US2918427A - Hydrodesulfurization process employing a presulfided platinum catalyst - Google Patents

Hydrodesulfurization process employing a presulfided platinum catalyst Download PDF

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Publication number
US2918427A
US2918427A US461312A US46131254A US2918427A US 2918427 A US2918427 A US 2918427A US 461312 A US461312 A US 461312A US 46131254 A US46131254 A US 46131254A US 2918427 A US2918427 A US 2918427A
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Prior art keywords
sulfur
catalyst
platinum
hydrogen
fraction
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US461312A
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English (en)
Inventor
Clark E Adams
Jr Charles N Kimberlin
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Priority to US461312A priority Critical patent/US2918427A/en
Priority to GB27210/55A priority patent/GB793817A/en
Priority to DEE11357A priority patent/DE1014259B/de
Priority to FR1137599D priority patent/FR1137599A/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/10—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing platinum group metals or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding

Definitions

  • the present invention concerns a process for desulfurizing sulfur-containing hydrocarbons. It particularly concerns the desulfurization of hydrocarbon mixtures that contain sulfur and also aromatic and/or oleiinic compounds.
  • the invention especially relates to the desulfurization of petroleum naphtha fractions that are derived from the catalytic cracking of petroleum and petroleum fractions.
  • catalysts essentially consist of platinum which is finely divided, dispersed or impregnated on a particulate catalyst support such as alumina, silica gel, silica-alumina, silica-magnesia, activated char, etc.
  • a particulate catalyst support such as alumina, silica gel, silica-alumina, silica-magnesia, activated char, etc.
  • platinum which is finely divided, dispersed or impregnated on a particulate catalyst support such as alumina, silica gel, silica-alumina, silica-magnesia, activated char, etc.
  • a particulate catalyst support such as alumina, silica gel, silica-alumina, silica-magnesia, activated char, etc.
  • platinum contain from about 0.05 to 2.0 wt. percent platinum and usually about 0.5 wt. percent platinum.
  • the catalysts are conventionally prepared according to a variety of well-known
  • a mol ratio of sulfur to platinum be maintained within the catalyst bed at a value between about 1.5/1 and 3/ 1, and more particularly about 2/1.
  • extraneous sulfur may be added to the feed which it is desired to desulfurize.
  • mols S and rnols H2 represent the mols of sulfur and hydrogen fed to the reaction zone
  • TR is the reaction temperature in degrees Rankine and lies between 800 and 1400 R.
  • the amount of hydrogen in the expression is xed by the amount of sulfur and by the temperature. It is also apparent that the logarithm of the S/H2 mol ratio is lixed by the temperature alone. In this connection it is a requirement of the present invention that the logarithm of the S/ H2 mol ratio, for a given temperature, be maintained at a value at least as great as the value that is derived from the equation.
  • the temperature of the reaction zone be maintained within the range of values presented earlier, but it is also desired that it be maintained high enough to realize the required degree of desulfurization.
  • the pressure should be in the range stated earlier but not so great as to cause the hydro carbon feed to be in the liquid phase.
  • the ligure that accompanies the present description illustrates one embodiment ot" the invention and the best mode contemplated for carrying out the invention.
  • the process of the present invention is parlticularly adapted for the desulfurization of distillate petroleum fractions that boil within the range from about 150 to 400 F. and that contain sulfur, oleins and aromatics. Naphthas that boil within the range from about 200 to 350 F. and that are derived from cracking and/or coking processes are especially benefitted by the invention.
  • Such naphthas generally contain about 20 to 40 volume percent aromatics, about l5 to 60 volume percent olens and about 0.03 to 1.5 weight percent sulfur.
  • These and other hydrocarbon feed stocks that contain from about 0.01 to 2 wt. percent sulfur, at least about l volume percent olens, and at least about 10 volume percent aromatics are especially well adapted to the purposes of the invention.
  • catalysts that are effective in the present process consist of conventional platinumimpregnated carriers such as alumina, silica gel, char and the like.
  • the chemical compositions of such catalysts and their methods of preparation are well known in the art, and a detailed discussion of these features will not therefore be included in the present description.
  • the present process may be carried out using catalysts in the form of fixed beds, moving beds or uidized beds. Accordingly, the particle size of the catalyst may vary depending upon the particular type of catalyst bed that it is desired ⁇ to employ.
  • the catalyst should have a range of particle sizes that falls within the range from about 1/16 to 3A; inch and especially about 1/16 to 1/8 inch.
  • the catalyst may be present in the form of lumps, crushed particles, pills, pellets, etc. In general, it is desired that extruded pellets be employed of about 1/16 in diameter.
  • the catalyst In the event that a iiuidized bed of catalyst is used it is desired that the catalyst have a particle size range of about 20 to 150 microns and especially about 40 to 80 microns.
