US3429803A - Method for converting hydrocarbons - Google Patents

Method for converting hydrocarbons Download PDF

Info

Publication number
US3429803A
US3429803A US569446A US3429803DA US3429803A US 3429803 A US3429803 A US 3429803A US 569446 A US569446 A US 569446A US 3429803D A US3429803D A US 3429803DA US 3429803 A US3429803 A US 3429803A
Authority
US
United States
Prior art keywords
hydrocarbons
reaction
conversion
hydrogen
hydrocracking
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US569446A
Other languages
English (en)
Inventor
Newt M Hallman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universal Oil Products Co
Original Assignee
Universal Oil Products Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Universal Oil Products Co filed Critical Universal Oil Products Co
Priority claimed from DE19691908867 external-priority patent/DE1908867C/de
Application granted granted Critical
Publication of US3429803A publication Critical patent/US3429803A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/22—Separation of effluents
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00

Definitions

  • This invention relates to a method for converting hydrocarbons into lower boiling hydrocarbon conversion products. It particularly relates to a catalytic hydrocracking method for converting hydrocarbons into lower molecular weight products. It specifically relates to an improved method for achieving thermal balance within a catalytic hydrocracking process.
  • Hydrocracking or destructive hydrogenation, as distinguished from relatively simple addition of hydrogen to unsaturated bonds between carbon atoms, effects definite changes in the molecular structure of hydrocarbons. It produces from a relatively heavy hydrocarbon feedstock relatively light or lower molecular weight hydrocarbon products.
  • the hydrocracking reaction can convert a petroleum feedstock, such as gas oil, almost completely into gasoline boiling range products and lighter. It is of significant commercial interest since hydrocracking offers unique advantages over conventional catalytic cracking operations. Therefore, hydrocracking may be designated as a conversion process wherein not only are lower molecular weight or lo'wer boiling conversion products produced, but these conversion products are substantially more saturated than when hydrogen or hydrogen-donor material is not present.
  • the preferred processing technique involves the utilization of a catalytic mass possessing a high degree of hydrocracking activity.
  • the hydrocracking reaction can selectively convert a wide variety of feedstocks to lower boiling distillates with significantly less coke and gas yield and with higher yields of quality liquid products than are usually produced by conventional catalytic cracking processes performed in the substantial absence of hydrogen or hydrogen-donor material.
  • a method for converting hydrocarbons by exothermic chemical reaction with hydrogen in a conversion zone comprises passing the hydrocarbon by first pumping means into indirect heat exchange with the reaction eluent from the conversion zone sufficient to preheat the hydrocarbons as hereinafter specified; subjecting said heated hydrocarbons at reaction temperature to catalytic exothermic conversion in the presence of hydrogen and conversion catalyst; withdrawing from said zone at a temperature of at least reaction temperature reaction efliuent containing the conversion products and unreacted hydrogen; cooling said effluent to a temperautre below reaction temperature by means comprising preheating said hydrocarbons by indirect heat exchange with the hydrocarbons, as specified, and generating steam by indirect heat exchange with water in a steam generation zone; passing the cooled efiiuent into a separation zone wherein a liquid conversion product stream and a hydrogen gas stream, including unreacted hydrogen, are formed; removing said conversion product stream and said hydrogen stream from the separation zone; recycling the removed hydrogen gas stream by second pumping means to the conversion zone;
  • a more particular embodiment ofthis invention includes the recycling of the condensate from turbine drive means to the steam generation zone as at least part of the water required for steam generation.
  • a still further specific embodiment of this invention includes the passing of substantially all of said generated steam into prime movers integrally associated with said method for operation thereby, and the passing of said removed conversion product stream into power recovery turbine means connected to said first pumping means.
  • reaction temperature is intended to encompass that temperature chosen by the operator to achieve conversion. Preferably, it is the feed inlet temperature to the reactor in question, but this invention is not to be limited thereto.
  • Suitable hydrocarbon charge stocks for the practice of the present invention include kerosene fractions, gas oil fractions, lubricating oil and white oil stocks, heavy cycle stocks, fuel oil stocks, reduced crudes, various high boiling bottoms fractions including vacuum residuum and other sources of hydrocarbons having a depreciated market demand due to the relatively high boiling points of these charge stocks, accompanied by the usual presence of ⁇ asphaltic and other heavy residues.
  • the present invention is particularly directed toward processing the heavier of the aforementioned hydrocarbon feedstocks, namely vacuum gas oil fractions, heavy cycle stocks, reduced crudes, etc.; that is, those hydrocarbons having an initial boiling point in excess of about 650 F., preferably having an ASTM boiling range from 650 F. to about 1,l00 F.
  • al1 of the sources of hydrocarbon feedstocks containing nitrogenous compounds and it is distinctly preferable for the practice of this invention to limit the nitrogen content of the hydrocarbon feedstock to less than 1500 ppm. total nitrogen.
