EP0107375A1 - Katalytischer Krackprozess unter Verwendung gepulverter Zeolithkatalysatoren - Google Patents

Katalytischer Krackprozess unter Verwendung gepulverter Zeolithkatalysatoren Download PDF

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Publication number
EP0107375A1
EP0107375A1 EP83305769A EP83305769A EP0107375A1 EP 0107375 A1 EP0107375 A1 EP 0107375A1 EP 83305769 A EP83305769 A EP 83305769A EP 83305769 A EP83305769 A EP 83305769A EP 0107375 A1 EP0107375 A1 EP 0107375A1
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EP
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Prior art keywords
catalyst
feed
zeolite
process according
solid
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Application number
EP83305769A
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English (en)
French (fr)
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EP0107375B1 (de
Inventor
Nai Yuen Chen
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ExxonMobil Oil Corp
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Mobil Oil Corp
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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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves

Definitions

  • This invention relates to a catalytic cracking process using a crystalline zeolite of extremely small particle size as cracking catalyst.
  • Crystalline zeolites are extensively employed in commercial operations as catalysts for the production of gasoline. In practice they are combined with a suitable matrix, such as an inorganic oxide, to form either a bead suitable for use in moving-bed installations or a fluidizable catalyst particle suitable for use in FCC installations.
  • Gas oil feed is contacted with the catalyst in a reactor until the catalyst is deactivated by deposition of coke.
  • the catalyst is then passed through a regenerator in which the coke is burned off. Hot regenerated catalyst is then re-introduced into the reactor to contact the feed again. The cycle repeats continuously.
  • Disclosures of catalytic cracking of gas oil with crystalline zeolites include U.S. Patent Nos. 3,140,249, 3,140,251 and 3,140,253, in which the particle size of the catalyst composite employed is either in the range of about 0.08 to 0.25 inches (for moving-bed operation) or the range of 10 to 150 microns (for FCC operation).
  • the matrices employed include both catalytically active materials, such as silica-alumina, and catalytically inactive materials, such as silica.
  • the circulation rate of such a catalyst composite is tied to its catalytic cracking function. Thus, for example, in a typical FCC operation, circulation rate of a matrix and circulation rate of a catalyst are inherently tied together and this rate is dependent on catalyst activity.
  • the extent to which coke is removed in regeneration is directly tied to the restoration of the catalytic activity of the catalyst composite which, in turn, controls the rate of circulation of the catalyst into the cracking unit in order to maintain a stable operation.
  • U.S. Patent No. 4,263,126 discloses the use as catalyst of a powdered crystalline aluminosilicate zeolite alone or in a matrix in order to aid in physical removal of the catalyst from the product or products.
  • a cracking process in which a hydrocarbon feed is contacted with a crystalline zeolite catalyst is characterized by the fact that said feed contacts both said catalyst, in the form of particles 0.01 to 5 ⁇ m in size and of an alpha activity of at least 500, and a hot, substantially catalytically inert solid in the form of particles 30 to 300 ⁇ m in size, whereafter said solid is separated and calcined and the resulting hot calcined solid recirculated to contact the feed, the weight ratio of zeolite catalyst to feed during the contacting being no greater than 0.1, preferably 40 to 2000 ppm.
  • Preferred zeolites are zeolite X, Y, L, ZSM-5, ZSM-11, ZSM-12 and/or beta; preferred solids comprise sand, clay, dolomite, glass and/or metal, advantageously processing a surface area of at least 10 m 2 /g.
  • the hot solid contacts unheated feed in which the zeolite catalyst is already dispersed; and at least part of the zeolite catalyst may, after contact with the feed, be separated therefrom, calcined and recirculated to contact the feed.
  • Contact between catalyst, solids and feed usually occurs at a temperature of 300 to 650 0 C, with a residence time of 2 to 10 seconds at a solids:oil ratio of 5:1 to 12:1. It is preferred that the particle size of the zeolite be no greater than 2 ⁇ m.
  • the powdered zeolite can thus either be discarded or a portion of the same entering an air calciner with the heat carrier solids can be recovered from the flue gas via conventional means, such as by using an electrostatic precipitator and/or bag filters, and recycled if desired.
