US3337447A - Selective hydrocracking with a sulfur containing cadmium zeolite catalyst - Google Patents

Selective hydrocracking with a sulfur containing cadmium zeolite catalyst Download PDF

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US3337447A
US3337447A US487026A US48702665A US3337447A US 3337447 A US3337447 A US 3337447A US 487026 A US487026 A US 487026A US 48702665 A US48702665 A US 48702665A US 3337447 A US3337447 A US 3337447A
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catalyst
zeolite
cadmium
naphtha
hydrocracking
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US487026A
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Rigney James Arthur
Mason Ralph Burgess
Glen P Hamner
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Priority to US487026A priority Critical patent/US3337447A/en
Priority to GB35471/66A priority patent/GB1126918A/en
Priority to DE19661545290 priority patent/DE1545290A1/de
Priority to FR75154A priority patent/FR1513302A/fr
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    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
    • 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
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers

Definitions

  • This invention relates to the removal of straight-chain hydrocarbons from petroleum-derived feedstocks by their selective conversion in the presence of hydrogen. More particularly, it relates to a selective hydrocracking process which is accomplished in the present of a crystalline metallo alumino-silicate having uniform pore openings less than about 6-Angstrom units in diameter, and preferably about 5 Angstroms.
  • Hydrocarbon conversion and upgrading with crystalline alumino-silicate zeolite catalysts is now well known in the art.
  • the use of these zeolites for hydrocracking has been generally directed to typical petroleumderived feedstocks, such as gas oil, etc., which are customarily converted to lower boiling products useful as gasoline.
  • the crystalline zeolites employed for such purposes usually have uniform pore openings of about 6 to Angstroms and are therefore nonselective; that is, substantially all of the feed molecules are admitted into the zeolite pore structure.
  • selective hyd-rocracking of only certain molecular species is obviously to be desired.
  • One such purpose for example, is the octane improvement of naphtha fractions by selectively hydrocracking only straight-chain hydrocarbons (e.g., olefins, paraifins, etc.) which tend to be low octane producing, and thereafter removing the hydrocracked products and recovering a higher octane product.
  • Another purpose is the selective hydrocracking of the straight-chain hydrocarbon content of lube oil and gas oil fractions for pour point reduction or dewaxing.
  • nonselective large pore (e.g., 6 to 15 Angstroms) crystalline zeolite for such purposes is ineifectual, since desired feed molecules, e.g., aromatics, are admitted into the zeolite pores and hydrocracked along with the straight-chain hydrocarbons.
  • Upgrading of cleanliness of gum-forming properties is also quite important with certain olefinic naphthas, especially naphthas produced in thermal cracking or coking operations.
  • upgrading is usually accomplished by either passing the naphtha over' a catalytic cracking catalyst or by hydrofining. Again the first of these alternates, i.e., catalytic cracking, results in an undesirable high gas and coke make; whereas the second, i.e., hydrofining, results in an octane number loss.
  • S-Angstrom zeolites having uniform pore openings of less than 6 Angstroms, preferably about 5 Angstroms.
  • the essence of this invention resides in the surprising discovery that a particular sulfided cation form of these S-Angstrom zeolites is substantially superior to other forms.
  • the S-Angstrom zeolite should be cadmium containing, preferably having a major portion of its cation content supplied by a cadmium cation, and most preferably having been ex changed solely with cadmium cation for replacement of alkali metal originally in the zeolite.
  • naphthas may be successfully upgraded by contacting them at suitable conditions of temperature and pressure in the presence of hydrogen with a sulfided cadmium-containing crystalline metallo alumino-silicate zeolite having uniform effective pore openings of less than 6 Angstroms, preferably about 5 Angstroms.
  • upgrading is meant any hydro technique resulting in the formation of an improved or preferred product. This would include improved octane rating and cleanliness, lower sulfur content, etc.
  • the hydro techniques contemplated include such processes as hydrofining, 'hydrocracking, hydrodealkylation, hydrogen transfer, etc., with the preferred process being hydrocracking. These processes will usually be con-ducted at elevated temperature and pressure in the presence of hydrogen.
  • the essence of the present invention which distinguishes it from the above prior art teachings, lies in the surprising discovery that certain unique S-Angstrom crystalline alumino-silicates are superior catalyst components for selective conversion reactions in general and selective hydrocracking in particular.