  • the catalyst used in the practice of the present invention may be any hydrocracking catalyst known to those skilled in the art as being selective for the hydrocracking reaction in the presence of nitrogenous compounds, such as ammonia.
  • metallic component or catalytically active metallic component is intended to encompass those catalytic components which are employed for their hydrocracking activity or for their propensity for the destructive removal of the nitrogenous compounds, aS the case may be.
  • These catalytically active metallic components are selected from the metals and compounds of Groups VI-A and VIII of the Periodic Table. In this manner, the metallic catalytic components are distinguished from those components that are employed as the solid support, or carrier material, or the acidic cracking component.
  • the metallic component of the catalyst which may be employed in the practice of this invention may comprise two or more of such metals.
  • the catalyst employed in the present method may comprise chromium, molybdenum, tungsten, iron, cobalt, nickel, palladium, platinum, ruthenium, rhodium, osmium, iridium, and mixtures of two or more including nickel-molybdenum, nickel-chromium, molybdenum-palladium, molybdenum-platinum, cobalt-nickel-molybdenum, chromium-platinum, chromium-palladium, molybdenum-nickel-palladium, etc.
  • the method of the present invention may be composed of a single reaction stage or of two or more separate but integral reaction stages representing a plural ystage conversion zone containing catalyst. If a plural stage conversion zone is used, each stage may contain a distinct catalytic composite of the same composition in each stage, or of a different composition in each stage, or any combination and mixtures of catalyst depending upon the needs of the business situation experienced by those skilled in the art.
  • a suitable solid carrier material which may be either naturally occurring or which may be synthetically prepared by means known to those in the art.
  • Naturally occurring carrier materials include various aluminum silicates, particularly when acid-treated to increase the activity thereof, -various aluminacontaining clays, sands, earths and the like.
  • the synthetically prepared components include at least a portion of both silica and aluminum.
  • Suitable carrier material components which may, in particular instances, be combined as an integral portion of the hydrocracking catalyst include zirconia, magnesia, thoria, boria, titania, strontia, hafnia, etc., with the preferred cracking component consisting essentially of the composite of silica and alumina.
  • the various embodiments of the present invention utilize 4hydrocarbon feedstocks generally containing nitrogenous compounds, it is preferable to practice the present invention in combination with a hydroning step which converts the nitrogenous compounds into ammonia.
  • a hydroning step which converts the nitrogenous compounds into ammonia.
  • the ammonia formed can be easily removed from the linal reaction product from the conversion zone by, say, Water washing, thereby leaving a product of lower boiling hydrocarbons which are substantially free from nitrogenous compounds.
  • a hydroning operation is to be conducted in conjunction with the present invention, it may be performed either adiabatically or isothermally, and generally is practiced at a temperature from 600 F. to 850 F., preferably from 650 F.
  • the hydrocarbon charge stock enters the process from line 10 and is pumped by rst pumping means 11 into line 12 wherein it is admixed with hydrogen which is introduced by recycle via line 30.
  • the hydrocarbon feedstock may have an ASTM boiling range from an initial boiling point of 650 F. to 1,100 F.
  • the hydrocarbon charge in line 10 is not intended to be limited thereto.
  • the mixture of hydrogen and hydrocarbon in line 12 is passed into exchanger 13 such that the temperature of the mixture is increased, for example, from F. to 380 F.
  • the hydrogen is present in an amount within the range of from 500 to 30,000 standard cubic feet per liquid barrel of charge, e.g. 20,000 s.c.f./ b.
  • the preheated mixture is then raised to about 760 F. by indirect heat exchange with the iinal reaction effluent in exchanger 16 and is passed through line 17 into -hydrocr-acking reactor 20.
  • recycle stock and/or hydrogen ygas may be introduced into the feed to reactor 20 via line 19.
  • the mixture of hydrogen and feed hydrocarbons in line 17 are preferably heated to reaction temperature of, say, 830 F., by passing through la conventional fired heater not shown.
  • reactor 20 will be maintained at a conversion temperature of from 650 F. to 900 F., preferably .about 830 F., and under an imposed pressure within the range of from 300 to 3,000 p.s.i.g., preferably about 2,200 p.s.i.g. Higher pressures appear to favor the destructive removal of any remaining nitrogenous compounds as Well as the conversion of those hydrocarbons boiling in excess of about 650 F.
  • the total hydrocarbons in the feedstock in reactor 20 will contact the particular catalyst 18 at a liquid hourly space velocity within the range of about 0.5 to about 10, preferably labout 0.75.
  • the catalyst deposed wit-hin the catalyst bed 18 serves a dual function: that is, the catalyst is non-sensitive to the presence of nitrogenous compounds, while at the same time it is capable of effecting the destructive removal thereof, and also is capable of effecting conversion of 'at least a portion of those hydrocarbons boiling, for example, at a temperature in excess of about 650 F. to 700 F.
  • the process conditions are adjusted in reactor to provide about 20% to 60% by volume conversion of the feedstock hydrocarbons to lower boiling hydrocarbons per pass.
