CA1226236A - Hydroconversion process for hydrocarbon liquids using supercritical vapor extraction of liquid fractions - Google Patents
Hydroconversion process for hydrocarbon liquids using supercritical vapor extraction of liquid fractionsInfo
- Publication number
- CA1226236A CA1226236A CA000447902A CA447902A CA1226236A CA 1226236 A CA1226236 A CA 1226236A CA 000447902 A CA000447902 A CA 000447902A CA 447902 A CA447902 A CA 447902A CA 1226236 A CA1226236 A CA 1226236A
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- Canada
- Prior art keywords
- liquid
- fraction
- separation zone
- hydrocarbon
- solvent vapor
- 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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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0403—Solvent extraction of solutions which are liquid with a supercritical fluid
- B01D11/0407—Solvent extraction of solutions which are liquid with a supercritical fluid the supercritical fluid acting as solvent for the solute
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
Abstract
ABSTRACT
A process for high hydroconversion of heavy hydrocarbon liquid feedstocks such as petroleum residua containing at least about 50 V % material boiling above 975°F to produce lower boiling hydrocarbon liquid and gas products, wherein heavy RCR materials and metals compounds are removed in-situ from the reactor effluent liquid by solvent vapor extraction using a process-derived solvent vapor at supercritical con-ditions. In the process, the feedstock is catalytically hydroconverted at 780-a60°F temperature, and the resulting liquid fraction is contacted with a process-derived solvent vapor fraction having a normal boiling range of 250-400°F
and heated to supercritical temperature to dissolve and extract substantially all the hydrocarbon liquid fractions, and separate heavy RCR materials and the metals compounds contained therein. The resulting supercritical solvent vapor with dissolved liquid fraction is pressure-reduced and distilled to recover the needed solvent fraction and to pro-vide a hydrocarbon liquid fraction product. The hydrogena-tion step preferably uses an ebullated catalytic bed. Also, if desired, the supercritical solvent vapor extraction step can be used intermediate two hydroconversion reaction zones connected in series to product additional desired lower boiling desulfuized hydrocarbon liquid fraction products.
A process for high hydroconversion of heavy hydrocarbon liquid feedstocks such as petroleum residua containing at least about 50 V % material boiling above 975°F to produce lower boiling hydrocarbon liquid and gas products, wherein heavy RCR materials and metals compounds are removed in-situ from the reactor effluent liquid by solvent vapor extraction using a process-derived solvent vapor at supercritical con-ditions. In the process, the feedstock is catalytically hydroconverted at 780-a60°F temperature, and the resulting liquid fraction is contacted with a process-derived solvent vapor fraction having a normal boiling range of 250-400°F
and heated to supercritical temperature to dissolve and extract substantially all the hydrocarbon liquid fractions, and separate heavy RCR materials and the metals compounds contained therein. The resulting supercritical solvent vapor with dissolved liquid fraction is pressure-reduced and distilled to recover the needed solvent fraction and to pro-vide a hydrocarbon liquid fraction product. The hydrogena-tion step preferably uses an ebullated catalytic bed. Also, if desired, the supercritical solvent vapor extraction step can be used intermediate two hydroconversion reaction zones connected in series to product additional desired lower boiling desulfuized hydrocarbon liquid fraction products.
Description
lZ~iZ36 HYDROCONVERSION PROCESS FOR HYDROCARBON LIQUIDS
USING SUPER CRITICAL VAPOR EXTRACTION OF LIQUID FRACTIONS
-BACKGROUND OF THE INVENTION
-This invention pertains to a catalytic hydroconversion process for heavy hydrocarbon liquid feedstoeks to produce lower boiling hydrocarbon liquid and gas products. It per-twins particularly to such a hydroconversion process in which supereritical solvent vapor extraction is used in-situ to dissolve the reactor liquid fraction and remove Rams bottom carbon residue (RCR) and metals containing compounds to avoid their precipitation in downstream processing equipment and achieve high conversion.
In hydroconversion processes such as for petroleum nest-due feeds for producing lower boiling liquid products, it is usually necessary to remove a substantial portion of RCR-containing and metals-eontaining compounds prom the liquid products to insure sustained operations. The solvent ox-traction of hydrocarbon materials using supereritieal vapor is generally known. or example, the extraction of coal solids materials using superieritieal vapor solvents is disk closed in US. Patent 3,558,468 to Wise, but does not disk close use of super critical vapor extraction of a eatalyti-early hydroeonverted liquid fraction incorporated into a hydroconversion process. Also, the extraction of petroleum residue feedstoeks using supereritieal vapor extraction pro-seedier before hydroconversion is disclosed in US. Patent 4,354,922 to Derbyshire et at and US. Patent 4,354,928 to Alden et at. However, the present invention utilizes in-situ supereritieal solvent vapor extraction following catalytic hydroconversion reaction to avoid the undesired precipita-lion of asphaltenes and provide sustained high hydroconver-:~Z26236 soon operations on heavy hydrocarbon liquid feed stocks, par-ticularaly those containing high Rams bottom carbon residue (RCR) materials and high metals containing compounds.
SUMMARY OF INVENTION
The present invention provides a process for catalytic hydroconversion of heavy hydrocarbon liquid feed stocks such as petroleum residue in which Rams bottom carbon residue (RCR) materials and metals-containing compounds are removed by on-line super critical solvent vapor extraction of the reactor effluent liquid fraction. The process comprises feeding a hydrocarbon liquid feed stock together with hydra-gun into a reaction zone, which is maintained at 780-860F
temperature and 1000-5000 prig hydrogen partial pressure for liquid phase hydroconversion reactions to provide a hydra-converted effluent material containing a mixture of gas and liquid fractions; separating said hydrocarbon effluent material in a first separation zone into a gas fraction and a liquid fraction; passing said liquid fraction to a second separation zone maintained at a temperature above the anti-eel temperature of a solvent vapor added to said liquid in said second separation zone to dissolve and extract sub Stan-tidally all the hydrocarbon liquid fraction from the liquid and provide substantial separation of the RCR material and metals-containing compounds therein; withdrawing said nest-due along with a minor portion of high boiling residual oil from said second separation zone; withdrawing and pressure-reducing the remaining extraction vapor from said second sop-aeration zone containing super critical solvent vapor and dissolved liquid, and separating a light solvent fraction from a remaining heavy liquid fraction; recycling a portion of the light solvent vapor fraction to said second swooper-lion zone to provide a super critical solvent vapor added :~L22~ 36 therein; and withdrawing hydrocarbon liquid and gas products from the process.
This hydroconversion process can be operated in either of two modes of operation. One mode utilizes a single hydroconversion reaction stage followed by maximum extract lion of the liquid fraction and rejection of the high RCR, high metal-containing heavy slurry material, and recycle of part of the heavy oil product to the reaction zone for increased conversion. This mode is useful mainly for high hydroconversion operations on high RCR - high metal con-twining feed stocks for which there is the usual possibility of operational problems. A second mode uses hydroconversion and moderate extraction of the hydrocarbon liquid fraction in a first separation zone, and recycle of high RCR, high metals-containing heavy slurry material to the reaction zone, and passing the high quality heavy oil on to a kettle-tic hydrodesulfurization reactor for hydrocracking and con-version to desired lighted hydrocarbon products. Alterna-lively, at least a portion of the super critical solvent vapor needed for liquid extraction in the second separation zone can be produced in the first separation zone and drained into the second separation zone and vaporized therein.
This process is useful for hydroconversion of hydrcar-bun liquid feed stocks, including petroleum whole crudest at-mospheric residue and vacuum residue materials, bitumen de-roved from tar sands and shale oil. It is an advantage of the process that the high RCR and metals-containing compounds are effectively removed from the reaction zone hydrocarbon effluent liquid fraction so as to permit achieving high hydroconversion of the feed stocks to produce lower boiling hydrocarbon liquid and gas products.
~%26Z36 BRIEF DESCRIPTION OF DRAWINGS
, FIG. 1 is a schematic diagram of a hydroconversion pro-cuss for hydrocarbon liquids using super critical vapor high extraction of the liquid fraction in accordance with this invention.
FIG. 2 shows another embodiment of the invention using a two-stage hydroconversionreaction zone and an alternative super critical vapor high extraction step located between the two stages.
FIG. 3 shows a petroleum hydroconversion process having two stages of catalytic reaction with the super critical Ye-pro extraction step located intermediate the two reaction stages.
DESCRIPTION OF INVENTION
.
In the present invention, a process for hydroconversion of heavy hydrocarbon feed stocks such as petroleum residue using super critical vapor extraction of a liquid fraction derived from a catalytic hydroconversion of the feed stock is described by reference to FIG. 1 As shown, a petroleum residue feed stock such as heavy Arabian vacuum resin or Bushwhacker vacuum bottoms, is provided at 10, pressurized at 12 and passed through preheater 14 for heating to at least about 500F. The heated feed stream at 15 is introduced into up flow ebullated bed catalytic reactor 20. Hydrogen at 13 is heated at 16, and also introduced at 17 into reactor 20.
The reactor 20 contains an inlet flow distributor and gala-lust support grid 21, so that the feed liquid and gas pass-in upwardly through the reactor 20 will expand the catalyst bed 22 by at least about 10% and usually up to about 50~
over its settled height, and place the catalyst in random motion in the liquid. This reactor is -typical of that desk cried in So Patent No. Rev 25,770, wherein a liquid phase reaction occurs in the presence of a reactant gas and a part-~Z'~6236 curate catalyst such that the catalyst bed is expanded.
The catalyst particles in bed 22 usually hove a rota-lively narrow size range for uniform bed expansion under controlled liquid and gas flow conditions. While the useful catalyst size range is between about 6 and 100 mesh (US.
Sieve Series) with an up flow liquid velocity between about 1.5 and 15 cubic feet per minute per square foot of reactor cross section area, the catalyst size is preferably particles of 6 - 60 mesh size including extradites of approximately 0.010 - 0.130 inch diameter. I also contemplate using a once-through type hydroconversion operation using fine sized catalyst in the 80-270 mesh size range (0.002- 0.007 inch) added with the feed, and with a liquid space velocity in the order of 0.1-2.5 volume of fresh feed per hour per volume of reactor (Vf/hr/Vr). In the reactor, the density of the cat-alyst particles, the liquid upward flow rate, and the lifting effect of the up flowing hydrogen gas are important factors in the expansion and operation of the catalyst bed. By control of the catalyst particle size and density and the liquid and gas velocities and taking into account the viscosity of the liquid at the operating conditions, the catalyst bed 22 is expanded to have an upper level or interface in the liquid as indicated at aye. The catalyst bed expansion should be at least about 10% and seldom more than 100% of the bed settled or static level.