  • the S-Angstrom crystalline alumino-silicate employed herein in the cadmium cationexchanged form can be free of any metallic hydrogenation catalyzing component and yet will surprisingly and uniquely exhibit selective hydrocracking activity.
  • the catalyst used in the present invention need not include such metallic hydrogenation component and yet, surprisingly, is a highly effective hydroconversion catalyst.
  • the process of the invention should also be distinguished from the conventional adsorption-desorption processes which are well known in the art.
  • the present process involves a selective hydrocr-acking of straight-chain hydrocarbons.
  • certain low octane-producing molecules such as straight-chain hydrocarbons
  • gaseous materials such as butane and lighter fractions
  • crystalline metallo alumino-silicate zeolites having uniform pore openings of about Angstroms contemplated for use in this invention are well known and available in synthetic or natural form.
  • a suitable starting material referred to as Zeolite A in US. Patent No. 2,882,243, has a molar formula (dehydrated form) of where M is a metal usually sodium and n is its valence. It may be prepared by heating a mixture containing Na O, A1 0 SiO and H 0 (supplied by suit-able source materials) at a temperature of about 100 C. for 15 mmutes to 90 hours or longer. Suitable ratios of these reactants are fully described in the aforementioned patent.
  • One suitable process for preparing such materials synthetically involves, for example, the mixing of sodium silicate, preferably sodium metasilicate, with sodium aluminate under carefully controlled conditions.
  • the sodium silicate employed should have a ratio of soda to silica between about 0.8 to 1 and about 2 to 1, and the sodium aluminate may have a ratio of soda to alumina in the range of from about 1 to 1 to about 3 to 1.
  • the amounts of the sodium silicate and sodium aluminate solutions employed should be such that the ratio of silica to alumina in the final mixture ranges from about 0.8 to 1 to about 3 to 1 and preferably from about 1.1
  • the aluminate is added to the silicate at ambient temperature with sufficient agitation to produce a homogeneous mixture.
  • the mixture is then heated to a temperature of from about to about 215 F. and held at that temperature for a period of from about 0.5 to about 3 hours or longer.
  • the crystals may be formed at lower temperatures but longer reaction periods will be required.
  • temperatures above about 250 F. a crystalline composition having the requisite uniform size pore openings is not obtained.
  • the pH of the solution should be main tained on the alkaline side, at about 12 or higher. At lower pH levels, crystals having the desired properties are not as readily formed.
  • the products produced by the above procedure will have uniform pore openings of about 4 Angstroms as produced in the sodium form. They may then be converted to products having uniform pore openings of about 5 Angstroms by replacement of the sodium via conventional ionexchange techniques with various cations, such as calcium, magnesium cobalt, nickel, iron, manganese, etc., all of which are not suitable for purposes of this invention.
  • Natural zeolites having effective pore diameters less than 6 Angstroms, and preferably about 5 Angstroms, are also herein contemplated and will include such materials as erionite, chabazite, analcite, lebrynite, natrolite, etc.
  • both the natural and synthetic varieties of 5-Angstrom zeolites are contemplated with the only limitation being one of pore size.
  • the pore size must be sufficient to substantially admit the straightchain hydrocarbons but insufficient to admit the valuable high octane-producing components, such as the aromatics, so as to avoid their hydrocracking. This capacity should, therefore, be demonstrated at the particular hydrocracking conditions contemplated, since the effective pore diameter of these zeolite materials often varies with temperature and pressure.
  • the catalyst used in the present invention is prepared from a crystalline alumino-silicate which, after cadmium cation exchange, has uniform effective pore openings less than 6 Angstroms, and preferably about 5 Angstroms, in diameter.
  • the most preferred cation solution will be an aqueous solution of a cadmium salt, such as cadmium chloride or cadmium nitrate.
  • the extent of ion exchange should be sufficient to reduce the alkali metal, e.g., sodium content of the zeolite to less than 10 wt. percent, and preferably less than 5 wt. percent.
  • the ion exchange is prefer ably conducted to cause at least 25%, and more prefer ably greater than 50%, of the exchangeable cation content to be divalent by replacement with the cadmium cation. It will be understood that although the most preferred catalysts will be prepared by using cadmium cation as the sole exchanging cation, the presence of cadmium together with other exchanging cations will also be highly useful.