  • the chemical hydrogen consumption for this reaction will range from about 500 to 5,000 s.c.f./b. of feed hydrocarbons.
  • the reaction eflluent from reactor 20 is withdrawn at a temperature of at least conversion temperature, and typically is substantially above the conversion temperature, eg. 880 F., through line 21 and passed into exchanger 16 wherein the reactor 20 efiuent is quenched to a temperature below the conversion temperature maintained in reactor 20, to wit: about 52.0 F., by indirect heat exchange with the feed hydrocarbons as hereinabove discussed.
  • the quenched effluent stream is now passed via line 22 from exchanger 16 into steam generator 23 wherein, for example, saturated steam at 250 pounds is generated.
  • the cooled effluent stream is withdrawn from steam generator 23 at a temperature of about 455 F.
  • heat exchanger 13 wherein it is further cooled to a temperature of about 300 F. by indirect heat exchange with the feed hydrocarbons as hereinabove discussed.
  • the cooled effluent stream is admixed with additional hydrogen from line 15, if desired, and passed from exchanger 13 via line 25 into separator 26.
  • the hydrogen-containing gas, including unreacted hydrogen, is removed via line 28 and compressed by second pumping means 29 to an elevated pressure for recycle via line 30 in admixture with the feed hydrocarbons in line 12 as hereinabove discussed.
  • the normally liquid products are removed from separator 26 via line 27 and passed into power recovery turbine means 31 wherein at least part of the power required to drive pumping means 11 is effected.
  • the desired lower boiling hydrocarbons are removed to storage or other processing means via line 32.
  • the generated steam is passed via line 33 and split into, for example, two portions for driving prime movers integrally associated with the method.
  • a first portion is passed via line 34 into condensing turbine drive means 35 under conditions suicient to drive pumping means 29 connected thereto as discussed hereinabove.
  • Another portion of the generated steam is passed via line into other condensing turbine drive means 41 under conditions suilcient to supply the remaining power requirements to drive the first pumping means 11 connected thereto.
  • the rst pumping means 11 is driven by a combination of the power train derived from condensing turbine 41 and power recovering turbine 31 both appropriately connected to the ⁇ iirst pumping means 11.
  • the generated steam in line 33 may be superheated by means not shown to eiectuate additional eiciencies in the condensing turbine drive means illustrated.
  • the steam condensate from condensing turbine 41 is removed via line 42, admixed with the condensate from condensing turbine 3S from line 36 and line 37, and passed into condensate separator 38. A minor proportion of vent gas is removed from separator 38 by means not shown.
  • the condensate water is passed from separator 38 via line 39 to steam generator 23 as at least part of the water required to generate the steam. Additional feed water, as needed or desired, can be added to the system via line 43.
  • the steam generator 23 is located in bet-Ween exchangers 16 and 13 respectively on the direction of reaction eluent ow from reactor 20.
  • the present invention be limited to such an arrangement.
  • Those skilled in the art and the design of the hydrocracking process utilizing the concepts described herein, can place the steam generator before the heat exchanger train, after the heat exchanger train, in between independent stages of a plural stage conversion process, or any other process location as long as the heat of reaction is substantially recovered by steam generation which is used to drive prime movers integrally associated with the method.
  • the present invention recovers to an optimum extent the exothermic heat of reaction generated by the hydrocracking reaction via means including steam generation for driving prime movers integrally associated 'with the method, and via means for recovering the potential energy contained in the high pressure reaction effluent using power recovery turbine drive means to drive prime movers integrally associated with the method.
  • EXAMPLE The practice of the present invention is further illustrated by the following example 'which indicates the products that may be obtained from the processing of a vacuum gas oil stream according to the scheme shown in the appended drawing and using typical conditions cited hereinabove.
  • the feedstock hydrocarbons had an API gravity of 23.1, a sulfur content of about 1.5 wt. percent, a nitrogen content of about 1200 ppm. by Weight, and an ASTM boiling range of from 660 F. to 1100 F.
  • the hydrogen purity was 97.5 mol percent.
  • the following products were obtained on the basis of charging 26,000 barrels per stream day of the feedstock:
  • API BPSD The invention claimed is:
  • Method for converting hydrocarbons by exothermic chemical reaction with hydrogen in a conversion zone which comprises:
  • Method according to claim 4 wherein said reaction temperature is from 625 F. to 900 F. and said reaction euent is withdrawn at a temperature substantially in excess of said reaction temperature.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US569446A 1966-08-01 1966-08-01 Method for converting hydrocarbons Expired - Lifetime US3429803A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US56944666A 1966-08-01 1966-08-01
GB863669 1969-02-18
NL6902733A NL6902733A (enrdf_load_stackoverflow) 1966-08-01 1969-02-21
DE19691908867 DE1908867C (de) 1969-02-21 Verfahren zur Umwandlung einer Kohlenwasserstoffbeschickung durch exotherme Umsetzung mit Wasserstoff
FR6904611A FR2061504A1 (enrdf_load_stackoverflow) 1966-08-01 1969-02-24