Recycle of reactor liquid from above the solids inter-face aye to below the flow distributor grid 21 is usually needed to establish a sufficient up flow liquid velocity to maintain the catalyst in random motion in the liquid and to facilitate an effective reaction. Such liquid recycle is preferably accomplished by the use of a central down comer conduit 18 which extends to a recycle pump 19 located below ~2~6~36 the flow distributor 21, to assure a positive and controlled upward movement of the liquid through the catalyst bed 22.
The recycle of liquid through internal conduit 18 has some mechanical advantages and tends to reduce the external high pressure piping connections needed in a hydroconversion reactor, however, liquid recycle upwardly through the react ion can be established by a recycle conduit and pump located external to the reactor.
The hydroconversion reaction in bed 22 is greatly fact-ligated by use of an effective catalyst. The catalysts use-fur in this invention are typical hydrogenation catalysts containing activation metals selected from the group con-sitting of cobalt, molybdenum, nickel and tungsten and mix-lures thereof, deposited on a support material selected from the group of alumina, silica, and combinations thereof. If a fine-size catalyst is used, it can be effectively intro-duped to the reactor at connection 24 by being added to the feed in the desired concentration, as in a slurry. Catalyst may also be periodically added directly into the reactor 20 through suitable inlet connection means 25 at a rate between about 0.1 and 2.0 lobs catalyst/barrel feed, and used gala-lust is withdrawn through suitable withdrawal means 26.
Operability of the ebullated catalyst bed reactor system to assure good contact and uniform (isothermal) temperature therein depends not only on the random motion of the relate-very small catalyst in the liquid environment resulting from the buoyant effect of the up flowing liquid and gas, but also requires the proper reaction conditions With improper no-action conditions insufficient hydroconversion is achieved, which results in a non-uniform distribution of liquid flow and operational upsets, usually resulting in excessive coke deposits on the catalyst. Different feed stocks are found to lZZ6Z36 have more or less asphaltene precursors which tend to agree-Yale the operability of the reactor system including the recycle pump and piping due to the plating out of tarry deposits. While these deposits can usually be washed off by lighter delineate materials, the catalyst in the reactor bed may become completely coked up, and this may lead to premature shut down of the process unless undesired precipitation of such asphaltenes materials is avoided.
For the heavy petroleum residue feed stocks of this invention, i.e. those containing about 10-22 W % RCR-con-twining materials and total metals at least about 0.02 W I, the operating conditions used in the reactor 20 are within the broad ranges of 780-860F temperature, 1000-5000 prig, hydrogen partial pressure, space velocity of 0.1-2.5 Vf/hr/Vr (volume feed per hour per volume of reactor), and a recycle ratio of vacuum bottoms material to feed stock within a range of 0.4-0.7. Preferred conditions are 790-850F them-portray, 1200-3000 prig, hydrogen partial pressure, and space velocity of 0.20-1.5 Vf/hr/Vr. Usually more preferred conditions are 800-840F temperature and 1250-2800 prig hydrogen partial pressure. The feed stock hydroconversion achieved is at least about 75 V % for once-through single stave type operations and preferably 90-98 V % for single or two-stage operation.
In the catalyst reactor 20, a vapor space 23 exists above the liquid level aye and an overhead stream containing both liquid and gas fractions is removed at 27, and passed to hot phase separator 28. The resulting gaseous portion 29 is principally hydrogen, which is cooled at heat exchanger 30, and passed to gas/liquid phase separator 32. The no-suiting gaseous fraction 31 is passed to gas purification step 34. The recovered hydrogen stream at 35 can be no-warmed at heat exchanger 30 and is recycled by compressor aye reheated at heater 16, and is passed as stream 17 into the bottom of reactor 20, along with make-up hydrogen at 35b ~Z26236 as needed. Also from separator 32, a liquid fraction 33 is withdrawn and passed to fractionator 50 as described further herein below.
From the first separator 28, liquid fraction 36 is with-drawn, cooled by 20-80F at heat exchanger 37 and introduced into second separator 38, which is maintained at 750-780F
temperature and at a pressure about 50-150psig below that in separator 28 so as to avoid any appreciable thermal cracking of the liquid. In second separator 38, a super critical sol-vent vapor fraction at 40 having a temperature about 15-50F
below the liquid temperature existing in the separator is added to the liquid therein to effectively dissolve and highly extract the liquid. A hydrocarbon fraction having normal boiling range of 250-450F provides a good supercri-tidal solvent vapor for extracting the liquid in separator-extractor 38. The weight ratio of the super critical solvent vapor added to the liquid in separator 38 should be within a range of about 1-5, and preferably is 2-4. The separator 38 will preferably have a smaller diameter at its lower end aye to facilitate withdrawal of stream 39 therefrom containing substantially all the RCR and metals-containing materials.
The extracted liquid fraction containing the supercriti-eel solvent is removed in substantially vapor form at 41, pressure-reduced at aye and flashed in flash vessel 42 so as to separate gases and oil vapors from the remaining heavy oil fraction. The pressure in flash vessel 42 should usually be less than about 70% of that in separator 38, and pro-fireball 30-60% of that pressure. From vessel 42, the vapor portion at 43 is usually condensed at cooler aye and a portion 43b recycled as super critical solvent vapor to separator 38, and the remainder passed to fractionator 50.
Liquid fraction 44 is preferably further pressure-reduced at ~L2Z~236 45 and passed to second flash vessel 46~ Overhead vapor 47 from flash vessel 46 is usually condensed at cooler aye, and a portion 47b is also recycled as solvent vapor, and the remainder is passed to fractionator 50. Liquid fraction I
is withdrawn and usually passed to vacuum distillation at 58.
Alternatively, the 250-450F oil fraction needed for the critical solvent vapor for extraction in separator 38 can be separated from the light oil fractions in fractionation tower 50. From fractionator 50, a gas product is removed at 51 and an oil product fraction removed at 52. A portion 53 needed for providing the critical solvent and preferably having normal boiling range of 300-360F fan be removed, pressurized at 54, heated at 55 to the desired super critical temperature and recycled to separator 38 as super critical vapor stream 40. If needed, some make-up solvent fraction can be added at aye, such as during process start-up con-dictions. From separator-extractor 38, the heavy oil material at 39 containing substantially all the RCR and metals-containing compounds is withdrawn for discard. Also, from fractionator 50, bottoms stream 56 is withdrawn as pro-duct. From vacuum distillation unit 58, a light hydrocarbon liquid product fraction is removed at 57 and a vacuum both toys material is withdrawn at 59. A portion aye of the vacuum bottoms material is preferably recycled to reactor 20 for further conversion to lower boiling hydrocarbon pro-ducts. The volume ratio of the recycled vacuum bottoms material aye to feed stream 10 should be between about 0.4 and about 0.7.
An alternative embodiment of the invention is shown in FIG. 2, in which the super critical solvent vapor fraction used for extraction is at least partly formed in a first hot separator and drained into a second separator-extractor unit, which is maintained at about 100F higher temperature ~Z2~%36 and 200-600 prig lower pressure than the first separator.
The increased temperature needed in the second separator is maintained by adding external heat as required.
As shown in FIG. 2, recycled hydrogen stream 13 can be added to the feed upstream of heater 14. Otherwise, reactor 20 is operated similarly as for the FIG. 1 embodiment. Folk lowing catalytic hydroconversion reactions on the feed stock in reactor 20 at 780-840F temperature and 1800-3000 prig hydrogen partial pressure and space velocity of 0.4-2.5 Vf/hr/Vr, the reactor effluent stream 27 is cooled at cooler aye and passed into first phase separator 60, which is us-ally maintained at 650-700F temperature. The separator overhead vapor stream 61 consists mainly of hydrogen and other gases as well as light oil vapors, and is passed with additional hydrogen at 73 to a second stage reactor 74 as described below. Liquid fraction 62 from first separator 60 flows into second separator 64, which is maintained at 1500-2500 prig pressure and 750-800F temperature, usually by using external heating means such as electric heating coils attached to the separator. The liquid fractions having critical temperatures between 650-800F vaporizes in the second separator 64 to provide super critical solvent vapor therein at the high pressure. This super critical sol-vent vapor dissolves and highly extracts most of the liquid material in the second separator, except for a heavy liquid slurry material which contains substantially all the solids, such as nickel- and vanadium-containing compounds, and a substantial part of the high RCR-containing material, which is withdrawn at 65. This heavy slurry material is usually discarded from the process, but if desired, a portion can be recycled to the reactor pa dry further hydroconversion.
The extracted hydrocarbon liquid and super critical sol-I I
vent vapor in separator 64 is withdrawn in vapor form at Andy flashed to lower pressure in flash vessel 66 to separate the oil vapors and dissolved gases from the heavy oil free-lions. Vapor fraction 67 is removed from flash vessel 66 and passed to a second catalytic reactor 74. If needed to supplement the super critical solvent vapor provided within second separator 64, a vapor portion 68 can be condensed at aye, pressurized at 69, reheated at aye and recycled to the separator 64 as super critical solvent vapor for producing further extraction therein.
From the flash step 66, the liquid fraction 70 is with-drawn and repressurized at 71 and introduced as stream 72 along with supplemental hydrogen 73 into second ebullated bed catalytic reactor 74, which is very similar in operation to first stage reactor 200 Suitable reaction conditions in the second stage reactor 74 are 780-820F temperature, 1800-2500 prig hydrogen partial pressure, and 0.4-2.0 Vf/hr/Vr space velocity.
From reactor 74, the effluent is passed to phase swooper-lion and fractionation steps and processed similarly as for FIG. 1. Specifically, reactor effluent stream 75 is passed to phase separator 76, from which the resulting vapor free-lion 77 is cooled at 78 and passed to phase separator 80, from which vapor portion 81 is passed to hydrogen purifica-lion system 34. Also from separator 80, liquid fraction 82 is withdrawn, pressure-reduced at 83 and passed to free-shunter 84 along with liquid fraction 79 withdrawn from separator 76.
From fractionator 84, a light hydrocarbon gas product is withdrawn at 85, a middle boiling range distillate liquid product stream at 86, and a bottom liquid product withdrawn at 87. If desired, a portion of the heavy oil 87 from free-~2;~623~
shunter 84 is passed to vacuum distillation at 88 for fur-then removal of light fractions. Also, from the flash step 66, a portion aye of the heavy oil fraction 70, can be passed to vacuum distillation at 88. From vacuum distill-lion step 88, a vacuum gas oil stream is removed at 89, and can be combined with fractionator bottoms liquid stream 87.
A vacuum bottoms material is withdrawn at aye, and a portion 89b can be recycled to reactor 20 for further conversion to lower boiling liquid products.