  • the present invention contemplates the use of about a S-Angstrom zeolite containing cadmium cation,
  • the zeolite will have a major portion of its cation content supplied by cadmium with perhaps minor portions of residual sodium, as well as minor portions of other ions which may also have been introduced via exchange for various purposes.
  • the catalyst can be combined with an active metallic hydrogenation component which may be chosen from Groups V-B, VI-B, VII-B, or VIII of the Periodic Table and which is suitably exemplified by the metals cobalt, nickel, platinum, palladium, etc.
  • the hydrogenation component may be in the form of the free metal as in the case of platinum group metals or as the oxide or sulfide as in the case of cobalt, etc., or mixtures of such metals, oxides, or sulfides.
  • Platinum group metals i.e., metals of the platinum and palladium series
  • palladium being particularly preferred.
  • Incorporation of the hydrogenation component may be accomplished by any conventional technique, such as ion exchange followed by reduction, impregnation, etc.
  • the cadmium-exchanged alumino-silicate is preferably impregnated with an ammoniacal solution of palladium chloride sufficient to produce the desired amount of hydrogenation metal in the final product, and then dried and calcined at a temperature of 800 to 1000 F. Reduction of the metal is then accomplished either separately or in the hydrocracking reaction per se.
  • the amount of hydrogenation component may range from about 0.1 to about 25 wt. percent, based on the weight of final product. In the case of platinum group metals, e.g., palladium, the preferred amount will be in the range of about 0.1 to 6, e.g., 0.5 to 3 wt. percent, based on dry catalyst.
  • the activity and effectiveness of the catalysts used herein are critically dependent upon contact with sulfur prior to their exposure to high temperature conditions employed in the selective conversion processes described herein.
  • the catalyst is sulfactivated by contact either with a sulfur-containing feed or, if the feed has a low sulfur content, with hydrogen sulfide or an added sulfur compound which is readily convertible to hydrogen sulfide at the hydroconditions employed, e.g., carbon disulfide, etc.
  • the extent of this sulfactivation treatment should be sufficient to incorporate 0.5 to 15 wt. percent sulfur into the catalyst. It has been further found that the temperature to which the catalyst is subjected during the sulfactivation step is also critical and must be maintained below about 1000 F., preferably 850 F., most preferably between about 450 and 750 F. The effect of sulfactivation will be demonstrated in the examples to follow.
  • the catalyst used in the present invention has been found to be highly effective for the upgrading of naphtha feeds, although the invention is not to be so limited. Markedly improved octane number is achieved with a very low loss of naphtha yield. Additionally, the coke make produced in the process is substantially lower than that experienced in catalytic cracking.
  • the feedstocks contemplated for use in the present invention may be any of the typical petroleum hydrocarbon feeds, containing straight-chain hydrocarbons which are desirably removed for the particular intended use of the end product.
  • the feeds contemplated include either low-boiling naphtha or high boiling naphtha-containing feeds, the latter typically having a boiling range of about 250 to 450, preferably 300 to 430 F.
  • These feeds may be exemplified by virgin naphtha fractions, heavy coker naphtha, heavy steamcracked naphtha, heavy catalytic naphtha, and the like.
  • Typical hydrocracking conditions which are suitable for purposes of the present invention include a temperature of 400 to 950 F., preferably 650 to 850 F.; a pressure of 200 to 4000, preferably 500 to 2500 p.s.i.g.; a space velocity of 0.2 to 20, preferably 0.4 to 2 v./v./hr.; and a hydrogen rate of 1,000 to 10,000, preferably 1500 to 5000 standard cubic feet of hydrogen per barrel of feed.
  • EXAMPLE 1 This example illustrates the preparation and use of a cadmium-containing crystalline alumino-silicate having uniform pore openings of about 5 Angstroms in the selective hydrocracking of a C 'to C naphtha feed derived from an Arabian crude.
  • the cadmium crystalline alumino-silicate was prepared as follows:
  • a charge of 500 grams of commercial sodium Zeolite A having pore openings of about 4 Angstroms in diameter and a silica-to-alumina mole ratio of about 2 to 1 was air-exposed overnight and then stirred in 2500 ml. of distilled water containing one pound of cadmium chloride hydrate. After 18 hours the solution was replaced with a fresh portion and stirring was resumed for 24 hours. Again, the solution was replaced with a fresh portion and stirring was resumed for 24 hours. The slurry was then filtered, washed free of chloride ion, and dried at 150 C. overnight. The catalyst had a uniform pore size of about 5 Angstroms, and analyzed 1.67 wt. percent sodium and 30.60 wt. percent cadmium.