  • the catalyst In the event that the catalyst is employed in a moving bed type of operation, it is contemplated that the catalyst should have a particle size range of about s to 3/16 inch and especially about s inch. In any event it is desired that the catalyst contain from about 0.05 to 2.0 wt. percent platinum and especially about 0.4 to 0.6 wt. percent.
  • the best mode of practicing the present invention lies in using the catalyst in the form of a xed bed. It is further contemplated ⁇ that the catalyst be alumina impregnated with about 0 .5
  • Av catalyst may be made up in accordance with any of the conventional methods of preparation.
  • a particularly attractive method is as follows: aluminum hydrosol isk prepared as described in U.S. Patent 2,656,321. The hydrosol is dried at about 250 F. The dried alumina gel is ground to pass mesh and mixed with an equal weight of Water to form a thick paste. The alumina paste is extruded through a 1/16" die. The extruded pellets are dried and calcined for four hours at l100 F. The calcined pellets are covered with a solution of chloroplatinic acid containing sufficient chloroplatinic acid to introduce 0.5 wt. percent of platinum into the alumina. The alumina adsorbs the chloroplatinic acid from solution. from the impregnated pellets. The catalyst is then dried and heated for 3 hours at 1000 F.
  • the process of the present invention employs a hydrogen-containing gas as one of the materials that enter the desulfurization zone.
  • the gas may be pure hydrogen or it may be a gas that contains hydrogen as one of its major components.
  • the gas may be pure hydrogen or it may be a gas that contains hydrogen as one of its major components.
  • the hydrogen-containing gas should contain at least 50 volume percent hydrogen and preferably at least 65 volume percent hydrogen. It is further desired that the gas contain substantially no carbon monoxide or carbon dioxide and less than 0.5 mol percent water.
  • the gasv may contain such gaseous components as light paratinic hydrocarbons such as methane, ethane, etc. Tail gas derived from conventional hydroforming operations with4 platinum or molybdena catalysts is suitable.
  • reaction zone 8 will initially contain no sulfur. And in this connection it will be recalled that a critical feature of- ⁇ theprlesent invention calls for the maintenance of a arid-.-
  • a vfirst phase of the present process is necessarily concerned with establishing the critical mol ratio of platinum to sulfui thatt is desired to maintain within this zone.
  • This ⁇ step may be accomplished in several ways.
  • a sulfurcontaining gas such as hydrogen rich in hydrogen sulde may be passed through zone 8 under conditions of temperature and pressure whereby the sulfur combines with the catalyst.
  • a sulfurcontaining hydrocarbon stream is passed through zone S for a period of time suicient to realize the platinum/sulfur mol ratios desired.
  • a particularly effective manner of achieving this objective lies in passing the feed stock itself through the reaction zone under conditions such that the sulfur inthe feedstock will combine with the catalyst.
  • the feed In any Acase involvingthe use of a hydrocarbon presulfiding feed, it is desired that the feed have a boiling range ofl about 150 to 400 F., preferably about 200 to 350 F., and that it contain at least about 1.0 wt. percent sulfur. In general, ⁇ it is desired that the presulfiding feed not contain in excess of about 2.0 wt. percent sulfur.
  • the feed stock be a virgin naphtha containing no olens and very little aromatics, "since this type of feed stock is not harmed or affected bythe hydrogenating activityv of the catalyst.
  • ⁇ it is desiredthat hydrogen be added with the presulfiding feed to avoid carburization of the catalyst.
  • reaction zone 8 be brought up to suitable conditions of temperature and pressure. This may be achieved by preheating the sultiding feed stock and/or the hydrogen stream that are introduced within zone 8. This may be done by the use of a suitable heating zone 7 which may be a conventional furnace, fired coil, heat exchanger, or the like.
  • reaction zone 8 ⁇ must be maintained at a temperature of at least 400 F. and ⁇ a pressure of at least 15 p.s.i.g., preferably about S p.s.i.g.
  • the temperature and pressure should not exceed the values of 1000 F. and 600 p.s.i.g. respectively.
  • a preferred temperature range for this step is about 500 ⁇ to 600 F., and a preferred pressure range is about 50 to 200 p.s.i.g.
  • the presulfiding reaction should be carried out at a hydrocarbon feed rate between about l v./hr./v. and 10 vt/hL/v. ⁇ and preferably' about 5 v./hr./v.
  • the hydro- ⁇ gen rate should be at least about 1000 s.c.f. of hydrogen per barrel of feed, and it is particularly desired that the sulfur to hydrogen mol ratio in the feed be maintained about a certain critical value. This ratio (i.e. the minimum value) is also described by the equation given hereinbefore relative to the desulfurization reaction.
  • the presulliding phase ofthe process must be continued until the catalyst is provided with at least 1.5 mols of sulfur per mol of platinum and preferably at least 2 mols of sulfur per mol of platinum. This point may be determined by conventional chemical analyses and material balances performedon the feed and product streams. It
  • ⁇ may also be determinedby running sulfur analyses on small samples of the catalyst bed itself.
  • the presuliiding step will normally require about 30 minutes to one hour.
  • the desulfurization phase of the ⁇ process should be initiated.