Thus, the present invention can be advantageously used in a hydrocarbon liquid hydroconversion process having two separate stages of catalytic reaction, wherein the supercri-tidal vapor extraction step is located intermediate the two hydroconversion reaction stages to remove substantially all the metal containing compounds and a substantial portion of the high boiling RCR containing residue from the first stage effluent before it is passed on to the second stage reactor for further hydroconversion, as shown in FIG. 2. In such a two-stage hydroconversion process, the feed to the second stage reactor is thus substantially free of RCR-containing asphaltenes and metals-containing compounds. This process arrangement improves catalyst life in the second stage react ion and also improves product quality. Selective recycle of heavy oil from vacuum distillation to the first stage react ion can also be used to improve resin hydroconversion and liquid product yields.
The present invention can also be advantageously used in a two stage reaction process for heavy hydrocarbon liquids in which the second stage is a fixed bed catalytic reactor, as generally shown in FIG. 3. Referring to FIG. 3, the first stage reactor 2Q is operated similarly to that for FIG. 1 and ma be either catalytic or non-catalytic type.
~ZZ6Z36 From reactor 20, the reactor effluent material 27 flows into the first separator 28, which is usually maintained at approximately 800-850F temperature and 15CC-4000 prig hydrogen partial pressure. From the first separator 28, overhead stream 29 consisting of hydrogen and other light gases and oil vapors is cooled at 30 and passed to the second separator 32. The slurry liquid fraction 36 from the first separator 28 is cooled and flows into the second separator 38, which is maintained at 750-820F temperature and about 1200-3800 prig pressure. The liquid from the first separator usually needs some intermediate cooling at 37 to maintain the second separator 38 at the desired 700-78CF temperature, so as to prevent thermal cracking of the liquid therein.
The super critical solvent vapor extraction of the slurry liquid occurs in second separator 38. A process-derived liquid fraction normally boiling between about 300-360F
provides a good super critical solvent extraction fluid at the preferred 730-780F temperature of the second separator.
The super critical oil vapor fraction along with the ox-treated material in vapor is withdrawn at 41, pressure-reduced to separate out vapor fractions, then condensed, pressurized and heated to the desired super critical them-portray to form a super critical solvent vapor, which is introduced into separator-extractor 38 to dissolve and extract part of the hydrocarbon liquid therein, including part of the 975F-~ fraction in the second separator.
Specifically, this super critical vapor together with dissolved liquid is removed as vapor stream 41 and flashed at suitable lower pressure conditions at flash vessel 42 to precipitate out heavy oils, including some resin from the oil vapor. The oil vapor portion 43b is cooled and con-~LZ26~36 dented to liquid form at 43c, then pressurized at 54, heated at 55 and recycled to the second separator 38 to provide the super critical solvent vapor needed for liquid extraction therein. The heavy liquid stream 39 discharged from second separator 38 consists of metals-containing compounds and some remaining 975F+ liquid fraction. This heavy oil stream aye is preferably recycled through heater 14 to react ion 20 for further hydroconversion.
From the flash step 42, the heavy oil fraction 44 along with vapor 43 and liquid stream 33 are passed together with additional hydrogen aye to a second reactor 90 for further catalytic desulfurization processing to remove sulfur and nitrogen compounds. Reactor 90 is usually a fixed catalyst bed type reactor. The catalyst used in reactor 90 can be any known hydrodesulfurization catalyst such as cobalt-molybdenum on alumina support. The reaction conditions in reactor 90 are maintained at 740-820F temperature and 1500-2800 prig hydrogen partial pressure.
From reactor 90 the effluent 91 is cooled at cooler 92 and passed to phase separator 94, from which the resulting vapor portion 93 is passed to hydrogen purification system 96. Liquid fraction 95 is withdrawn, and passed along with recycled hydrogen 99 from purification system 96 to hydra-cracker 100 for cracking of heavy fractions into lighter hydrocarbon fractions. Useful hydrocracking conditions are 780-820F temperature and 1800~2800 prig pressure. From hydrocracker 100, the effluent 101 is passed to fractionator 102, from which hydrocarbon gas products are withdrawn at 103, a middle boiling range distillate product stream at 104, and a bottom liquid product is withdrawn at 105. Be-cause the 975F~ fractions are substantially eliminated in the hydrocracking step 100, a vacuum distillation step is ~Z2~;Z36 usually not required.
If desired, a portion aye of the heavy oil from flash step 42 can be recycled to the first stage reactor 20 to improve the resin conversion and liquid products yields.
Also, a portion of bottoms material withdrawn at 105 can be preferably recycled to the reactor 90 for increased hydra-conversion such as to at least about go V % and preferably to 92-98 V % to material boiling below 975~F.
An advantage of the intermediate super critical extract lion step for a petroleum hydroconversion process is that very effective RCR and metals removal is accomplished in-situ in the second separator-extractor. Thus, because the feed to the second stage reactor is low in RCR and metals, the catalyst activity and product quality in the second stage reactor is substantially improved.
This invention will be more fully described by the following examples of petroleum hydroconversion operations, which should not be construed as limiting in scope.
A petroleum residuum feed stock material containing about 20 W % RCR, 0.075 W % total metals is fed together with hydrogen to a catalytic hydroconversion process having an ebullated catalyst bed reactor. The resulting hydrogenated effluent material is passed from the reactor to a phase separator, from which a liquid fraction is withdrawn, cooled and passed to a second separator-extractor. A hydrocarbon solvent vapor fraction at super critical conditions is added to the liquid in the second separator to dissolve and extract the hydrocarbon liquid fraction therein and to pro-vise effective separation ox heavy asphaltenes and metals-containing compounds. The resulting extracted vapor is withdrawn, flashed at lower pressure to recover the desired ~!LZ~236 solvent fraction for recycle to the extraction step, and the resulting liquid fraction withdrawn and distilled to provide desired liquid products.
Results of this super critical vapor extraction operation are presented in Table 1.
TABLE l Feed stock Bushwhacker Vacuum Bottoms Reaction Conditions Temperature, OF 830 Hydrogen Partial Pressure, swig Liquid Space Velocity, Vf/hr/Vr 2.0 Catalyst Age, bbls/lb Conversion of 975F~ Material, V ~85 LIQUID EXTRACTION CONDITIONS
Liquid Temperature, OF 760 Liquid Pressure, prig 1800 Solvent Temperature, OF 740 Solvent Normal Boiling Range, F300-400 Weight Ratio Solvent Added to Liquid Fraction 3:1 Residence Time in Second Separator, Min. 2 RCR Content of Second Separator Effluent, W I
RCR Content of Second Separator Bottoms, W 50 Metals Content of Second Separator Effluent, Pam <50 Metals Content of Second Separator Bottoms, Pam 3000 Based on the above results it is noted that substantial removal of RCR and metals-containing compounds occurs following extraction with the super critical vapor in the second separator, so that the vapor effluent stream leaving the separator contains less than about 2 W % RCR material and less than 50 Pam metals content. The separator bottoms streams contains substantially all the RCR and metals in the reactor effluent stream.
A petroleum vacuum residuum material containing about 20 W RCR material and 0.075 W total metals is fed together with hydrogen into the first stage ebullated gala-lust hod reactor of a two-stage catalytic hydroconversion process. The resulting hydrogenated effluent materials is ~Z2~23~
passed from the reactor to a hot phase separator, from which a liquid fraction is withdrawn, cooled and passed to a second separator-extracter. A hydrocarbon solvent vapor fraction at super critical conditions is added to the liquid in the second separator to dissolve and extract the hydra-carbon liquid fraction therein and to allow the separation of heavy asphaltenes and metals-containing compounds. The resulting extracted vapor is withdrawn, flashed at lower pressure to recover the desired solvent fraction for recycle to the extraction step. The resulting liquid fraction is withdrawn and combined with the vapor fraction from the hot separator and passed iota second catalytic reactor for further hydroconversion reactions followed by phase swooper-lion and distillation steps.
Results of this super critical extraction operations are provided in Table 2.
FeedstockBachaquero Vacuum Bottoms First Stage Reaction Conditions Temperature, OF 830 Hydrogen Partial Pressure, prig 2000 Liquid Space Velocity, Vf/hr/Vr 2.0 Catalyst Age, bbls/lb.4.0 LIQUID EXTRACTION CONDITIONS
Liquid Temperature, F760 Liquid Pressure, swig Solvent Temperature, F740 Solvent Normal Broiling Range, F300-~00 Weight Ratio Solvent Added to Liquid Fraction 2:1 Residence Time in Second Separator, Min. 2 RCR Content of Second Separator Effluent, W % I
RCR Content of Second Separator Bottoms, W % 35 Metals Content of Second Separator Effluent, Pam 80 Metals Content of Second Separator Bottoms, Pam 2000 Second Stage Reaction Conditions Temperature, OF 800 Hydrogen Partial Pressure, swig Liquid Space Velocity, V~/hr/Vr 2.5 Catalyst Age, bbls/lb. 1.5 Conversion of 975F+ Material, V % 97 Based on the above results, it is noted that substantial removal of RCR and metals-containing compounds occurs in the second separator, so that the vapor effluent stream leaving the separator contains less than about 8.0 % RCR materials less than about 80 Pam metals. The separator bottoms streams contains substantially all the RCR and metals in the reactor effluent stream.
Although this invention has been described broadly and in terms of certain preferred embodiments, it will be under-stood that modifications and variations to the process can remade within the spirit and scope of the invention, which is defined by the following claims.
USING SUPER CRITICAL VAPOR EXTRACTION OF LIQUID FRACTIONS
-BACKGROUND OF THE INVENTION
-This invention pertains to a catalytic hydroconversion process for heavy hydrocarbon liquid feedstoeks to produce lower boiling hydrocarbon liquid and gas products. It per-twins particularly to such a hydroconversion process in which supereritical solvent vapor extraction is used in-situ to dissolve the reactor liquid fraction and remove Rams bottom carbon residue (RCR) and metals containing compounds to avoid their precipitation in downstream processing equipment and achieve high conversion.
In hydroconversion processes such as for petroleum nest-due feeds for producing lower boiling liquid products, it is usually necessary to remove a substantial portion of RCR-containing and metals-eontaining compounds prom the liquid products to insure sustained operations. The solvent ox-traction of hydrocarbon materials using supereritieal vapor is generally known. or example, the extraction of coal solids materials using superieritieal vapor solvents is disk closed in US. Patent 3,558,468 to Wise, but does not disk close use of super critical vapor extraction of a eatalyti-early hydroeonverted liquid fraction incorporated into a hydroconversion process. Also, the extraction of petroleum residue feedstoeks using supereritieal vapor extraction pro-seedier before hydroconversion is disclosed in US. Patent 4,354,922 to Derbyshire et at and US. Patent 4,354,928 to Alden et at. However, the present invention utilizes in-situ supereritieal solvent vapor extraction following catalytic hydroconversion reaction to avoid the undesired precipita-lion of asphaltenes and provide sustained high hydroconver-:~Z26236 soon operations on heavy hydrocarbon liquid feed stocks, par-ticularaly those containing high Rams bottom carbon residue (RCR) materials and high metals containing compounds.