  • the above catalyst was presulfided prior to use in the selective hydrocracking of the C to C naphtha feed. Specifically, the catalyst was charged to a testing unit and sulfided with a mixture of'10% hydrogen sulfide in hydrogen at the rate of 1.5 c.f./hr. for each cc. of catalyst. The temperature was maintained at 200 F. for two hours, then raised at a rate of F./ hr. to 600 P. where it was held for one hour. The procedure is known to incorporate between 2.5 and 4.5 wt. percent sulfur into the catalyst.
  • the presulfided catalyst was then used to selectively hydrocrack a C to C naphtha feed having the following analysis at 850 F., 500 p.s.i.g., 0.5 v./v./hr. and 2000 s.c.f. H /B.
  • the feed contained 0.25 wt. percent added CS to ensure retention of the cadmium metal by the catalyst.
  • EXAMPLE 3 The effect of sulfur activation of cadmium zeolite A was further demonstrated.
  • sodium zeolite A was ion exchanged at room temperature with cadmium chloride solution using concentrations disclosed in Example 1.
  • a portion of the product was compacted into A -inch pellets and 170 cc. of the pellets were charged to a fixed bed testing unit.
  • the catalyst was heated to 300 F. in a stream of nitrogen and then hydrogen at atmospheric pressure.
  • the system was then maintained for about 64 hours at 400 F. with hydrogen flow at atmospheric pressure.
  • the system was pressurized with hydrogen at 500 p.s.i.g. and upon increasing the temperature to 500 F.
  • Conversion was conducted at 500 p.s.i.g., 0.5 v./v./hr., and an exit hydrogen rate of 1895 c.f./B.
  • the temperature was varied over different time periods, as follows:
  • a palladium-zinc S-Angstrom zeolite prepared in substantial accordance with the procedure described on pages 13 and 14 of copending application Ser. No. 444,796 was utilized, after presulfiding in hydrocracking operation with a light naphtha feed containing 0.25 wt. percent carbon disulfide, at 700 to 850 F., and 500 to 1000 p.s.i.g., to selectively hydrocrack the C to C naphtha feed of Example 1. Under comparable conditions of temperature, pressure, feed rate and hydrogen rate, the following comparison with the results of Example 1 was obtained.
  • a process for reducing the straight-chain hydrocarbon content of a hydrocarbon feedstock by selectively hydrocracking same which comprises contacting said feedstock at elevated temperature and pressure in the presence of hydrogen with a catalyst comprising a crystalline alumino-silicate zeolite containing cadmium in an amount corresponding to at least 25% of its cationic content and having uniform pore openings of about 5 Angstrom units, wherein said catalyst contains 0.5 to 15 wt. percent sulfur, and recovering a hydrocarbon product having a substantially reduced straight-chain hydrocarbon content.
  • a catalyst composition comprising a metallic hydrogenation component combined with a crystalline alumino-silicate zeolite containing cadmium in an amount corresponding to at least 25% of its cationic content and having uniform pore openings of about Angstrom units, said catalyst composition additionally comprising 0.5 to 15 wt. percent sulfur.
  • composition of claim 10 wherein said hydrogenation component comprises a platinum group metal.
  • a process for improving the octane rating of naphtha fractions by selective hydrocracking of straightchain hydrocarbons contained therein which comprises contacting said naphtha fractions at elevated temperature and pressure in the presence of hydrogen with a catalyst comprising a crystalline alumino-silicate zeolite having uniform pore openings of about 5 Angrstoms, said zeolite having at least 25% of its cation content supplied by cadmium cation, said catalyst containing 0.5 to 15 wt. percent sulfur, and recovering a naphtha product having substantially reduced straight-chain hydrocarbon content and an improved octane rating.
  • a process for selectively hydrocracking naphtha fractions containing straight-chain hydrocarbons and nonstraight-chain hydrocarbons which comprises contacting said fractions in a catalyst zone maintained at elevated temperature and pressure, flowing a substantial amount of hydrogen gas into said pressurized catalyst zone, and recovering naphtha product having a substantially reduced straight-chain hydrocarbon content and a substantially improved motor octane rating, wherein.
  • the catalyst in said zone comprises a sulfactivated crystalline alumino-silicate zeolite having uniform pore openings of about 5 Angstrom units and containing cadmium in an amount corresponding to at least 25% of its cationic content and further containing 0.5 to 15 wt. percent sulfur.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
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US487026A 1965-09-13 1965-09-13 Selective hydrocracking with a sulfur containing cadmium zeolite catalyst Expired - Lifetime US3337447A (en)