  • the feed stock ⁇ is introduced via lines 5 and 6 and heating zone 7 into zone 8.
  • a hydrogen-containing gas is simultaneously introduced by means of lines 9 and 6 and zone 7 into zone 8.
  • the relative amounts of hydrogen and hydrocarbon feed that flow into zone 8 must be determined on the basis of the temperature that is maintained within zone 8.
  • the feed rates are ⁇ further determined by the contact times that it is desiredI to maintain ⁇ for both of these streamsv within ⁇ zone 8.
  • the temperature of zone 8 will, of course, be governed by the sulfur content of the feed, the activity of the catalyst, and the degree of desulfurization desired.
  • reaction zone 8 Assuming that reaction zone 8 is operated at 600 F., it necessarily follows that the feed rates of hydrocarbon and hydrogen-containing gas that enter zone 8 must be regulated so as to realize a sulfur to hydrogen mol ratio within zone 8 of at least 0.004/1. A ratio much above this value, however, should be avoided since higher ratios tend to decrease the efficiency of desulfurization. f
  • the feed rate of the hydrocarbon feed to zone 8 must additionally be maintained within the range of from about 0.1 to 20 ⁇ volumes of liquid per hour per volume of cata-4 lyst and preferably about 5 v./hr./v.
  • the pressure within zone 8 may be maintained from atmospheric up to 600 p.s.i.g., preferably from 50 to 200 p.s.i.g.v and especially about p.s.i.g.
  • sulfur compounds contained within the hydrocarbon feed are converted to hydrogen sulfide and without substantially hydrogenating the olenic or aromatic components of the feed.
  • the resulting mixture of gas, hydrocarbons and hydrogen sulde is conveyed as by means of line 10 t0 a separation zone 11.
  • gaseous components including hydrogen and hydrogen sulfide are separated from the desulfurized hydrocarbons as by cooling the mixture sufficiently to condense the hydrocarbons.
  • the gases are conveyed by means of lines 12 and 14 to sulfur recovery zone 15.
  • the gas stream may be scrubbed with alkaline materials such as aqueous so-dium carbonate, caustic or lime solutions.
  • the gas stream may be here treated with a reagent such as diethanolamine which recovers the sulfur as hydrogen su 1- fide which in turn can be converted to elemental sulfur.
  • a reagent such as diethanolamine which recovers the sulfur as hydrogen su 1- fide which in turn can be converted to elemental sulfur.
  • zone 1S it is generally desired that zone 1S be operated so as to provide a hydrogen-containing gas in line 16 that contains less than 0.1 wt. percent sulfur and preferably less than 0.01%.
  • the naphtha feed does not contain enough sulfur to maintain the;
  • Makeup or fresh hydrogen gas may be introduced within the system by means of line 17.
  • hydrogen gas that contains substantial amounts of sulfur may be introduced within zone 8 by merely recycling at least a portion of the stream in line 12 directly back to zone 8 by means of lines 18, 9 and 6.
  • the use of this procedure and/ or the use of auxiliary feed stocks in line 19 may be particularly followed in order to realize the sulfur/hydrogen mol ratios that are desired in zone 8. Such an eventuality may arise in those instances where the feed stock in line 5 contains such very small amounts of sulfur that the desired sulfur-hydrogen ratios within Zone 8 are impossible to achieve under the feed rates that are otherwise necessary to employ.
  • a hydrocarbon feed mixture consisting of about 1A, benzene, 2/3 normal heptane and 0.5 volume percent thiophene was fed at a rate of 75 cc. per hour over 150 cc. g.) of a catalyst consisting of 0.5 wt. percent Pt on an alumina base maintained at a temperature of 500 F, and 200 p.s.i.g. pressure.
  • Hydrogen was also introduced at a rate of 2.8 c.f./hr. which is equivalent to about 6000 s.c.f. Hz/bbl. of feed.
  • the invention is very effective in providing naphtha of very W sulfur content.
  • the invention is not to be limited to the scope of this particular example. Rather, it has application especially for thermally or catalyticallyy cracked fractions that are incorporated within gasolines, since it desulfurizes such fractions without decreasing their octane ratings, Furthermore, the invention decreases the gumand deposit-forrning tendencies of the fractions without adversely affecting their lead response.
  • a method of desulfurizing a petroleum fraction boiling within the range from about 150 to 400 F. and containing olens, aromatics and from 0.01 to 2 wt. percent sulfur which comprises initially contacting a platinum hydrogenation catalyst that contains from 0.05 to 2 wt. percent platinum with a hydrocarbon mixture boiling within the range from about 150 to 400 F.; said mixture containing no olelins, substantially no aromatics and more than 1 wt. percent sulfur; the mixture being contacted with the catalyst between 400 F. and 1000" F. and -600 p.s.i.g.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US461312A 1954-10-11 1954-10-11 Hydrodesulfurization process employing a presulfided platinum catalyst Expired - Lifetime US2918427A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US461312A US2918427A (en) 1954-10-11 1954-10-11 Hydrodesulfurization process employing a presulfided platinum catalyst
GB27210/55A GB793817A (en) 1954-10-11 1955-09-23 Desulfurization of hydrocarbons and mixtures of hydrocarbons
DEE11357A DE1014259B (de) 1954-10-11 1955-09-30 Verfahren zum Entschwefeln schwefelhaltiger Kohlenwasserstoffgemische
FR1137599D FR1137599A (fr) 1954-10-11 1955-10-06 Procédé de désulfuration d'hydrocarbures