SUMMARY OF INVENTION
The present invention provides a process for catalytic hydroconversion of heavy hydrocarbon liquid feed stocks such as petroleum residue in which Rams bottom carbon residue (RCR) materials and metals-containing compounds are removed by on-line super critical solvent vapor extraction of the reactor effluent liquid fraction. The process comprises feeding a hydrocarbon liquid feed stock together with hydra-gun into a reaction zone, which is maintained at 780-860F
temperature and 1000-5000 prig hydrogen partial pressure for liquid phase hydroconversion reactions to provide a hydra-converted effluent material containing a mixture of gas and liquid fractions; separating said hydrocarbon effluent material in a first separation zone into a gas fraction and a liquid fraction; passing said liquid fraction to a second separation zone maintained at a temperature above the anti-eel temperature of a solvent vapor added to said liquid in said second separation zone to dissolve and extract sub Stan-tidally all the hydrocarbon liquid fraction from the liquid and provide substantial separation of the RCR material and metals-containing compounds therein; withdrawing said nest-due along with a minor portion of high boiling residual oil from said second separation zone; withdrawing and pressure-reducing the remaining extraction vapor from said second sop-aeration zone containing super critical solvent vapor and dissolved liquid, and separating a light solvent fraction from a remaining heavy liquid fraction; recycling a portion of the light solvent vapor fraction to said second swooper-lion zone to provide a super critical solvent vapor added :~L22~ 36 therein; and withdrawing hydrocarbon liquid and gas products from the process.
This hydroconversion process can be operated in either of two modes of operation. One mode utilizes a single hydroconversion reaction stage followed by maximum extract lion of the liquid fraction and rejection of the high RCR, high metal-containing heavy slurry material, and recycle of part of the heavy oil product to the reaction zone for increased conversion. This mode is useful mainly for high hydroconversion operations on high RCR - high metal con-twining feed stocks for which there is the usual possibility of operational problems. A second mode uses hydroconversion and moderate extraction of the hydrocarbon liquid fraction in a first separation zone, and recycle of high RCR, high metals-containing heavy slurry material to the reaction zone, and passing the high quality heavy oil on to a kettle-tic hydrodesulfurization reactor for hydrocracking and con-version to desired lighted hydrocarbon products. Alterna-lively, at least a portion of the super critical solvent vapor needed for liquid extraction in the second separation zone can be produced in the first separation zone and drained into the second separation zone and vaporized therein.
This process is useful for hydroconversion of hydrcar-bun liquid feed stocks, including petroleum whole crudest at-mospheric residue and vacuum residue materials, bitumen de-roved from tar sands and shale oil. It is an advantage of the process that the high RCR and metals-containing compounds are effectively removed from the reaction zone hydrocarbon effluent liquid fraction so as to permit achieving high hydroconversion of the feed stocks to produce lower boiling hydrocarbon liquid and gas products.
~%26Z36 BRIEF DESCRIPTION OF DRAWINGS
, FIG. 1 is a schematic diagram of a hydroconversion pro-cuss for hydrocarbon liquids using super critical vapor high extraction of the liquid fraction in accordance with this invention.
FIG. 2 shows another embodiment of the invention using a two-stage hydroconversionreaction zone and an alternative super critical vapor high extraction step located between the two stages.
FIG. 3 shows a petroleum hydroconversion process having two stages of catalytic reaction with the super critical Ye-pro extraction step located intermediate the two reaction stages.
DESCRIPTION OF INVENTION
.
In the present invention, a process for hydroconversion of heavy hydrocarbon feed stocks such as petroleum residue using super critical vapor extraction of a liquid fraction derived from a catalytic hydroconversion of the feed stock is described by reference to FIG. 1 As shown, a petroleum residue feed stock such as heavy Arabian vacuum resin or Bushwhacker vacuum bottoms, is provided at 10, pressurized at 12 and passed through preheater 14 for heating to at least about 500F. The heated feed stream at 15 is introduced into up flow ebullated bed catalytic reactor 20. Hydrogen at 13 is heated at 16, and also introduced at 17 into reactor 20.
The reactor 20 contains an inlet flow distributor and gala-lust support grid 21, so that the feed liquid and gas pass-in upwardly through the reactor 20 will expand the catalyst bed 22 by at least about 10% and usually up to about 50~
over its settled height, and place the catalyst in random motion in the liquid. This reactor is -typical of that desk cried in So Patent No. Rev 25,770, wherein a liquid phase reaction occurs in the presence of a reactant gas and a part-~Z'~6236 curate catalyst such that the catalyst bed is expanded.
The catalyst particles in bed 22 usually hove a rota-lively narrow size range for uniform bed expansion under controlled liquid and gas flow conditions. While the useful catalyst size range is between about 6 and 100 mesh (US.
Sieve Series) with an up flow liquid velocity between about 1.5 and 15 cubic feet per minute per square foot of reactor cross section area, the catalyst size is preferably particles of 6 - 60 mesh size including extradites of approximately 0.010 - 0.130 inch diameter. I also contemplate using a once-through type hydroconversion operation using fine sized catalyst in the 80-270 mesh size range (0.002- 0.007 inch) added with the feed, and with a liquid space velocity in the order of 0.1-2.5 volume of fresh feed per hour per volume of reactor (Vf/hr/Vr). In the reactor, the density of the cat-alyst particles, the liquid upward flow rate, and the lifting effect of the up flowing hydrogen gas are important factors in the expansion and operation of the catalyst bed. By control of the catalyst particle size and density and the liquid and gas velocities and taking into account the viscosity of the liquid at the operating conditions, the catalyst bed 22 is expanded to have an upper level or interface in the liquid as indicated at aye. The catalyst bed expansion should be at least about 10% and seldom more than 100% of the bed settled or static level.
Recycle of reactor liquid from above the solids inter-face aye to below the flow distributor grid 21 is usually needed to establish a sufficient up flow liquid velocity to maintain the catalyst in random motion in the liquid and to facilitate an effective reaction. Such liquid recycle is preferably accomplished by the use of a central down comer conduit 18 which extends to a recycle pump 19 located below ~2~6~36 the flow distributor 21, to assure a positive and controlled upward movement of the liquid through the catalyst bed 22.
The recycle of liquid through internal conduit 18 has some mechanical advantages and tends to reduce the external high pressure piping connections needed in a hydroconversion reactor, however, liquid recycle upwardly through the react ion can be established by a recycle conduit and pump located external to the reactor.
The hydroconversion reaction in bed 22 is greatly fact-ligated by use of an effective catalyst. The catalysts use-fur in this invention are typical hydrogenation catalysts containing activation metals selected from the group con-sitting of cobalt, molybdenum, nickel and tungsten and mix-lures thereof, deposited on a support material selected from the group of alumina, silica, and combinations thereof. If a fine-size catalyst is used, it can be effectively intro-duped to the reactor at connection 24 by being added to the feed in the desired concentration, as in a slurry. Catalyst may also be periodically added directly into the reactor 20 through suitable inlet connection means 25 at a rate between about 0.1 and 2.0 lobs catalyst/barrel feed, and used gala-lust is withdrawn through suitable withdrawal means 26.
Operability of the ebullated catalyst bed reactor system to assure good contact and uniform (isothermal) temperature therein depends not only on the random motion of the relate-very small catalyst in the liquid environment resulting from the buoyant effect of the up flowing liquid and gas, but also requires the proper reaction conditions With improper no-action conditions insufficient hydroconversion is achieved, which results in a non-uniform distribution of liquid flow and operational upsets, usually resulting in excessive coke deposits on the catalyst. Different feed stocks are found to lZZ6Z36 have more or less asphaltene precursors which tend to agree-Yale the operability of the reactor system including the recycle pump and piping due to the plating out of tarry deposits. While these deposits can usually be washed off by lighter delineate materials, the catalyst in the reactor bed may become completely coked up, and this may lead to premature shut down of the process unless undesired precipitation of such asphaltenes materials is avoided.
For the heavy petroleum residue feed stocks of this invention, i.e. those containing about 10-22 W % RCR-con-twining materials and total metals at least about 0.02 W I, the operating conditions used in the reactor 20 are within the broad ranges of 780-860F temperature, 1000-5000 prig, hydrogen partial pressure, space velocity of 0.1-2.5 Vf/hr/Vr (volume feed per hour per volume of reactor), and a recycle ratio of vacuum bottoms material to feed stock within a range of 0.4-0.7. Preferred conditions are 790-850F them-portray, 1200-3000 prig, hydrogen partial pressure, and space velocity of 0.20-1.5 Vf/hr/Vr. Usually more preferred conditions are 800-840F temperature and 1250-2800 prig hydrogen partial pressure. The feed stock hydroconversion achieved is at least about 75 V % for once-through single stave type operations and preferably 90-98 V % for single or two-stage operation.
In the catalyst reactor 20, a vapor space 23 exists above the liquid level aye and an overhead stream containing both liquid and gas fractions is removed at 27, and passed to hot phase separator 28. The resulting gaseous portion 29 is principally hydrogen, which is cooled at heat exchanger 30, and passed to gas/liquid phase separator 32. The no-suiting gaseous fraction 31 is passed to gas purification step 34. The recovered hydrogen stream at 35 can be no-warmed at heat exchanger 30 and is recycled by compressor aye reheated at heater 16, and is passed as stream 17 into the bottom of reactor 20, along with make-up hydrogen at 35b ~Z26236 as needed. Also from separator 32, a liquid fraction 33 is withdrawn and passed to fractionator 50 as described further herein below.
From the first separator 28, liquid fraction 36 is with-drawn, cooled by 20-80F at heat exchanger 37 and introduced into second separator 38, which is maintained at 750-780F
temperature and at a pressure about 50-150psig below that in separator 28 so as to avoid any appreciable thermal cracking of the liquid. In second separator 38, a super critical sol-vent vapor fraction at 40 having a temperature about 15-50F
below the liquid temperature existing in the separator is added to the liquid therein to effectively dissolve and highly extract the liquid. A hydrocarbon fraction having normal boiling range of 250-450F provides a good supercri-tidal solvent vapor for extracting the liquid in separator-extractor 38. The weight ratio of the super critical solvent vapor added to the liquid in separator 38 should be within a range of about 1-5, and preferably is 2-4. The separator 38 will preferably have a smaller diameter at its lower end aye to facilitate withdrawal of stream 39 therefrom containing substantially all the RCR and metals-containing materials.
The extracted liquid fraction containing the supercriti-eel solvent is removed in substantially vapor form at 41, pressure-reduced at aye and flashed in flash vessel 42 so as to separate gases and oil vapors from the remaining heavy oil fraction. The pressure in flash vessel 42 should usually be less than about 70% of that in separator 38, and pro-fireball 30-60% of that pressure. From vessel 42, the vapor portion at 43 is usually condensed at cooler aye and a portion 43b recycled as super critical solvent vapor to separator 38, and the remainder passed to fractionator 50.
