EP0143862A1 - Verfahren zur Umwandlung von Erdölrückständen - Google Patents
Verfahren zur Umwandlung von Erdölrückständen Download PDFInfo
- Publication number
- EP0143862A1 EP0143862A1 EP83306743A EP83306743A EP0143862A1 EP 0143862 A1 EP0143862 A1 EP 0143862A1 EP 83306743 A EP83306743 A EP 83306743A EP 83306743 A EP83306743 A EP 83306743A EP 0143862 A1 EP0143862 A1 EP 0143862A1
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- EP
- European Patent Office
- Prior art keywords
- solvent
- range
- boiling point
- fraction
- petroleum
- 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
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/32—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions in the presence of hydrogen-generating compounds
- C10G47/34—Organic compounds, e.g. hydrogenated hydrocarbons
-
- 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
Definitions
- This invention relates to an improved process for converting petroleum residuals. More particularly, this invention relates to an improved process for hydrocracking petroleum residuals.
- the foregoing and other objects and advantages are accomplished by converting a petroleum residual in the presence of molecular hydrogen and a hydrogen donor solvent at an elevated pressure and temperature.
- the total conversion of petroleum residual to lower boiling materials is increased by controlling the pressure within a relatively narrow critical range, by effecting the conversion in the presence of a hydrogen donor solvent containing at least 0.8 weight percent donatable hydrogen and by recycling substantially all of the liquid product having an initial boiling point within the range from about 600 o F to about 750°F as all or part of said solvent.
- the actual initial boiling point of this recycle fraction which is sometimes referred to herein as heavy solvent or heavy solvent fraction, will depend upon the final boiling point of the product desired.
- the improved process of this invention will yield a normally gaseous hydrocarbon product and a normally liquid product having an initial boiling point at or near atmospheric temperature and a final boiling point within the range from about 600°F to about 750°F.
- continuous operation of the process can be maintained by controlling the concentration of aromatic and hydroaromatic materials in the solvent relative to the amount of paraffinic materials therein.
- the Figure is a schematic flow diagram of a process within the scope of the present invention.
- the present invention relates to an improved process for converting petroleum residuals to lower boiling materials wherein total conversion of the petroleum residual and the yield of lighter boiling materials is increased.
- the liquefaction be accomplished in the presence of a solvent containing at least about 0.8 weight percent donatable hydrogen at the time the solvent is fed to the conversion step; that all of the liquid product from the conversion stage having an initial boiling point equal to the final boiling point of the recovered product and within the range from about 600°F to about 750°F be used as all or part of said solvent; and that the conversion be accomplished in the presence of molecular hydrogen at a partial pressure within the range from about 1500 to about 2500 psia.
- the ratio of paraffinic materials to aromatic and hydroaromatic materials in the solvent is controlled such that the ratio is within the range from about 0:1 to about 0.5:1.
- the method of the present invention can be used to convert any petroleum residual material.
- petroleum residual material shall mean the material remaining after a crude oil has been processed to separate lower boiling constitutents.
- the petroleum residuals will have an initial boiling point within the range from about 850 to about 1050°F and will be normally solid at atmospheric conditions.
- the petroleum residuals will, however, be liquid at the conditions used to effect the conversion.
- the petroleum residuals may be derived or separated from essentially any crude including those generally classed as aromatic, napthenic and paraffinic.
- the petroleum residuals useful in the method of this invention will be bottoms from a vacuum distillation column but the same could be any residual from a carbonaceous material having an initial boiling point within the range hereinbefore noted that is also liquid at the conditions used to effect the conversion.
- the petroleum residual will be combined with a solvent or diluent capable of donating hydrogen at the conditions employed to effect the conversion and containing at least 0.8 weight percent donatable hydrogen.
- the solvent is preferably a mixture of components, some of which are capable of donating hydrogen at the conversion conditions and some of which are not.
- At least a portion of the solvent will be a distillate fraction separated from the conversion liquid product and, depending on the particular petroleum residual subjected to conversion, this distillate fraction may be separately hydrotreated to produce components therein which are capable of donating hydrogen during conversion.
