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
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
  • C10G65/10—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking steps
• • 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
• • 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
  • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
  • B01J29/068—Noble metals
• • 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
• • 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
  • C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
• • 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
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
  • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps

Definitions

• This invention relates to the upgrading of naphtha by selective hydro conversion processes, particularly hydrocracking. More particularly, it relates to the upgrading of naphthas by selective hydrocracking which is accomplished in the presence of a catalyst comprising a specific form of a crystalline metallo alumino-silicate having uniform pore openings of about 5 A.
• the upgrading will consist of either improving the octane rating or improving the cleanliness or gum forming properties of the naphtha.
• Upgrading of the octane rating is usually accomplished by means of such processes as thermal or catalytic reforming.
• the desired product is usually of about the same boiling range as the feed, with the molecules having been rearranged or reformed into higher octaneproducing compounds.
• naphthas may be successfully upgraded by contacting them at suitable conditions of temperature and pressure in the'presence of hydrogen with a zinc-containing crystalline metallo alumino-silicate zeolite having uniform effective pore openings of about 5 A.
• 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 conducted at elevated temperature and pressure in the presence of hydrogen.
• the following table sets forth suitable operating conditions for typical hydro techniques contemplated by the present invention.
• hydrocracking for example, to upgrade naphthas is often selfdefeating since products boiling below the range of the feed are formed, thereby lowering the naphtha yield.
• Hydroforming or catalytic reforming are also not practical with certain naphtha feeds, e.g., coker naphthas, which contain appreciable sulfur, nitrogen and diolefins, again because of excessive coke make and rapid catalyst deactivation.
• catalytic hydroforming which depends
• the catalyst used in the present invention has been found to be highly effective for the upgrading of naphtha feeds. Markedly improved octane number is achieved with a very low loss in naphtha yield, and a substantially lower coke make than that experienced in catalytic cracking. It should be emphasized that the zinc 5 A. alumino-silicate zeolite need not be combined with a metallic catalytic hydrogenation component, and yet effective selective hydrocracking can be achieved.
• the activity and effectiveness of the catalysts used herein may be substantially improved by contact with sulfur prior to their use in the selective hydrocracking processes.
• the catalyst is preferably sulfactivated to enhance its activity 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 hydro conditions 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. The beneficial effect of sulfactivation will be demonstrated in the examples to follow.
• molecular sieves for such purposes as dewaxing, etc. These uses derive from the ability of these crystalline zeolite materials to selectively admit certain sized molecules into their pores while rejecting others. Since these materials are now well known adsorbents and catalysts, they provide highly efficient and valuable tools for selectively converting specified constituents of a hydrocarbon feed.
• US. Patent 3,039,953 discloses the selective conversion of normal paraflins with a 5 A. molecular sieve zeolite.
• U.S. Patent 3,140,322 relates generally to selective catalytic conversion utilizing crystalline zeolites, and mentions dehydration, catalytic cracking, hydrogenation, etc.
• the present invention is to be distinguished from these and similar teachings.
• the 5 A. crystalline aluminosilicate employed herein in the zinc cation exchanged 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 present invention is to be further distinguished from the above prior art teachings by the surprising discovery that a particular 5 A. crystalline aluminosilicate zeolite; namely, the zinc-containing form, is so superior to other cation exchanged forms, including the nickel form, as to clearly be the material of choice.
• the use of the surprisingly more active zinc form in the process of the invention is therefore to be regarded as essential.
• 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 selective treatment of certain less desired components to lower boiling components and does not involve merely a mechanical separation as does the .conventional adsorption-desorption phenomenon.
• the increase in octane number of the naphtha product is due to conversion of normally liquid, straight chain hydrocarbons, both parafiinic or olefinic, to butane and lighter components.
• the converted products are not re tained within the pores of the zeolite Which remain relatively free of hydrocarbons, and a desorption step is unnecessary thereby making the process economically attractive.
• contemplated for 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' l, 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 l.