Liquid fraction 44 is preferably further pressure-reduced at ~L2Z~236 45 and passed to second flash vessel 46~ Overhead vapor 47 from flash vessel 46 is usually condensed at cooler aye, and a portion 47b is also recycled as solvent vapor, and the remainder is passed to fractionator 50. Liquid fraction I
is withdrawn and usually passed to vacuum distillation at 58.
Alternatively, the 250-450F oil fraction needed for the critical solvent vapor for extraction in separator 38 can be separated from the light oil fractions in fractionation tower 50. From fractionator 50, a gas product is removed at 51 and an oil product fraction removed at 52. A portion 53 needed for providing the critical solvent and preferably having normal boiling range of 300-360F fan be removed, pressurized at 54, heated at 55 to the desired super critical temperature and recycled to separator 38 as super critical vapor stream 40. If needed, some make-up solvent fraction can be added at aye, such as during process start-up con-dictions. From separator-extractor 38, the heavy oil material at 39 containing substantially all the RCR and metals-containing compounds is withdrawn for discard. Also, from fractionator 50, bottoms stream 56 is withdrawn as pro-duct. From vacuum distillation unit 58, a light hydrocarbon liquid product fraction is removed at 57 and a vacuum both toys material is withdrawn at 59. A portion aye of the vacuum bottoms material is preferably recycled to reactor 20 for further conversion to lower boiling hydrocarbon pro-ducts. The volume ratio of the recycled vacuum bottoms material aye to feed stream 10 should be between about 0.4 and about 0.7.
An alternative embodiment of the invention is shown in FIG. 2, in which the super critical solvent vapor fraction used for extraction is at least partly formed in a first hot separator and drained into a second separator-extractor unit, which is maintained at about 100F higher temperature ~Z2~%36 and 200-600 prig lower pressure than the first separator.
The increased temperature needed in the second separator is maintained by adding external heat as required.
As shown in FIG. 2, recycled hydrogen stream 13 can be added to the feed upstream of heater 14. Otherwise, reactor 20 is operated similarly as for the FIG. 1 embodiment. Folk lowing catalytic hydroconversion reactions on the feed stock in reactor 20 at 780-840F temperature and 1800-3000 prig hydrogen partial pressure and space velocity of 0.4-2.5 Vf/hr/Vr, the reactor effluent stream 27 is cooled at cooler aye and passed into first phase separator 60, which is us-ally maintained at 650-700F temperature. The separator overhead vapor stream 61 consists mainly of hydrogen and other gases as well as light oil vapors, and is passed with additional hydrogen at 73 to a second stage reactor 74 as described below. Liquid fraction 62 from first separator 60 flows into second separator 64, which is maintained at 1500-2500 prig pressure and 750-800F temperature, usually by using external heating means such as electric heating coils attached to the separator. The liquid fractions having critical temperatures between 650-800F vaporizes in the second separator 64 to provide super critical solvent vapor therein at the high pressure. This super critical sol-vent vapor dissolves and highly extracts most of the liquid material in the second separator, except for a heavy liquid slurry material which contains substantially all the solids, such as nickel- and vanadium-containing compounds, and a substantial part of the high RCR-containing material, which is withdrawn at 65. This heavy slurry material is usually discarded from the process, but if desired, a portion can be recycled to the reactor pa dry further hydroconversion.
The extracted hydrocarbon liquid and super critical sol-I I
vent vapor in separator 64 is withdrawn in vapor form at Andy flashed to lower pressure in flash vessel 66 to separate the oil vapors and dissolved gases from the heavy oil free-lions. Vapor fraction 67 is removed from flash vessel 66 and passed to a second catalytic reactor 74. If needed to supplement the super critical solvent vapor provided within second separator 64, a vapor portion 68 can be condensed at aye, pressurized at 69, reheated at aye and recycled to the separator 64 as super critical solvent vapor for producing further extraction therein.
From the flash step 66, the liquid fraction 70 is with-drawn and repressurized at 71 and introduced as stream 72 along with supplemental hydrogen 73 into second ebullated bed catalytic reactor 74, which is very similar in operation to first stage reactor 200 Suitable reaction conditions in the second stage reactor 74 are 780-820F temperature, 1800-2500 prig hydrogen partial pressure, and 0.4-2.0 Vf/hr/Vr space velocity.
From reactor 74, the effluent is passed to phase swooper-lion and fractionation steps and processed similarly as for FIG. 1. Specifically, reactor effluent stream 75 is passed to phase separator 76, from which the resulting vapor free-lion 77 is cooled at 78 and passed to phase separator 80, from which vapor portion 81 is passed to hydrogen purifica-lion system 34. Also from separator 80, liquid fraction 82 is withdrawn, pressure-reduced at 83 and passed to free-shunter 84 along with liquid fraction 79 withdrawn from separator 76.
From fractionator 84, a light hydrocarbon gas product is withdrawn at 85, a middle boiling range distillate liquid product stream at 86, and a bottom liquid product withdrawn at 87. If desired, a portion of the heavy oil 87 from free-~2;~623~
shunter 84 is passed to vacuum distillation at 88 for fur-then removal of light fractions. Also, from the flash step 66, a portion aye of the heavy oil fraction 70, can be passed to vacuum distillation at 88. From vacuum distill-lion step 88, a vacuum gas oil stream is removed at 89, and can be combined with fractionator bottoms liquid stream 87.
A vacuum bottoms material is withdrawn at aye, and a portion 89b can be recycled to reactor 20 for further conversion to lower boiling liquid products.
Thus, the present invention can be advantageously used in a hydrocarbon liquid hydroconversion process having two separate stages of catalytic reaction, wherein the supercri-tidal vapor extraction step is located intermediate the two hydroconversion reaction stages to remove substantially all the metal containing compounds and a substantial portion of the high boiling RCR containing residue from the first stage effluent before it is passed on to the second stage reactor for further hydroconversion, as shown in FIG. 2. In such a two-stage hydroconversion process, the feed to the second stage reactor is thus substantially free of RCR-containing asphaltenes and metals-containing compounds. This process arrangement improves catalyst life in the second stage react ion and also improves product quality. Selective recycle of heavy oil from vacuum distillation to the first stage react ion can also be used to improve resin hydroconversion and liquid product yields.
The present invention can also be advantageously used in a two stage reaction process for heavy hydrocarbon liquids in which the second stage is a fixed bed catalytic reactor, as generally shown in FIG. 3. Referring to FIG. 3, the first stage reactor 2Q is operated similarly to that for FIG. 1 and ma be either catalytic or non-catalytic type.
~ZZ6Z36 From reactor 20, the reactor effluent material 27 flows into the first separator 28, which is usually maintained at approximately 800-850F temperature and 15CC-4000 prig hydrogen partial pressure. From the first separator 28, overhead stream 29 consisting of hydrogen and other light gases and oil vapors is cooled at 30 and passed to the second separator 32. The slurry liquid fraction 36 from the first separator 28 is cooled and flows into the second separator 38, which is maintained at 750-820F temperature and about 1200-3800 prig pressure. The liquid from the first separator usually needs some intermediate cooling at 37 to maintain the second separator 38 at the desired 700-78CF temperature, so as to prevent thermal cracking of the liquid therein.
The super critical solvent vapor extraction of the slurry liquid occurs in second separator 38. A process-derived liquid fraction normally boiling between about 300-360F
provides a good super critical solvent extraction fluid at the preferred 730-780F temperature of the second separator.
The super critical oil vapor fraction along with the ox-treated material in vapor is withdrawn at 41, pressure-reduced to separate out vapor fractions, then condensed, pressurized and heated to the desired super critical them-portray to form a super critical solvent vapor, which is introduced into separator-extractor 38 to dissolve and extract part of the hydrocarbon liquid therein, including part of the 975F-~ fraction in the second separator.
Specifically, this super critical vapor together with dissolved liquid is removed as vapor stream 41 and flashed at suitable lower pressure conditions at flash vessel 42 to precipitate out heavy oils, including some resin from the oil vapor. The oil vapor portion 43b is cooled and con-~LZ26~36 dented to liquid form at 43c, then pressurized at 54, heated at 55 and recycled to the second separator 38 to provide the super critical solvent vapor needed for liquid extraction therein. The heavy liquid stream 39 discharged from second separator 38 consists of metals-containing compounds and some remaining 975F+ liquid fraction. This heavy oil stream aye is preferably recycled through heater 14 to react ion 20 for further hydroconversion.
From the flash step 42, the heavy oil fraction 44 along with vapor 43 and liquid stream 33 are passed together with additional hydrogen aye to a second reactor 90 for further catalytic desulfurization processing to remove sulfur and nitrogen compounds. Reactor 90 is usually a fixed catalyst bed type reactor. The catalyst used in reactor 90 can be any known hydrodesulfurization catalyst such as cobalt-molybdenum on alumina support. The reaction conditions in reactor 90 are maintained at 740-820F temperature and 1500-2800 prig hydrogen partial pressure.
From reactor 90 the effluent 91 is cooled at cooler 92 and passed to phase separator 94, from which the resulting vapor portion 93 is passed to hydrogen purification system 96. Liquid fraction 95 is withdrawn, and passed along with recycled hydrogen 99 from purification system 96 to hydra-cracker 100 for cracking of heavy fractions into lighter hydrocarbon fractions. Useful hydrocracking conditions are 780-820F temperature and 1800~2800 prig pressure. From hydrocracker 100, the effluent 101 is passed to fractionator 102, from which hydrocarbon gas products are withdrawn at 103, a middle boiling range distillate product stream at 104, and a bottom liquid product is withdrawn at 105. Be-cause the 975F~ fractions are substantially eliminated in the hydrocracking step 100, a vacuum distillation step is ~Z2~;Z36 usually not required.
If desired, a portion aye of the heavy oil from flash step 42 can be recycled to the first stage reactor 20 to improve the resin conversion and liquid products yields.
Also, a portion of bottoms material withdrawn at 105 can be preferably recycled to the reactor 90 for increased hydra-conversion such as to at least about go V % and preferably to 92-98 V % to material boiling below 975~F.
An advantage of the intermediate super critical extract lion step for a petroleum hydroconversion process is that very effective RCR and metals removal is accomplished in-situ in the second separator-extractor. Thus, because the feed to the second stage reactor is low in RCR and metals, the catalyst activity and product quality in the second stage reactor is substantially improved.
This invention will be more fully described by the following examples of petroleum hydroconversion operations, which should not be construed as limiting in scope.