- the distillate fraction when the petroleum residual is highly aromatic, the distillate fraction will, generally, contain sufficient aromatic materials, that can be converted via hydrotreating to corresponding hydroaromatic materials to provide all of the donatable hydrogen required in the solvent. Moreover, by using all of the liquid product having an initial boiling point within the range of about 600°F to about 750°F as solvent, the amount of aromatics in the solvent fraction will be increased. Notwithstanding this, and when the petroleum residuals are primarily napthenic or paraffinic, however, it may be necessary to add aromatic and/or hydroaromatic materials to the distillate fraction which has been separated from the conversion product for use as a solvent but the amount of extraneous solvent required will, generally, be less when the heavy solvent fraction is used.
- paraffins are the principal contributor to coke formation during conversion and that the presence of aromatics and hydroaromatics during such conversions either inhibit the formation of coke or solubilize the same to avoid plugging during conversion operations.
- a solvent having characteristics similar to the characteristics of the conversion product increases total conversion of the petroleum residuals.
- the use of a solvent which is a distillate fraction containing a relatively broad range of compounds is, therefore, particularly advantageous and when the petroleum residual is an aromatic, the solvent should contain aromatic materials, when the petroleum residual is napthenic, the solvent should contain napthenic materials and when the residual is paraffinic, the solvent should contain paraffins.
- Particularly effective mixed solvents for use in the present invention include mixtures comprising a distillate fraction separated from the conversion product which is separately hydrotreated to convert at least a portion of the aromatic materials contained therein to the corresponding hydroaromatic components, hydrogenated creosote oils and hydrogenated catalytic cracking cycle stock and mixtures of such mixtures.
- Particularly effective solvents include distillate fractions of such mixtures having an initial boiling point within the range from about 350 to about 750°F and a final boiling point within the range from about 850 to about 1050°F which have been hydrogenated so as to contain at least 25 weight percent of hydrogen donor species and preferably at least 50 weight percent of such species.
- the petroleum residual and the solvent will be combined in a solvent-to-residual weight ratio within the range from about 0.5:1 to about 2:1.
- the combination may be effected in accordance with any procedure obvious to one of ordinary skill in the art which will be effective in uniformly distributing the petroleum residual throughout the solvent. Best results are generally, however, obtained at elevated temperatures within the range from about 100 to about 350°F in suitable mixing equipment.
- the amount of the liquid recycle solvent (heavy solvent) having an initial boiling point equal to the final boiling point of the recovered product and within the range from about 600°F to about 750 o F will be sufficient to provide from about 20 weight percent to about 100 weight percent of the solvent required.
- the weight ratio of heavy solvent-to- petroleum residual will be within the range from about 0.2:1 to about 1.0:1.
- the remaining portion of the solvent, when necessary or desired, may be separated from the recovered product and recycled to the conversion step.
- the mixture of petroleum residual and solvent is prepared, the same is then subjected to conversion at a temperature within the range from about 800 to about 880°F in the presence of molecular hydrogen.
- molecular hydrogen will be present at a concentration within the range from about 4 to about 8 weight percent based on petroleum residual and the partial pressure of molecular hydrogen will be within the range from about 1500 to about 2500.
- the mixture will be held at these conditions for nominal holding time within the range from about 30 to about 120 minutes.
- the liquid product will have an initial boiling point at or near the atmospheric temperature and a final boiling point equal to the initial boiling point of the petroleum residual and within the range from about 850 to about 1050°F.
- the liquid product may then be fractionated into any desired fractions for further upgrading or direct use as an end product provided that all of the heavier fraction, i.e., the fraction having an initial boiling point equal to the final boiling point of the desired product is recycled as solvent.
- Unconverted material i.e., material having a boiling point equal to or greater than the initial boiling point of the petroleum residual subjected to conversion may either be recycled to the conversion step, subjected to further conversion in a separate stage, burned directly as a fuel or discarded.
- a portion of the liquid product including at least the heavy solvent fraction, will be separated and recycled to provide at least a portion of the solvent required to effect the conversion.
