099A3 (en) | 1988-02-03 |
EP0202099B1 EP0202099B1 (fr) | 1991-08-21 |
Family
ID=14293319
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86303612A Expired - Lifetime EP0202099B1 (fr) | 1985-05-13 | 1986-05-13 | Procédé de traitement de résidus lourds d'huile pétrolière |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0202099B1 (fr) |
JP (1) | JPS61261391A (fr) |
KR (1) | KR900000861B1 (fr) |
CN (1) | CN86102643B (fr) |
DD (1) | DD251781A5 (fr) |
DE (1) | DE3680944D1 (fr) |
MX (1) | MX169003B (fr) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0272577A1 (fr) * | 1986-12-18 | 1988-06-29 | Lummus Crest, Inc. | Traitement de la charge pour une viscoréduction sévère |
EP0274604A1 (fr) * | 1986-12-18 | 1988-07-20 | Abb Lummus Crest Inc. | Viscoréduction sévère |
EP0343371A1 (fr) * | 1988-05-26 | 1989-11-29 | Abb Lummus Crest Inc. | Viscoréduction cévère avec rècirculation |
EP0372652A1 (fr) * | 1988-12-05 | 1990-06-13 | Shell Internationale Researchmaatschappij B.V. | Procédé de conversion d'une charge lourde d'hydrocarbures |
EP0999200A1 (fr) * | 1998-11-04 | 2000-05-10 | Rohm And Haas Company | Installation et procédé de préparation avec un rendement élevé du méthacrylate de méthyle ou de l'acide acrylique |
US20170067330A1 (en) * | 2013-09-09 | 2017-03-09 | Rahman Khaledi | Recovery From A Hydrocarbon Reservoir |
CN112708436A (zh) * | 2019-10-25 | 2021-04-27 | 国家能源投资集团有限责任公司 | 中间相沥青制备系统和中间相沥青制备方法 |
CN112870753A (zh) * | 2021-01-26 | 2021-06-01 | 广东申菱环境系统股份有限公司 | 一种冷凝式油气回收装置 |
WO2022084046A1 (fr) | 2020-10-23 | 2022-04-28 | Röhm Gmbh | Procédé amélioré de préparation de méthacrylate de méthyle et/ou d'acide méthacrylique par mélange à contre-courant réduit pendant la conversion |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1076749C (zh) * | 1998-04-24 | 2001-12-26 | 中国石油化工集团公司 | 缓和热转化——溶剂脱沥青组合工艺 |
ID29093A (id) * | 1998-10-16 | 2001-07-26 | Lanisco Holdings Ltd | Konversi mendalam yang menggabungkan demetalisasi dan konversi minyak mentah, residu atau minyak berat menjadi cairan ringan dengan senyawa-senyawa oksigenat murni atau tak murni |
CN102220166A (zh) * | 2010-04-13 | 2011-10-19 | 中国石油化工集团公司 | 一种延迟焦化方法 |
CN102220165A (zh) * | 2010-04-13 | 2011-10-19 | 中国石油化工集团公司 | 一种延迟焦化工艺 |
CN102485839B (zh) * | 2010-12-03 | 2014-11-19 | 中国石油天然气股份有限公司 | 一种橡胶油基础油原料的制备方法 |
CN103045281B (zh) * | 2011-10-17 | 2014-08-06 | 中国石油天然气股份有限公司 | 一种提高低沥青质原料中沥青质含量的方法 |
CN103044932B (zh) * | 2011-10-17 | 2015-08-19 | 中国石油天然气股份有限公司 | 用低沥青质含量的原料制备改性沥青的方法 |
CN103773446B (zh) * | 2012-10-18 | 2015-09-23 | 中国石油化工股份有限公司 | 一种重油裂化反应器和重油裂化方法 |
CN103773447B (zh) * | 2012-10-18 | 2015-09-23 | 中国石油化工股份有限公司 | 一种重油接触裂化方法和重油接触裂化装置 |
CN103059887B (zh) * | 2013-01-28 | 2014-06-25 | 天津市东盛工贸有限公司 | 卧式反应釜延迟焦化设备及其工艺 |
KR101470458B1 (ko) | 2013-03-11 | 2014-12-08 | 주식회사 시알아이 | 오일셰일로부터 중질유를 회수하는 장치 및 이를 이용한 회수방법 |
CA3044527A1 (fr) * | 2016-12-01 | 2018-06-07 | Bp Corporation North America Inc. | Procede de prediction de la puissance de solvant critique d'un flux de residu viscoreduit d'interet |
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US4239616A (en) * | 1979-07-23 | 1980-12-16 | Kerr-Mcgee Refining Corporation | Solvent deasphalting |
US4290880A (en) * | 1980-06-30 | 1981-09-22 | Kerr-Mcgee Refining Corporation | Supercritical process for producing deasphalted demetallized and deresined oils |
US4435276A (en) * | 1982-04-09 | 1984-03-06 | Toyo Engineering Corporation | Method of treating heavy oil |
GB2138840A (en) * | 1983-02-28 | 1984-10-31 | Fuji Oil Co Ltd | Thermal cracking of heavy hydrocarbon oils |
EP0166604A2 (fr) * | 1984-06-27 | 1986-01-02 | Fuji Standard Research Inc. | Procédé pour le craquage thermique d'huiles hydrocarbonées lourdes |