• 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 to 1 to about 2 to 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 180 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. At 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 maintained on the alkaline side, at about 12 or higher.
• a suitable starting material referred to as Zeolite A in US. Patent 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 0, A1 0 SiO and H 0 (supplied by suitable source materials) at a temperature of about 100 C. for 15 minutes to 90 hours or longer. Suitable ratios of these reactants are fully described in the aforementioned patent.
• the products produced by the above procedure will have uniform pore openings of about '4 A. as produced in the sodium form. They may then be converted to products having uniform pore openings of about 5 A. by replacement of the sodium via conventional ionexchange techniques with various cations such as calcium, magnesium, cobalt, nickel, iron, manganese, zinc, etc., all of which are not suitable for purposes of this invention. 7
• Natural zeolites having elfective pore diameters of about 5 A. are also herein contemplated and will include such materials as erionite, chabazite, analcite,'mordenite,
• lebrynite lebrynite, natrolite, etc.
• both the natural and synthetic varieties of 5 A. zeolites are contemplated with the only limitation being one of pore size.
• the pore size must "be sufiicient to substantially admit the straight chain 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 cation utilized must specifically be a polyvalent, difiicultly reducible cation.
• difiiculty reducible is meant a cation which is not reducible to a lower valence state or to the free metal by hydrogen at the hydrocracking conditions utilized.
• manganese and zinc have been found suitable for purposes of the present invention, with zinc being so substantially better than manganese that it is the cation of choice.
• the catalyst used in the present invention is prepared from a crystalline alumino-silicate which, after zinc cation exchange, has uniform eifective pore openings of about 5 A. in diameter.
• the most preferred cation solution will be an aqueous solution of a zinc salt such as zinc chloride, Zinc acetate, etc.
• the extent of ion excations by either ion-exchanging the zeolite with mixed salt solution or by sequential ion-exchange treatments.
• the zeolite will have a major portion of its cation content supplied by zinc with perhaps minor portions of residual sodium as well as minor portions of other ions which may also have been introduced via ion exchange for various purposes.
• the feedstocks contemplated for use in the present process will generally be naphtha or high naphtha-containing feeds and may consist of either low boiling or high boiling naphthas.
• a typical low boiling feed has a boiling range of about 50 to 350 F., preferably 80 to 200 F.
• the heavy naphtha has a boiling range of 275 to 550 F., preferably 300 to 450 F.
• These naphthas, both low boiling and high boiling are exemplified by virgin naphtha fractions such as C C naphtha, heavy virgin naphtha, heavy coker naphtha, heavy steam cracked naphtha, heavy catalytic naphtha, etc.
• Example 1 This example illustrates the preparation and use of a Zinc-containing crystalline alumino-silicate having uniform pore openings of about 5 A. in the selective hydrocracking of a heavy coker naptha feed and a C C naphtha feed.
• the zinc crystalline alumino-silicate was prepared as follows:
• the excellent catalyst performance with the light C -C naphtha is attributed to previous sulfactivation by the sulfur in the coker naphtha feed which initially contacted the catalyst.
• the octane number improvement in the coker naphtha feed which ordinarily does not respond Well to conventional treatment such as hydroforming, is con sidered to be outstanding.
• the superior upgrading ability of the selective hydrocracking process of the invention is compared toconventional hydrofining or catalytic cracking in the folowing table.
• the dried product was pelleted and charged to small pilot plant reactors, heated in a hydrogen stream at atmospheric pressure and 850 F.', and used to successively selectively hydrocrack the above feeds at 0.5 v./v./hr., 500 p.s.i.g., and a hydrogen rate of 2000 to 3000 s.c./bbl. of feed.
• the results are shown in the following table.
• Example 2 This example demonstrates the superiority of the zinc modification of the catalyst of the invention over other cationic forms.
• the catalyst of Example 1 was used. An Arabian C -C light naphtha having a boiling range of 110 to 156 F. overhead) and a sulfur content of 1% was employed as the feedstock. The catalyst was sulfactivated by contact with the feed containing 1% added carbon disulfide. Catalyst performance was measured by the disappearance of normal C and C parafiins and their conversion to C gas produced by selective hydrocracking of these components. The results are shown below in Table III.