- the separated fraction contains sufficient aromatics and/or hydroaromatics, it will not be necessary to combine this fraction with any extraneous solvent fractions.
- this fraction may be subjected to hydrotreating to convert at least a portion of the aromatics to a corresponding hydroaromatic material.
- this fraction does not, however, contain sufficient aromatic or hydroaromatic materials, it will be necessary to combine the same with an extraneous solvent fraction to produce a solvent having an aromatic/hydroaromatic concentration within the range heretofore specified.
- a catalytic cracking recycle oil is particularly preferred extraneous fraction to employ since this oil is particularly high in aromatic materials. Creosote oils may also be used as an extraneous solvent fraction since these oils, too, generally, contain significant concentrations of aromatic materials.
- the petroleum residual will be converted at a temperature within the range from about 820 to about 845 o F in the presence of a solvent capable of donating at least about 1.0 weight percent hydrogen, based on petroleum resid in the initial mixture of petroleum resid and solvent, and in the presence of molecular hydrogen at a hydrogen partial pressure within the range from about 1700 to about 2200 psia.
- the petroleum residual will be maintained at these conditions for a nominal holding time within the range from about 60 to about 90 minutes.
- the solvent will contain at least 60 weight percent aromatic and hydroaromatic components and the ratio of paraffinic materials to aromatic and hydroaromatic materials will be within the range from about 0:1 to about 0.25.
- the aromatic and hydroaromatic materials will be contained in a distillate fraction of the conversion liquid product and the solvent will contain all the liquid product having an initial boiling point within the range from about 650°F to about 700 o F, depending upon the cut point selected for the final boiling point of a light distillate product.
- a petroleum residual containing sufficient aromatic materials will be subjected to liquefaction and a sufficient concentration of aromatic materials will be present in a distillate fraction separated from the conversion liquid product and the required hydroaromatic concentration will be provided by hydrotreating this fraction to convert at least a portion of the aromatic materials to corresponding hydroaromatic materials.
- Any suitable catalyst may be used during the hydrotreating.
- a petroleum resid, a suitable solvent and molecular hydrogen are fed into mixing manifold 101 through lines 102, 103 and 104 respectively.
- the petroleum resid will be introduced at a temperature above the temperature at which the same is liquid and pumpable, generally at a temperature within the range from about 100 to about 250°F.
- any suitable solvent may be introduced through line 103 to effect "start up" of a commercial operation but at steady state recycle solvent comprising all of the liquid product having an initial boiling point equal to the final boiling point of the recovered product, generally between about 600 o F and about 750 o F will be introduced through line 105 and only makeup or extraneous solvent will be introduced through line 103. Extraneous solvent will, of course, be introduced when the recycle solvent introduced through line 105 is deficient in aromatic and/or hydroaromatic content.
- the solvent will, preferably, be a hydrogenated creosote oil or a hydrogenated catalytic cracking cycle stock.
- the solvent and molecular hydrogen will be preheated to a temperature within the range from about 800 to about 850 0 F.
- the solvent will contain sufficient donatable hydrogen to provide at least 0.4 weight percent donatable hydrogen based on petroleum resid in the initial mixture and the combined aromatic/hydroaromatic concentration in the solvent will be at least 50 weight percent.
- the solvent will be combined with a petroleum resid in a ratio within the range from about 0.5:1 to about 2:1, preferably from about 1:1 to about 1.5:1 such that the weight ratio of heavy solvent-to-resid is within the range from about 0.5:1 to about 0.7:1; and hydrogen will be added at a rate within the range from about 4 to about 8 weight percent based on petroleum residual in the initial mixture.
- the petroleum resid, solvent and molecular hydrogen mixture is fed to conversion reactor 106.
- the mixture is heated to a temperature within the range from about 800 to about 880°F at a hydrogen partial pressure within the range from about 1500 to about 2500 psig and at a total pressure within the range of about 1800 to about 2800 psig.
- the nominal holding time in conversion reactor 106 will range from about 30 to about 120 minutes.