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JPS5655490A (en) * | 1979-10-12 | 1981-05-16 | Mitsubishi Heavy Ind Ltd | Conversion method of heavy oil to light oil |
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- 1985-05-13 JP JP60101161A patent/JPS61261391A/ja active Granted
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1986
- 1986-04-21 CN CN86102643A patent/CN86102643B/zh not_active Expired
- 1986-05-12 KR KR1019860003676A patent/KR900000861B1/ko not_active IP Right Cessation
- 1986-05-13 DD DD86290198A patent/DD251781A5/de not_active IP Right Cessation
- 1986-05-13 DE DE8686303612T patent/DE3680944D1/de not_active Expired - Fee Related
- 1986-05-13 EP EP86303612A patent/EP0202099B1/fr not_active Expired - Lifetime
- 1986-05-13 MX MX002465A patent/MX169003B/es unknown
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US4239616A (en) * | 1979-07-23 | 1980-12-16 | Kerr-Mcgee Refining Corporation | Solvent deasphalting |
US4290880A (en) * | 1980-06-30 | 1981-09-22 | Kerr-Mcgee Refining Corporation | Supercritical process for producing deasphalted demetallized and deresined oils |
US4435276A (en) * | 1982-04-09 | 1984-03-06 | Toyo Engineering Corporation | Method of treating heavy oil |
GB2138840A (en) * | 1983-02-28 | 1984-10-31 | Fuji Oil Co Ltd | Thermal cracking of heavy hydrocarbon oils |
EP0166604A2 (fr) * | 1984-06-27 | 1986-01-02 | Fuji Standard Research Inc. | Procédé pour le craquage thermique d'huiles hydrocarbonées lourdes |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0272577A1 (fr) * | 1986-12-18 | 1988-06-29 | Lummus Crest, Inc. | Traitement de la charge pour une viscoréduction sévère |
EP0274604A1 (fr) * | 1986-12-18 | 1988-07-20 | Abb Lummus Crest Inc. | Viscoréduction sévère |
EP0343371A1 (fr) * | 1988-05-26 | 1989-11-29 | Abb Lummus Crest Inc. | Viscoréduction cévère avec rècirculation |
EP0372652A1 (fr) * | 1988-12-05 | 1990-06-13 | Shell Internationale Researchmaatschappij B.V. | Procédé de conversion d'une charge lourde d'hydrocarbures |
US6610177B2 (en) * | 1998-11-04 | 2003-08-26 | Rohm And Haas Company | Apparatus and process for the high yield production of methyl methacrylate or methacrylic acid |
US6545176B1 (en) | 1998-11-04 | 2003-04-08 | Rohm And Haas Company | Apparatus and process for the high yield production of methyl methacrylate or methacrylic acid |
EP0999200A1 (fr) * | 1998-11-04 | 2000-05-10 | Rohm And Haas Company | Installation et procédé de préparation avec un rendement élevé du méthacrylate de méthyle ou de l'acide acrylique |
US20170067330A1 (en) * | 2013-09-09 | 2017-03-09 | Rahman Khaledi | Recovery From A Hydrocarbon Reservoir |
US9970282B2 (en) * | 2013-09-09 | 2018-05-15 | Exxonmobil Upstream Research Company | Recovery from a hydrocarbon reservoir |
CN112708436A (zh) * | 2019-10-25 | 2021-04-27 | 国家能源投资集团有限责任公司 | 中间相沥青制备系统和中间相沥青制备方法 |
CN112708436B (zh) * | 2019-10-25 | 2022-09-02 | 国家能源投资集团有限责任公司 | 中间相沥青制备系统和中间相沥青制备方法 |
WO2022084046A1 (fr) | 2020-10-23 | 2022-04-28 | Röhm Gmbh | Procédé amélioré de préparation de méthacrylate de méthyle et/ou d'acide méthacrylique par mélange à contre-courant réduit pendant la conversion |
CN112870753A (zh) * | 2021-01-26 | 2021-06-01 | 广东申菱环境系统股份有限公司 | 一种冷凝式油气回收装置 |
Also Published As
Publication number | Publication date |
---|---|
CN86102643B (zh) | 1988-11-09 |
JPS61261391A (ja) | 1986-11-19 |
JPH0426360B2 (fr) | 1992-05-07 |
CN86102643A (zh) | 1986-11-12 |
EP0202099B1 (fr) | 1991-08-21 |
DD251781A5 (de) | 1987-11-25 |
DE3680944D1 (de) | 1991-09-26 |
KR860009104A (ko) | 1986-12-20 |
EP0202099A3 (en) | 1988-02-03 |
KR900000861B1 (ko) | 1990-02-17 |
MX169003B (es) | 1993-06-17 |
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