Publications (1)

Publication Number Publication Date
US3429803A true US3429803A (en) 1969-02-25

Family

ID=33136205

Family Applications (1)

Application Number Title Priority Date Filing Date
US569446A Expired - Lifetime US3429803A (en) 1966-08-01 1966-08-01 Method for converting hydrocarbons

Country Status (4)

Country Link
US (1) US3429803A (enrdf_load_stackoverflow)
FR (1) FR2061504A1 (enrdf_load_stackoverflow)
GB (1) GB1234132A (enrdf_load_stackoverflow)
NL (1) NL6902733A (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3855113A (en) * 1972-12-21 1974-12-17 Chevron Res Integrated process combining hydrofining and steam cracking
US20110180456A1 (en) * 2010-01-22 2011-07-28 Stephen Mark Davis Integrated Process and System for Steam Cracking and Catalytic Hydrovisbreaking with Catalyst Recycle
US20110315601A1 (en) * 2009-12-17 2011-12-29 H R D Corporation High shear process for processing naphtha
US20230024175A1 (en) * 2021-07-16 2023-01-26 Uop Llc Process for saturating aromatics in a pyrolysis stream

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1951792A (en) * 1930-10-30 1934-03-20 Standard Ig Co Process for hydrogenating hydrocarbon oils
US2491303A (en) * 1946-09-23 1949-12-13 Texas Co Catalytic conversion of hydrocarbon oil
US2953521A (en) * 1957-03-18 1960-09-20 Socony Mobil Oil Co Inc Liquid-liquid heat exchange in mixed phase hydrocarbon conversions
US3329605A (en) * 1963-07-23 1967-07-04 Michikazu Takeyoshi Gaseous phase cracking reaction methods