- at least a portion of the petroleum resid will be converted to a normally gaseous product and at least a portion will be converted to a normally liquid product. Generally, at least a portion of the petroleum resid will remain unconverted.
- the entire conversion product is withdrawn through line 107 and passed to a first separator 108.
- a product containing the normally gaseous product and all of the liquid product which is to be recycled as solvent is separated overhead through line 109 and a bottoms product is separated through line 110.
- the fraction withdrawn overhead through line 109 is passed to hydrotreater 111.
- the hydrotreater In the hydrotreater, at least a portion of the aromatic materials are converted to corresponding hydroaromatic materials. Such conversion is believed to be well known in the prior art. Normally, such hydrotreatment will be accomplished at a temperature within the range from about 600°F to about 950°F, preferably at a pressure within the range from about 650 to about 2000 psia, preferably 1000 to about 1500 psia.
- the hydrogen treat rate during such hydrotreating generally will be within the range from about 1000 to about 10,000 scf/bbl. Any of the known hydrogenation catalyst may be employed, but a "nickel moly" catalyst is more preferred.
- the hydrotreated fraction is withdrawn through line 112 and recombined with the bottoms fraction from separator 108 in line 113.
- the recombined fractions are then passed to a second separator 114.
- product boiling below the initial boiling point of the solvent fraction ar separated overhead through line 115, a light distill fraction, a portion of which may be used as recycle solvent, is withdrawn through, line 116, a fraction having an initial boiling point equal to the higher boiling point of the light distillate fraction is withdrawn through line 117 and a bottoms product generally having an initial boiling point equal to the intial boiling point of the petroleum resid subjected to conversion is withdrawn through line 118.
- the light distillate fraction a portion of which may be recycled as solvent will have an initial boiling point within the range from about 350 to about 450°F and preferably an initial boiling point within the range from about 400 to about 450°F and, generally, a final boiling point within the range from about 600 to about 750°F and preferably a final boiling point within the range from about 650 to about 700°F.
- this fraction will, be withdrawn as product through line 119 and the remainder, when necessary or desirable, recycled as solvent through line 105.
- hydrotreating has been illustrated on a relatively broad boiling range product and between a first and second separator, the hydrotreating could be accomplished after the solvent fraction has been separated from the second separator through line 116 and 118.
- hydrogenation does alter the boiling range of the solvent and further separation after hydrogenation affords better control over the boiling range of the solvent fraction.
- operation in the manner illustrated in the Figure is preferred.
- the overhead product withdrawn through line 115 may be further separated into a normally gaseous product and a liquid product boiling, generally, in the naphtha ranger i.e., having an initial boiling point at or near atmospheric temperature and a final boiling point within the range from about 250°F to about 450 0 F.
- the gas may be scrubbed to remove impurities and used as a pipeline gas or as a process fuel.
- the naphtha fraction may be further upgraded in accordance with well-known procedures to yield a high quality gasoline.
- the light distillate fraction withdrawn through line 119 boils, generally, within the known fuel oil ranges and may be used as such or further upgraded and used either as a diesel fuel or as a fuel oil.
- the material withdrawn through line 117 boils, generally, within the vacuum gas oil range and will be recycled as solvent.
- the bottoms product withdrawn through line 118 may be at least partially recycled to the conversion reactor, burned for fuel value or discarded.
- a series of runs were com pleted in an autoclave at a temperature of 840°F, a nominal holding time of 80 minutes and in the presence of molecular hydrogen at a total pressure of 2000 psig using a solvent separated from liquid products from earlier autoclave runs having an initial boiling point of about 350°F and a final boiling point of about 1000°F.
- a vacuum petroleum residual obtained from a pipestill processing a heavy Arab crude and having a nominal initial boiling of about 1000°F was used.
- the solvent was separately hydrogenated to contain about 1.0 weight percent donatable hydrogen and was used in all runs at a weight ratio of 1.5:1 based on petroleum resid.
- the ratio of heavy solvent-to-resid (650/1000°F) and the net yield of 650/1000°F liquid product for each run is summarized in the following table.