A petroleum residuum feed stock material containing about 20 W % RCR, 0.075 W % total metals is fed together with hydrogen to a catalytic hydroconversion process having an ebullated catalyst bed reactor. The resulting hydrogenated effluent material is passed from the reactor to a phase separator, from which a liquid fraction is withdrawn, cooled and passed to a second separator-extractor. A hydrocarbon solvent vapor fraction at super critical conditions is added to the liquid in the second separator to dissolve and extract the hydrocarbon liquid fraction therein and to pro-vise effective separation ox heavy asphaltenes and metals-containing compounds. The resulting extracted vapor is withdrawn, flashed at lower pressure to recover the desired ~!LZ~236 solvent fraction for recycle to the extraction step, and the resulting liquid fraction withdrawn and distilled to provide desired liquid products.
Results of this super critical vapor extraction operation are presented in Table 1.
TABLE l Feed stock Bushwhacker Vacuum Bottoms Reaction Conditions Temperature, OF 830 Hydrogen Partial Pressure, swig Liquid Space Velocity, Vf/hr/Vr 2.0 Catalyst Age, bbls/lb Conversion of 975F~ Material, V ~85 LIQUID EXTRACTION CONDITIONS
Liquid Temperature, OF 760 Liquid Pressure, prig 1800 Solvent Temperature, OF 740 Solvent Normal Boiling Range, F300-400 Weight Ratio Solvent Added to Liquid Fraction 3:1 Residence Time in Second Separator, Min. 2 RCR Content of Second Separator Effluent, W I
RCR Content of Second Separator Bottoms, W 50 Metals Content of Second Separator Effluent, Pam <50 Metals Content of Second Separator Bottoms, Pam 3000 Based on the above results it is noted that substantial removal of RCR and metals-containing compounds occurs following extraction with the super critical vapor in the second separator, so that the vapor effluent stream leaving the separator contains less than about 2 W % RCR material and less than 50 Pam metals content. The separator bottoms streams contains substantially all the RCR and metals in the reactor effluent stream.
A petroleum vacuum residuum material containing about 20 W RCR material and 0.075 W total metals is fed together with hydrogen into the first stage ebullated gala-lust hod reactor of a two-stage catalytic hydroconversion process. The resulting hydrogenated effluent materials is ~Z2~23~
passed from the reactor to a hot phase separator, from which a liquid fraction is withdrawn, cooled and passed to a second separator-extracter. A hydrocarbon solvent vapor fraction at super critical conditions is added to the liquid in the second separator to dissolve and extract the hydra-carbon liquid fraction therein and to allow the separation of heavy asphaltenes and metals-containing compounds. The resulting extracted vapor is withdrawn, flashed at lower pressure to recover the desired solvent fraction for recycle to the extraction step. The resulting liquid fraction is withdrawn and combined with the vapor fraction from the hot separator and passed iota second catalytic reactor for further hydroconversion reactions followed by phase swooper-lion and distillation steps.
Results of this super critical extraction operations are provided in Table 2.
FeedstockBachaquero Vacuum Bottoms First Stage Reaction Conditions Temperature, OF 830 Hydrogen Partial Pressure, prig 2000 Liquid Space Velocity, Vf/hr/Vr 2.0 Catalyst Age, bbls/lb.4.0 LIQUID EXTRACTION CONDITIONS
Liquid Temperature, F760 Liquid Pressure, swig Solvent Temperature, F740 Solvent Normal Broiling Range, F300-~00 Weight Ratio Solvent Added to Liquid Fraction 2:1 Residence Time in Second Separator, Min. 2 RCR Content of Second Separator Effluent, W % I
RCR Content of Second Separator Bottoms, W % 35 Metals Content of Second Separator Effluent, Pam 80 Metals Content of Second Separator Bottoms, Pam 2000 Second Stage Reaction Conditions Temperature, OF 800 Hydrogen Partial Pressure, swig Liquid Space Velocity, V~/hr/Vr 2.5 Catalyst Age, bbls/lb. 1.5 Conversion of 975F+ Material, V % 97 Based on the above results, it is noted that substantial removal of RCR and metals-containing compounds occurs in the second separator, so that the vapor effluent stream leaving the separator contains less than about 8.0 % RCR materials less than about 80 Pam metals. The separator bottoms streams contains substantially all the RCR and metals in the reactor effluent stream.
Although this invention has been described broadly and in terms of certain preferred embodiments, it will be under-stood that modifications and variations to the process can remade within the spirit and scope of the invention, which is defined by the following claims.
Claims (19)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS.
1. A process for high hydroconversion of heavy hydro-carbon liquid feedstocks containing at least about 50 V %
material normally boiling above about 975°F to produce lower boiling hydrocarbon liquid and gas products wherein Ramsbottom carbon residue (RCR) materials and metals-containing compounds are removed by supercritical solvent extraction from the liquid fraction, said process comprising:
(a) feeding a hydrocarbon liquid feedstock together with hydrogen into a reaction zone, said reaction zone being maintained at 780-860°F temperature and 1000-5000 psig hydrogen partial pressure for liquid phase hydroconversion reaction to provide a hydro-converted effluent material containing a mixture of gas and liquid fractions;
(b) separating said hydrocarbon effluent material in a first separation zone into a gas fraction and a liquid fraction;
(c) passing said liquid fraction to a second separation zone maintained at a temperature above the critical temperature of a solvent vapor added to said liquid in said second separation zone to dissolve and extract the hydrocarbon liquid fraction from the liquid to provide substantial sepration of the RCR
material and metals-containing compounds residue therein;
(d) withdrawing said residue along with a minor portion of high boiling residual oil from said second separation zone;
(e) withdrawing and pressure-reducing the remaining extract vapor from said second separation zone containing supercritical solvent vapor and dis-solved liquid, and separating a light solvent fraction from a remaining heavy liquid fraction;
(f) recycling a portion of said light solvent vapor fraction to said second separation zone to provide the supercritical solvent vapor added therein; and (g) withdrawing hydrocarbon liquid and gas products from the process.
material normally boiling above about 975°F to produce lower boiling hydrocarbon liquid and gas products wherein Ramsbottom carbon residue (RCR) materials and metals-containing compounds are removed by supercritical solvent extraction from the liquid fraction, said process comprising:
(a) feeding a hydrocarbon liquid feedstock together with hydrogen into a reaction zone, said reaction zone being maintained at 780-860°F temperature and 1000-5000 psig hydrogen partial pressure for liquid phase hydroconversion reaction to provide a hydro-converted effluent material containing a mixture of gas and liquid fractions;
(b) separating said hydrocarbon effluent material in a first separation zone into a gas fraction and a liquid fraction;
(c) passing said liquid fraction to a second separation zone maintained at a temperature above the critical temperature of a solvent vapor added to said liquid in said second separation zone to dissolve and extract the hydrocarbon liquid fraction from the liquid to provide substantial sepration of the RCR
material and metals-containing compounds residue therein;
(d) withdrawing said residue along with a minor portion of high boiling residual oil from said second separation zone;
(e) withdrawing and pressure-reducing the remaining extract vapor from said second separation zone containing supercritical solvent vapor and dis-solved liquid, and separating a light solvent fraction from a remaining heavy liquid fraction;
(f) recycling a portion of said light solvent vapor fraction to said second separation zone to provide the supercritical solvent vapor added therein; and (g) withdrawing hydrocarbon liquid and gas products from the process.
2. The process of claim 1, wherein said supercritical solvent vapor is process-derived, said vapor having a criti-cal temperature 15-50°F below the liquid temperature in said second separation zone.
3. The process of claim 1, wherein said supercritical solvent vapor fraction has a normal boiling range of 250-450°F.
4. The process of claim 1, wherein said supercritical solvent vapor fraction is added to said second separation zone in a weight ratio range of 1 - 5.
5. The process of claim 1, wherein said liquid frac-tion is cooled between the first and second separation zones sufficient that said second separation zone operates at a temperature 20-80°F below said first separation zone.
6. The process of claim 1, wherein said reaction zone contains an ebullated bed of catalyst.
7. The process of claim 5, wherein said reaction zone is maintained at 790-850°F temperature and 1200-3000 psig hydrogen partial pressure.
8. The process of claim 1, wherein the hydrocarbon liquid feedstock is a petroleum residua material.
9. The process of claim 1, wherein at least a portion of said solvent vapor added to said second separation zone is condensed in said first separation zone and is drained into said second separation zone.
10. The process of claim 1, wherein a light liquid fraction and a heavy oil fraction from said separation zones are passed with hydrogen to a second catalytic reaction zone for further hydroconversion to provide increased yield of low-boiling hydrocarbon liquid and gas products.
11. A process for high hydroconversion of a petroleum residua feedstock containing at least about 50 V % material normally boiling above about 975°F to produce lower boiling hydrocarbon liquid and gas products wherein Ramsbottom car-bon residue (RCR) materials and metals-containing compounds are solvent separated and removed from the liquid fraction, said process comprising:
(a) feeding a petroleum residua feedstock together with hydrogen into a reaction zone containing a catalyst bed, said reaction zone being maintained at 780-860°F temperature and 1000-5000 psig hydrogen partial pressure for liquid phase hydroconversion reactions to provide a hydroconverted effluent material containing a mixture of gas and liquid fractions;
(b) separating said hydrocarbon effluent material in a first separation zone into a gas fraction and a liquid fraction;
(c) cooling said liquid fraction and passing it to a second separation zone maintained at a temperature 15-50°F above the critical temperature of a solvent vapor having a normal boiling range of 250-450°F
which is added to said liquid fraction in said second separation zone for dissolving and extrac-ting substantially all the hydrocarbon liquid fraction from the liquid and providing substantial separation of the RCR materials and metals-con-taining compound residue therein;
(d) withdrawing said residue along with a minor portion of high boiling residual oil from said second separation zone;
(e) withdrawing and pressure-reducing the remaining vapor extract from said second separation zone con-taining supercritical solvent vapor and dissolved liquid, and separating a light solvent fraction from a remaining heavy liquid fraction;
(f) recycling a portion of said light solvent vapor fraction to said second separation zone to provide the supercritical solvent vapor added therein; and (g) withdrawing hydrocarbon liquid and gas products from the process.
(a) feeding a petroleum residua feedstock together with hydrogen into a reaction zone containing a catalyst bed, said reaction zone being maintained at 780-860°F temperature and 1000-5000 psig hydrogen partial pressure for liquid phase hydroconversion reactions to provide a hydroconverted effluent material containing a mixture of gas and liquid fractions;
(b) separating said hydrocarbon effluent material in a first separation zone into a gas fraction and a liquid fraction;
(c) cooling said liquid fraction and passing it to a second separation zone maintained at a temperature 15-50°F above the critical temperature of a solvent vapor having a normal boiling range of 250-450°F
which is added to said liquid fraction in said second separation zone for dissolving and extrac-ting substantially all the hydrocarbon liquid fraction from the liquid and providing substantial separation of the RCR materials and metals-con-taining compound residue therein;
(d) withdrawing said residue along with a minor portion of high boiling residual oil from said second separation zone;
(e) withdrawing and pressure-reducing the remaining vapor extract from said second separation zone con-taining supercritical solvent vapor and dissolved liquid, and separating a light solvent fraction from a remaining heavy liquid fraction;
(f) recycling a portion of said light solvent vapor fraction to said second separation zone to provide the supercritical solvent vapor added therein; and (g) withdrawing hydrocarbon liquid and gas products from the process.