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Application Number Priority Date Filing Date Title
US487026A US3337447A (en) 1965-09-13 1965-09-13 Selective hydrocracking with a sulfur containing cadmium zeolite catalyst
GB35471/66A GB1126918A (en) 1965-09-13 1966-08-08 Selective conversion process
DE19661545290 DE1545290A1 (de) 1965-09-13 1966-08-12 Verfahren zur Qualitaetsverbesserung von geradkettige Kohlenwasserstoffe enthaltenden Erdoel-Kohlenwasserstoffgemischen
FR75154A FR1513302A (fr) 1965-09-13 1966-09-02 Procédé de conversion sélective de produits pétroliers

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3471412A (en) * 1967-01-25 1969-10-07 Mobil Oil Corp Catalyst for hydrocarbon conversion and method for its preparation
US3516947A (en) * 1967-05-04 1970-06-23 Canadian Patents Dev Catalysts having stable free radicals containing sulfur
US5141906A (en) * 1990-06-29 1992-08-25 Toyota Jidosha Kabushiki Kaisha Catalyst for purifying exhaust gas

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2971904A (en) * 1957-02-12 1961-02-14 Exxon Research Engineering Co Petroleum process catalyst supported on a molecular sieve zeolite
US3013983A (en) * 1958-09-24 1961-12-19 Union Carbide Corp Cadmium-loaded molecular sieve
US3039953A (en) * 1958-09-17 1962-06-19 Exxon Research Engineering Co Selective conversion of normal paraffins with a crystalline zeolite
US3175967A (en) * 1962-01-11 1965-03-30 Socony Mobil Oil Co Inc Catalytic conversion with activated catalyst
US3243366A (en) * 1958-08-18 1966-03-29 Exxon Research Engineering Co Dewaxing by contact with a crystalline zeolitic adsorbent

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2971904A (en) * 1957-02-12 1961-02-14 Exxon Research Engineering Co Petroleum process catalyst supported on a molecular sieve zeolite
US3243366A (en) * 1958-08-18 1966-03-29 Exxon Research Engineering Co Dewaxing by contact with a crystalline zeolitic adsorbent
US3039953A (en) * 1958-09-17 1962-06-19 Exxon Research Engineering Co Selective conversion of normal paraffins with a crystalline zeolite
US3013983A (en) * 1958-09-24 1961-12-19 Union Carbide Corp Cadmium-loaded molecular sieve
US3175967A (en) * 1962-01-11 1965-03-30 Socony Mobil Oil Co Inc Catalytic conversion with activated catalyst

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3471412A (en) * 1967-01-25 1969-10-07 Mobil Oil Corp Catalyst for hydrocarbon conversion and method for its preparation
US3516947A (en) * 1967-05-04 1970-06-23 Canadian Patents Dev Catalysts having stable free radicals containing sulfur
US5141906A (en) * 1990-06-29 1992-08-25 Toyota Jidosha Kabushiki Kaisha Catalyst for purifying exhaust gas

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FR1513302A (fr) 1968-02-16
DE1545290A1 (de) 1970-07-09
GB1126918A (en) 1968-09-11

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