- a net yield of 650°F/1000°F material is about 25 weight percent based on resid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP83306743A EP0143862A1 (de) | 1983-11-04 | 1983-11-04 | Verfahren zur Umwandlung von Erdölrückständen |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP83306743A EP0143862A1 (de) | 1983-11-04 | 1983-11-04 | Verfahren zur Umwandlung von Erdölrückständen |
Publications (1)
Publication Number | Publication Date |
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EP0143862A1 true EP0143862A1 (de) | 1985-06-12 |
Family
ID=8191337
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83306743A Withdrawn EP0143862A1 (de) | 1983-11-04 | 1983-11-04 | Verfahren zur Umwandlung von Erdölrückständen |
Country Status (1)
Country | Link |
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EP (1) | EP0143862A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3030564A1 (fr) * | 2014-12-22 | 2016-06-24 | Axens | Procede et dispositif pour la reduction des composes aromatiques polycycliques lourds dans les unites d'hydrocraquage |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2953513A (en) * | 1956-03-05 | 1960-09-20 | Exxon Research Engineering Co | Hydrogen donor diluent cracking process |
US3549519A (en) * | 1968-10-28 | 1970-12-22 | Universal Oil Prod Co | Mixed-phase thermal cracking process |
US3707459A (en) * | 1970-04-17 | 1972-12-26 | Exxon Research Engineering Co | Cracking hydrocarbon residua |
DE2949935A1 (de) * | 1979-12-12 | 1981-06-19 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur umwandlung von hochsiedenden rohoelen in erdoelaehnliche produkte |
US4294686A (en) * | 1980-03-11 | 1981-10-13 | Gulf Canada Limited | Process for upgrading heavy hydrocarbonaceous oils |
US4425224A (en) * | 1982-01-04 | 1984-01-10 | Exxon Research And Engineering Co. | Process for converting petroleum residuals |
-
1983
- 1983-11-04 EP EP83306743A patent/EP0143862A1/de not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2953513A (en) * | 1956-03-05 | 1960-09-20 | Exxon Research Engineering Co | Hydrogen donor diluent cracking process |
US3549519A (en) * | 1968-10-28 | 1970-12-22 | Universal Oil Prod Co | Mixed-phase thermal cracking process |
US3707459A (en) * | 1970-04-17 | 1972-12-26 | Exxon Research Engineering Co | Cracking hydrocarbon residua |
DE2949935A1 (de) * | 1979-12-12 | 1981-06-19 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur umwandlung von hochsiedenden rohoelen in erdoelaehnliche produkte |
US4294686A (en) * | 1980-03-11 | 1981-10-13 | Gulf Canada Limited | Process for upgrading heavy hydrocarbonaceous oils |
US4425224A (en) * | 1982-01-04 | 1984-01-10 | Exxon Research And Engineering Co. | Process for converting petroleum residuals |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3030564A1 (fr) * | 2014-12-22 | 2016-06-24 | Axens | Procede et dispositif pour la reduction des composes aromatiques polycycliques lourds dans les unites d'hydrocraquage |
WO2016102302A1 (fr) * | 2014-12-22 | 2016-06-30 | Axens | Procede et dispositif pour la reduction des composes aromatiques polycycliques lourds dans les unites d'hydrocraquage |
CN107429169A (zh) * | 2014-12-22 | 2017-12-01 | 阿克森斯公司 | 减少加氢裂化单元中的重质多环芳族化合物的方法和装置 |
US10533142B2 (en) | 2014-12-22 | 2020-01-14 | Axens | Method and device for reducing heavy polycyclic aromatic compounds in hydrocracking units |
CN107429169B (zh) * | 2014-12-22 | 2020-09-15 | 阿克森斯公司 | 减少加氢裂化单元中的重质多环芳族化合物的方法和装置 |
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
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AK | Designated contracting states |
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17P | Request for examination filed |
Effective date: 19851113 |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
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18W | Application withdrawn |
Withdrawal date: 19860503 |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: JACOBS, FRITZ, E., DR. Inventor name: BAUMAN, RICHARD FRANK Inventor name: VERNON, LONNIE WILLIAM, DR. |