12. A process for high hydroconversion of a petroleum residua feedstock containing at least about 50 V material normally boiling above about 975°F to produce lower boiling hydrocarbon liquid and gas products wherein Ramsbottom car-bon residue (RCR) materials and metals-containing compounds are solvent separated and removed from the liquid fraction by supercritical solvent extraction, said process comprising:
(a) feeding a petroleum residua feedstock together with hydrogen into a reaction zone containing a catalyst bed, said reaction zone being maintained at 780-850°F temperature and 1000-5000 psig hydrogen partial pressure for liquid phase hydroconversion reaction to provide a hydroconverted effluent material containing a mixture of gas and liquid fractions;
(b) separating said hydrocarbon effluent material in a first separation zone into a gas fraction and a liquid fraction;
(c) cooling said liquid fraction and passing it to a second separation zone maintained at a temperature 15-50°F above the critical temperature of a solvent vapor having a normal boiling range of 250-450°F
which is added to said liquid fraction in the second separation zone for dissolving and extracting substantially all the hydrocarbon liquid fraction from the liquid therein to provide substantial separation of the RCR materials and metals-con-taining compound residue therein;
(d) withdrawing said residue along with a minor portion of high boiling residual oil from said second separation zone;
(e) withdrawing and pressure-reducing the remaining extract vapor from said second separation zone con-taining the supercritical solvent vapor and dis-solved liquid, and separating a light solvent fraction from a remaining heavy liquid fraction;
(f) recycling a portion of said light solvent vapor fraction to said second separation zone to provide the supercritical solvent vapor added therein;
(g) combining a light liquid fraction and the remaining portion of heavy liquid fraction and introducing the combined stream with hydrogen into a second catalytic reaction zone being maintained at 700-820°F temperature and 1000-4500 psig hydrogen partial pressure for further hydroconversion and desulfurization to provide a hydrocarbon effluent material containing liquid and gas fractions;
(h) separating said hydrocarbon effluent material in a third separation zone into a gas fraction and a liquid fraction; and (i) withdrawing hydrocarbon liquid and gas products from the process.
(a) feeding a petroleum residua feedstock together with hydrogen into a reaction zone containing a catalyst bed, said reaction zone being maintained at 780-850°F temperature and 1000-5000 psig hydrogen partial pressure for liquid phase hydroconversion reaction to provide a hydroconverted effluent material containing a mixture of gas and liquid fractions;
(b) separating said hydrocarbon effluent material in a first separation zone into a gas fraction and a liquid fraction;
(c) cooling said liquid fraction and passing it to a second separation zone maintained at a temperature 15-50°F above the critical temperature of a solvent vapor having a normal boiling range of 250-450°F
which is added to said liquid fraction in the second separation zone for dissolving and extracting substantially all the hydrocarbon liquid fraction from the liquid therein to provide substantial separation of the RCR materials and metals-con-taining compound residue therein;
(d) withdrawing said residue along with a minor portion of high boiling residual oil from said second separation zone;
(e) withdrawing and pressure-reducing the remaining extract vapor from said second separation zone con-taining the supercritical solvent vapor and dis-solved liquid, and separating a light solvent fraction from a remaining heavy liquid fraction;
(f) recycling a portion of said light solvent vapor fraction to said second separation zone to provide the supercritical solvent vapor added therein;
(g) combining a light liquid fraction and the remaining portion of heavy liquid fraction and introducing the combined stream with hydrogen into a second catalytic reaction zone being maintained at 700-820°F temperature and 1000-4500 psig hydrogen partial pressure for further hydroconversion and desulfurization to provide a hydrocarbon effluent material containing liquid and gas fractions;
(h) separating said hydrocarbon effluent material in a third separation zone into a gas fraction and a liquid fraction; and (i) withdrawing hydrocarbon liquid and gas products from the process.
13. A process for high hydroconversion of heavy hydro-carbon liquid feedstock containing at least about 50 V %
material normally boiling above about 975°F to produce lower boiling hydrocarbon liquid and gas products wherein Rams-bottom carbon residue (RCR) materials and metals-containing compounds are removed from the liquid fraction by supercri-tical solvent vapor extraction, said process comprising:
(a) feeding a hydrocarbon liquid feedstock together with hydrogen into a reaction zone, said reaction zone being maintained at 780-850°F temperature and 1000-5000 psig hydrogen partial pressure for liquid phase hydroconversion reaction to provide a hydro-converted effluent material containing a mixture of gas and liquid fractions;
(b) separating said hydrocarbon effluent material in a first separation zone into a gas fraction and a liquid fraction;
(c) draining said liquid fraction to a second separa-tion zone maintained at a temperature 50-150°F
above that in the first separation zone so as to vaporize a solvent fraction and form a supercriti-cal solvent vapor therein to dissolve and extract the hydrocarbon liquid fraction from the liquid to provide substantial separation of the RCR material and metals-containing compound residue therein;
(d) withdrawing said residue along with a minor portion of high boiling residual oil from said second separation zone;
(e) withdrawing and pressure-reducing the remaining extracted vapor from said second separation zone containing supercritical solvent vapor and dis-solved liquid, and separating a light solvent fraction from a remaining heavy liquid fraction;
and (f) withdrawing hydrocarbon liquid and gas products from the process.
material normally boiling above about 975°F to produce lower boiling hydrocarbon liquid and gas products wherein Rams-bottom carbon residue (RCR) materials and metals-containing compounds are removed from the liquid fraction by supercri-tical solvent vapor extraction, said process comprising:
(a) feeding a hydrocarbon liquid feedstock together with hydrogen into a reaction zone, said reaction zone being maintained at 780-850°F temperature and 1000-5000 psig hydrogen partial pressure for liquid phase hydroconversion reaction to provide a hydro-converted effluent material containing a mixture of gas and liquid fractions;
(b) separating said hydrocarbon effluent material in a first separation zone into a gas fraction and a liquid fraction;
(c) draining said liquid fraction to a second separa-tion zone maintained at a temperature 50-150°F
above that in the first separation zone so as to vaporize a solvent fraction and form a supercriti-cal solvent vapor therein to dissolve and extract the hydrocarbon liquid fraction from the liquid to provide substantial separation of the RCR material and metals-containing compound residue therein;
(d) withdrawing said residue along with a minor portion of high boiling residual oil from said second separation zone;
(e) withdrawing and pressure-reducing the remaining extracted vapor from said second separation zone containing supercritical solvent vapor and dis-solved liquid, and separating a light solvent fraction from a remaining heavy liquid fraction;
and (f) withdrawing hydrocarbon liquid and gas products from the process.
14. The process of claim 13, wherein said reaction zone contains an ebullated bed of catalyst.
15. The process of claim 13, wherein the hydrocarbon liquid feedstock is a petroleum residua material.
16. The process of claim 13, wherein a portion of said light solvent fraction is heated to supercritical temperature and recycled to said second separation zone to supplement the solvent vapor therein.
17. The process of claim 13, wherein a light liquid fraction and a heavy oil fraction from said separation zones are passed with hydrogen to a second catalytic reaction zone for further hydroconversion to provide increased yield of low-boiling hydrocarbon liquid and gas products.
18. A process for high hydroconversion of a petroleum residua feedstock containing at least about 50 V % material normally boiling above about 975°F to produce lower boiling hydrocarbon liquid and gas products wherein Ramsbottom car-bon residue (RCR) materials and metals-containing compounds are separated and removed from the liquid product by super-critical solvent extraction, said process comprising:
(a) feeding a petroleum residua feedstock together with hydrogen into a reaction zone containing a catalyst bed, said reaction zone being maintained at 780-860°F temperature and 1000-5000 psig hydrogen partial pressure for liquid phase hydroconversion reaction to provide a hydroconverted effluent material containing a mixture of gas and liquid fractions;
(b) separating said hydrocarbon effluent material in a first separation zone into a gas fraction and a liquid fraction;
(c) draining said liquid fraction from said first separation zone into a second separation zone main-tained at a temperature 50-150°F above that in the first separation zone so as to vaporize a 250-450°F
boiling range solvent fraction and form a supercri-ticial solvent vapor therein to dissolve and extract substantially all the hydrocarbon liquid fraction from the liquid to provide substantial separation of the RCR material and metals-containing compound residue therein;
(d) withdrawing said residue along with a minor portion of high boiling residual oil from said second separation zone;
(e) withdrawing and pressure-reducing the remaining extracted vapor from said second separation zone containing supercritical solvent vapor and dis-solved liquid, and separating a light solvent fraction from a remaining heavy liquid fraction;
(f) heating a portion of said light solvent fraction and recycling it to said second separation zone to supplement the critical solvent vapor therein; and (g) withdrawing hydrocarbon liquid and gas products from the process.
(a) feeding a petroleum residua feedstock together with hydrogen into a reaction zone containing a catalyst bed, said reaction zone being maintained at 780-860°F temperature and 1000-5000 psig hydrogen partial pressure for liquid phase hydroconversion reaction to provide a hydroconverted effluent material containing a mixture of gas and liquid fractions;
(b) separating said hydrocarbon effluent material in a first separation zone into a gas fraction and a liquid fraction;
(c) draining said liquid fraction from said first separation zone into a second separation zone main-tained at a temperature 50-150°F above that in the first separation zone so as to vaporize a 250-450°F
boiling range solvent fraction and form a supercri-ticial solvent vapor therein to dissolve and extract substantially all the hydrocarbon liquid fraction from the liquid to provide substantial separation of the RCR material and metals-containing compound residue therein;
(d) withdrawing said residue along with a minor portion of high boiling residual oil from said second separation zone;
(e) withdrawing and pressure-reducing the remaining extracted vapor from said second separation zone containing supercritical solvent vapor and dis-solved liquid, and separating a light solvent fraction from a remaining heavy liquid fraction;
(f) heating a portion of said light solvent fraction and recycling it to said second separation zone to supplement the critical solvent vapor therein; and (g) withdrawing hydrocarbon liquid and gas products from the process.