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US461312A US2918427A (en) 1954-10-11 1954-10-11 Hydrodesulfurization process employing a presulfided platinum catalyst

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3640686A (en) * 1970-11-02 1972-02-08 Robert A Farnham Waste water purification

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2440673A (en) * 1946-06-15 1948-05-04 Standard Oil Dev Co Method of utilizing a fuel gas in refining a petroleum fraction
US2512570A (en) * 1948-07-20 1950-06-20 Shell Dev Desulfurization of hydrocarbon oils
US2542970A (en) * 1946-06-15 1951-02-27 Standard Oil Dev Co Refining of cracked naphthas by selective hydrogenation
US2656302A (en) * 1949-09-22 1953-10-20 Anglo Iranian Oil Co Ltd Catalytic desulfurization of petroleum hydrocarbons
US2694671A (en) * 1950-09-01 1954-11-16 Standard Oil Dev Co Selective hydrogenation process
US2697683A (en) * 1950-02-27 1954-12-21 Shell Dev Treatment of hydrocarbon oils
US2761816A (en) * 1954-06-21 1956-09-04 Exxon Research Engineering Co Hydrodesulfurization process using a cobalt molybdate catalyst presulfided with the feed under specific conditions
US2761817A (en) * 1954-06-21 1956-09-04 Exxon Research Engineering Co Hydrodesulfurization process with precoditioned catalyst
US2774718A (en) * 1952-02-19 1956-12-18 Hydrocarbon Research Inc Process for hydrofining a highly olefinic gasoline
US2774719A (en) * 1952-05-16 1956-12-18 Hydrocarbon Research Inc Hydrodesulfurizing a highly olefinic gasoline containing cyclic sulfur compounds

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2440673A (en) * 1946-06-15 1948-05-04 Standard Oil Dev Co Method of utilizing a fuel gas in refining a petroleum fraction
US2542970A (en) * 1946-06-15 1951-02-27 Standard Oil Dev Co Refining of cracked naphthas by selective hydrogenation
US2512570A (en) * 1948-07-20 1950-06-20 Shell Dev Desulfurization of hydrocarbon oils
US2656302A (en) * 1949-09-22 1953-10-20 Anglo Iranian Oil Co Ltd Catalytic desulfurization of petroleum hydrocarbons
US2697683A (en) * 1950-02-27 1954-12-21 Shell Dev Treatment of hydrocarbon oils
US2694671A (en) * 1950-09-01 1954-11-16 Standard Oil Dev Co Selective hydrogenation process
US2774718A (en) * 1952-02-19 1956-12-18 Hydrocarbon Research Inc Process for hydrofining a highly olefinic gasoline
US2774719A (en) * 1952-05-16 1956-12-18 Hydrocarbon Research Inc Hydrodesulfurizing a highly olefinic gasoline containing cyclic sulfur compounds
US2761816A (en) * 1954-06-21 1956-09-04 Exxon Research Engineering Co Hydrodesulfurization process using a cobalt molybdate catalyst presulfided with the feed under specific conditions
US2761817A (en) * 1954-06-21 1956-09-04 Exxon Research Engineering Co Hydrodesulfurization process with precoditioned catalyst

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3640686A (en) * 1970-11-02 1972-02-08 Robert A Farnham Waste water purification

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DE1014259B (de) 1957-08-22
FR1137599A (fr) 1957-05-31
GB793817A (en) 1958-04-23

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