• Example 4 To demonstrate the advantage of the selective hydrocracking process of the invention, the zinc catalyst of the previous examples was used for the selective catalytic cracking of the Arabian C -C naphtha feed at the same temperature and feed rate but in the absence of hydrogen pressure and hydrogen flow. (To avoid eflfects of extraneous gases the system was purged with nitrogen and then with hydrogen, and hydrogen was present at one atmosphere pressure at the start of the operation.) The results,
• Example 3 The disappearance of normal paraffins, the amount of C4- gas from the selective hydrocracking of the normal paraffins, and the high ratio of paraffins to olefins in the C; gas, all demonstrate the superiority of the hydro operation as compared to the non-hydro operation.
• Example 5 Foregoing examples have illustrated selective hydrocracking of normal parafiins with sulfactivated zinc 5 A.
• Aromatics wt. percent 1. 5 4. 2 0. 3 O. 5 Naphthenes, wt. percent- 8. 7 16.2 4. 0 3. 2 Parafiins, wt. percent 89. 8 79. G 95. 7 96. 3
• the zinc faujasite produced more extensive overall hydrocracking, but of a relatively nonselective nature, as indicated by the loss of aromatics and naphthenes.
• a process for improving the octane rating of naphtha fractions which comprises contacting said fractions at elevated temperature and pressure in the presence of hydrogen with a sulfactivated catalyst comprising a zinc-containing crystalline alumino-silicate zeolite having uniform pore openings of about 5 A.
• a process for improving the octane rating of naphtha fractions by selectively hydrocracking straight chain hydrocarbons contained therein which comprises contacting said naphtha fractions at hydrocracking conditions in the presence of hydrogen with a sulfactivated catalyst comprising a crystalline alumino-silicate zeolite having uniform pore openings of about 5 A., said zeolite having a major proportion of its cation content supplied by zinc cation, and recovering a naphtha product of improved octane rating.
• a catalyst composition comprising a sulfactivated zinc-containing crystalline alumino-silicate zeolite having uniform pore openings of about 5 A.
• composition of claim 13 wherein a major proportion of the cation content of said zeolite is supplied by zinc cation.
• composition of claim 13 which contains about 0.5 to 15 wt. percent sulfur.
• hydrocracking conditions include a temperature of 600 to 850 F., a pressure of 500 to 2500 p.s.i.g., a hydrogen rate of 1000 to 10,000 cubic feet per barrel and a feed rate of 0.25 to 5 v./v./-h r.
• a process for selectively hydrocracking naphtha fractions containing straight-chain hydrocarbons and non-straight chain hydrocarbons to thereby improve the octane rating 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 straightchain 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 augstrom units and containing zinc.
• a catalyst composition comprising a sulfactivated crystalline aluminosilicate zeolite having uniform pore openings of about 5 angstrom units, said zeolite containing zinc but being otherwise free of added metallic hydrogenation component.

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• 1965
  • 1965-04-01 US US444812A patent/US3331768A/en not_active Expired - Lifetime
  • 1965-04-01 US US444796A patent/US3331767A/en not_active Expired - Lifetime
• 1966
  • 1966-03-21 GB GB12370/66A patent/GB1133386A/en not_active Expired
  • 1966-03-26 NO NO162310A patent/NO119753B/no unknown
  • 1966-03-31 DE DEE31356A patent/DE1301409B/de active Pending
  • 1966-03-31 SE SE04326/66A patent/SE339852B/xx unknown
  • 1966-04-01 BE BE678909D patent/BE678909A/xx unknown
  • 1966-04-01 NL NL666604373A patent/NL152294B/xx not_active IP Right Cessation
  • 1966-04-01 CH CH481366A patent/CH490475A/de not_active IP Right Cessation
• 1968
  • 1968-04-17 GB GB08082/68A patent/GB1214705A/en not_active Expired

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