19. A process for high hydroconversion of a petroleum residua feedstock containing at least about 50 V % material normally boiling above about 975°F to produce power boiling hydrocarbon liquid and gas products wherein Ramsbottom car-bon residue (RCR) materials and metals-containing compounds are separated and removed from the liquid product by super-critical solvent extraction, said process comprising:
(a) feeding a petroleum residua feedstock together with hydrogen into a reaction zone containing a catalyst bed, said reaction zone being maintained at 780-860°F temperature and 1000-5000 psig hydrogen partial pressure for liquid phase hydroconversion reaction to provide a hydroconverted effluent material containing a mixture of gas and liquid fractions;
(b) separating said hydrocarbon effluent material in a first separation zone into a gas fraction and a liquid fraction;
(c) draining said liquid fraction from said first separation zone into a second separation zone main-tained at a temperature 15-50°F above that in the first separation zone so as to vaporize a fraction having a normal boiling range of 250-450°F and forming a supercritical solvent vapor in the second separation zone for dissolving and extracting the hydrocarbon liquid fraction therein to provide substantial separation of the RCR materials and metals-containing compound residue therein;
(d) withdrawing said residue along with a minor portion of high boiling residual oil from said second separation zone;
(e) withdrawing and pressure-reducing the remaining extracted vapor from said second separation zone con-taining the supercritical solvent vapor and dissolved liquid, and separating a light solvent fraction from a remaining heavy liquid fraction;
(f) combining said gas fraction and the remaining por-tion of said heavy liquid fraction and introducing the combined stream along with hydrogen into a second ebullated bed catalytic reaction zone main-tained at 700-820°F temperature and 1000-4500 psig hydrogen partial pressure for further hydroconver-sion and desulfurization to provide a hydrocarbon effluent material containing liquid and gas fractions;
(g) separating said hydrocarbon effluent material in a third separation zone into a gas fraction and a liquid fraction; and (h) withdrawing hydrocarbon liquid and gas products from the process.
(a) feeding a petroleum residua feedstock together with hydrogen into a reaction zone containing a catalyst bed, said reaction zone being maintained at 780-860°F temperature and 1000-5000 psig hydrogen partial pressure for liquid phase hydroconversion reaction to provide a hydroconverted effluent material containing a mixture of gas and liquid fractions;
(b) separating said hydrocarbon effluent material in a first separation zone into a gas fraction and a liquid fraction;
(c) draining said liquid fraction from said first separation zone into a second separation zone main-tained at a temperature 15-50°F above that in the first separation zone so as to vaporize a fraction having a normal boiling range of 250-450°F and forming a supercritical solvent vapor in the second separation zone for dissolving and extracting the hydrocarbon liquid fraction therein to provide substantial separation of the RCR materials and metals-containing compound residue therein;
(d) withdrawing said residue along with a minor portion of high boiling residual oil from said second separation zone;
(e) withdrawing and pressure-reducing the remaining extracted vapor from said second separation zone con-taining the supercritical solvent vapor and dissolved liquid, and separating a light solvent fraction from a remaining heavy liquid fraction;
(f) combining said gas fraction and the remaining por-tion of said heavy liquid fraction and introducing the combined stream along with hydrogen into a second ebullated bed catalytic reaction zone main-tained at 700-820°F temperature and 1000-4500 psig hydrogen partial pressure for further hydroconver-sion and desulfurization to provide a hydrocarbon effluent material containing liquid and gas fractions;
(g) separating said hydrocarbon effluent material in a third separation zone into a gas fraction and a liquid fraction; and (h) withdrawing hydrocarbon liquid and gas products from the process.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/468,108 US4478705A (en) | 1983-02-22 | 1983-02-22 | Hydroconversion process for hydrocarbon liquids using supercritical vapor extraction of liquid fractions |
| US468,108 | 1983-02-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1226236A true CA1226236A (en) | 1987-09-01 |
Family
ID=23858462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000447902A Expired CA1226236A (en) | 1983-02-22 | 1984-02-21 | Hydroconversion process for hydrocarbon liquids using supercritical vapor extraction of liquid fractions |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4478705A (en) |
| JP (1) | JPH08911B2 (en) |
| CA (1) | CA1226236A (en) |
| MX (1) | MX164692B (en) |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3442506A1 (en) * | 1984-11-22 | 1986-05-22 | Union Rheinische Braunkohlen Kraftstoff AG, 5000 Köln | METHOD FOR PROCESSING CARBON-CONTAINING WASTE AND BIOMASS |
| US4778586A (en) * | 1985-08-30 | 1988-10-18 | Resource Technology Associates | Viscosity reduction processing at elevated pressure |
| FR2586938B1 (en) * | 1985-09-06 | 1989-10-20 | Commissariat Energie Atomique | METHOD AND DEVICE FOR EXTRACTING CONSTITUENTS WITH A SUPERCRITICAL FLUID |
| FR2588877B1 (en) * | 1985-10-17 | 1988-01-15 | Inst Francais Du Petrole | DEASPHALTING PROCESS COMPRISING ENERGY RECOVERY DURING SEASPHALTED OIL-DESASPHALTING SOLVENT SEPARATION |
| US4818371A (en) * | 1987-06-05 | 1989-04-04 | Resource Technology Associates | Viscosity reduction by direct oxidative heating |
| US4808289A (en) * | 1987-07-09 | 1989-02-28 | Amoco Corporation | Resid hydrotreating with high temperature flash drum recycle oil |
| FR2764902B1 (en) * | 1997-06-24 | 1999-07-16 | Inst Francais Du Petrole | PROCESS FOR THE CONVERSION OF HEAVY OIL FRACTIONS COMPRISING A STEP OF CONVERSION INTO A BOILING BED AND A STEP OF HYDROCRACKING |
| JP2001308828A (en) * | 2000-04-24 | 2001-11-02 | Temuko Japan:Kk | Method and device for arranging confidentiality in radio equipment |
| US7034084B2 (en) * | 2002-07-08 | 2006-04-25 | Bridgestone Corporation | Process and apparatus for the hydrogenation of polymers under supercritical conditions |
| US7809538B2 (en) | 2006-01-13 | 2010-10-05 | Halliburton Energy Services, Inc. | Real time monitoring and control of thermal recovery operations for heavy oil reservoirs |
| US7770643B2 (en) | 2006-10-10 | 2010-08-10 | Halliburton Energy Services, Inc. | Hydrocarbon recovery using fluids |
| US7832482B2 (en) | 2006-10-10 | 2010-11-16 | Halliburton Energy Services, Inc. | Producing resources using steam injection |
| SG11201402970RA (en) | 2011-12-22 | 2014-11-27 | Uop Llc | Uzm-39 aluminosilicate zeolite |
| CN104024184B (en) | 2011-12-22 | 2016-04-20 | 环球油品公司 | Use the aromatic conversion of UZM-39 aluminosilicate zeolite |
| EP2874944A4 (en) | 2011-12-22 | 2016-04-27 | Uop Llc | Layered conversion synthesis of zeolites |
| US8609910B1 (en) | 2012-12-12 | 2013-12-17 | Uop Llc | Catalytic pyrolysis using UZM-39 aluminosilicate zeolite |
| US8921634B2 (en) | 2012-12-12 | 2014-12-30 | Uop Llc | Conversion of methane to aromatic compounds using UZM-44 aluminosilicate zeolite |
| US8609921B1 (en) | 2012-12-12 | 2013-12-17 | Uop Llc | Aromatic transalkylation using UZM-44 aluminosilicate zeolite |
| US8609920B1 (en) | 2012-12-12 | 2013-12-17 | Uop Llc | UZM-44 aluminosilicate zeolite |
| US20140163281A1 (en) | 2012-12-12 | 2014-06-12 | Uop Llc | Conversion of methane to aromatic compounds using a catalytic composite |
| US8618343B1 (en) | 2012-12-12 | 2013-12-31 | Uop Llc | Aromatic transalkylation using UZM-39 aluminosilicate zeolite |
| US8912378B2 (en) | 2012-12-12 | 2014-12-16 | Uop Llc | Dehydrocyclodimerization using UZM-39 aluminosilicate zeolite |
| US8609911B1 (en) | 2012-12-12 | 2013-12-17 | Uop Llc | Catalytic pyrolysis using UZM-44 aluminosilicate zeolite |
| US8609919B1 (en) | 2012-12-12 | 2013-12-17 | Uop Llc | Aromatic transformation using UZM-44 aluminosilicate zeolite |
| US8889939B2 (en) | 2012-12-12 | 2014-11-18 | Uop Llc | Dehydrocyclodimerization using UZM-44 aluminosilicate zeolite |
| CA2972203C (en) | 2017-06-29 | 2018-07-17 | Exxonmobil Upstream Research Company | Chasing solvent for enhanced recovery processes |
| CA2974712C (en) | 2017-07-27 | 2018-09-25 | Imperial Oil Resources Limited | Enhanced methods for recovering viscous hydrocarbons from a subterranean formation as a follow-up to thermal recovery processes |
| CA2978157C (en) | 2017-08-31 | 2018-10-16 | Exxonmobil Upstream Research Company | Thermal recovery methods for recovering viscous hydrocarbons from a subterranean formation |
| KR102201310B1 (en) * | 2017-09-12 | 2021-01-11 | 주식회사 엘지화학 | Method and apparatus for separating solvent |
| CA2983541C (en) | 2017-10-24 | 2019-01-22 | Exxonmobil Upstream Research Company | Systems and methods for dynamic liquid level monitoring and control |
| JP6849574B2 (en) * | 2017-11-07 | 2021-03-24 | 株式会社神戸製鋼所 | Mixer |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2875149A (en) * | 1955-11-18 | 1959-02-24 | Texas Co | Treatment of residual asphaltic oils with light hydrocarbons |
| US2847353A (en) * | 1955-12-30 | 1958-08-12 | Texas Co | Treatment of residual asphaltic oils with light hydrocarbons |
| US2943050A (en) * | 1957-12-03 | 1960-06-28 | Texaco Inc | Solvent deasphalting |
| US3507777A (en) * | 1968-01-25 | 1970-04-21 | Exxon Research Engineering Co | Cracking process |
| JPS5410539A (en) * | 1977-06-24 | 1979-01-26 | Matsushita Electric Works Ltd | Door |
| US4354922A (en) * | 1981-03-31 | 1982-10-19 | Mobil Oil Corporation | Processing of heavy hydrocarbon oils |
| US4358365A (en) * | 1981-04-24 | 1982-11-09 | Uop Inc. | Conversion of asphaltene-containing charge stocks |
-
1983
- 1983-02-22 US US06/468,108 patent/US4478705A/en not_active Expired - Lifetime
-
1984
- 1984-02-21 MX MX200419A patent/MX164692B/en unknown
- 1984-02-21 CA CA000447902A patent/CA1226236A/en not_active Expired
- 1984-02-22 JP JP59030455A patent/JPH08911B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US4478705A (en) | 1984-10-23 |
| JPS59193990A (en) | 1984-11-02 |
| MX164692B (en) | 1992-09-17 |
| JPH08911B2 (en) | 1996-01-10 |
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