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE501920A (enrdf_load_stackoverflow) * 1950-03-15
US3043769A (en) * 1953-10-19 1962-07-10 Kellogg M W Co Destructive hydrogenation of heavy hydrocarbons
US3077448A (en) * 1960-05-03 1963-02-12 Kellogg M W Co Desulfurization process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1951792A (en) * 1930-10-30 1934-03-20 Standard Ig Co Process for hydrogenating hydrocarbon oils
US2491303A (en) * 1946-09-23 1949-12-13 Texas Co Catalytic conversion of hydrocarbon oil
US2953521A (en) * 1957-03-18 1960-09-20 Socony Mobil Oil Co Inc Liquid-liquid heat exchange in mixed phase hydrocarbon conversions
US3329605A (en) * 1963-07-23 1967-07-04 Michikazu Takeyoshi Gaseous phase cracking reaction methods

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3855113A (en) * 1972-12-21 1974-12-17 Chevron Res Integrated process combining hydrofining and steam cracking
US20110315601A1 (en) * 2009-12-17 2011-12-29 H R D Corporation High shear process for processing naphtha
US20140161683A1 (en) * 2009-12-17 2014-06-12 H R D Corporation High shear process for processing naphtha
US8821713B2 (en) * 2009-12-17 2014-09-02 H R D Corporation High shear process for processing naphtha
US9222033B2 (en) * 2009-12-17 2015-12-29 H R D Corporation High shear process for processing naphtha
US20110180456A1 (en) * 2010-01-22 2011-07-28 Stephen Mark Davis Integrated Process and System for Steam Cracking and Catalytic Hydrovisbreaking with Catalyst Recycle
US20230024175A1 (en) * 2021-07-16 2023-01-26 Uop Llc Process for saturating aromatics in a pyrolysis stream

Also Published As

Publication number Publication date
FR2061504A1 (enrdf_load_stackoverflow) 1971-06-25
DE1908867A1 (de) 1970-09-03
DE1908867B2 (de) 1973-02-01
NL6902733A (enrdf_load_stackoverflow) 1970-08-25
GB1234132A (enrdf_load_stackoverflow) 1971-06-03

Similar Documents

Publication Publication Date Title
US2642381A (en) Heat transfer between exothermic and endothermic reactions
US2671754A (en) Hydrocarbon conversion process providing for the two-stage hydrogenation of sulfur containing oils
US3488279A (en) Two-stage conversion of coal to liquid hydrocarbons
US3726784A (en) Integrated coal liquefaction and hydrotreating process
US4197184A (en) Hydrorefining and hydrocracking of heavy charge stock
US5200063A (en) Coal hydroconversion process comprising solvent enhanced pretreatment with carbon monoxide
US3119765A (en) Catalytic treatment of crude oils
ZA200908036B (en) Process for upgrading coal pyrolysis oils
US3841981A (en) Hydrogenation of tar sand bitumen
GB1584582A (en) Process for liquefying coal employing a vented dissolver
US3489674A (en) Method for the conversion of hydrocarbons
US4207167A (en) Combination hydrocarbon cracking, hydrogen production and hydrocracking
GB1584586A (en) Process for producing coal liquid product
US3402121A (en) Method for controlling the conversion of hydrocarbons
US3574090A (en) Recovery and reuse of hydrogen from a catalytic hydroprocessing process
US3429803A (en) Method for converting hydrocarbons
US2738311A (en) Coal hydrogenation process
US3475322A (en) Hydrocracking process
US4283267A (en) Staged temperature hydrogen-donor coal liquefaction process
US3207688A (en) Hydrocracking process in two stages employing finely divided catalyst particles
US2513022A (en) Manufacture of hydrogen
GB1584584A (en) Coal liquefaction process employing carbon monoxide
US1984596A (en) Destructive hydrogenation
US3224958A (en) Hydroconversion of light and heavy hydrocarbon fractions in separate reaction zones and contacting of the liquid portion of the heavy fraction hydroconversion product with the light fraction hydroconversion product
US2422672A (en) Selective demethylation of trimethylpentanes to form triptane