  • a key aspect of the invention is the separation of the catalytic cracking function from the circulating solids.
  • the circulation rate of the solids is not tied to the catalytic activity but can be varied to the limit of the particular catalytic cracking unit being utilized, taking full advantage of its mechanical and material design.
  • neither the circulating solids themselves or the rate at which they are recirculated are determined by properties of the crystalline zeolite, which need not be recycled at all or can be recycled at a rate which is different from the rate at which the solids are recirculated.
  • the catalyst-to-oil.ratio is reduced from the conventional commercial operation of about 5:1 down to 40-2000 ppm per weight of oil - a reduction of more than 125,000-fold. Larger quantities of catalyst may be used but there is no particular added advantage to using more catalyst than is necessary effectively to catalyze the cracking of gas oil to gasoline.
  • the hot solids which are circulated to provide the necessary heat for the cracking reaction are not narrowly critical in nature, and since their circulation rate is divorced from the catalytic cracking activity of the powdered zeolite catalyst they can include such relatively low-cost substances as sand, dolomite, clay minerals, glass and metal particles.
  • the prefrred solid materials which are used as circulating heat carriers are materials which have substantially no catalytic cracking activity and their function would be merely to provide the necessary heat for the catalytic cracking reaction.
  • catalytically active materials though not preferred, can also be used. Such materials include silica alumina, silica-zirconia, silica-titania, acid treated clays, etc.
  • the circulating solid have a high surface area, particularly when normally bothersome feeds such as heavy oils, resids or high metal containing feeds are used.
  • the circulating solid of high surface area serves to trap out metal and coke.
  • the preferred surface area should be greater than about 10 sq. meters/gm.
  • coke particles can serve as the circulating solids.
  • the powdered superactive crystalline aluminosilicate zeolite may be dispersed in a coke gas oil or vacuum resid and introduced into a fluid coker.
  • Crystalline aluminosilicate zeolites which are useful in the novel process of this invention are extremely well known in the art and include zeolite X, Y, Beta, L, as well as mixtures of the above with smaller pore zeolites such as erionite, mordenite, ZSM-5, ZSM-8, ZSM-11 and ZSM-12 - providing they possess the appropriate alpha activity.
  • the preferred crystalline aluminosilicate zeolites may include zeolite X and Y, particularly in their rare earth, acid, or rare earth-acid form. A mixture of zeolites can be used. One may commence the process with one zeolite then change it to another in order to meet product demand.
  • the heat carrier solid be of a particle size which is substantially in excess of the micron size of the powdered crystalline aluminosilicate zeolite. Since it is desired to separate the heat transfer function from the catalytic function, it is also necessary to be able to separate the heat circulating solids from the powdered crystalline aluminosilicate zeolite. To the extent that the heat circulating solids have a particle size greater than the powdered crystalline aluminosilicate zeolite, separation is easier.
  • the expression "heat circulating solid” as used throughout the specification and claims is intended to mean a solid material which is preferably catalytically inert and which has a particle size of from 30 to 300 microns and even more desirably from 45 to 200 microns. Blending of feedstock and catalyst may be carried out before the feedstock is introduced into the reactor. In such a mode of operation, it is preferred to bypass or to eliminate the feed preheater in order to avoid catalyst deactivation. However, if it becomes necessary to use a feed preheater, another mode of operation is to disperse the catalyst in a separate cold hydrocarbon stream and inject it directly into the catalytic cracker whilst the remaining portion of the hydrocarbon feed, e.g. gas oil, is passed through the feed preheater.
  • the hydrocarbon feed e.g. gas oil
  • Another advantage of the invention is that it is possible to incorporate additional functions into the circulating solids, such as so 2 emission control by the use of antimony compounds or carbon monoxide combustion catalysts such as trace amounts of platinum or other well known materials which have an oxidation function.
  • the single figure of the Drawing is a schematic diagram of a process in accordance with the invention.
  • a powdered crystalline aluminosilicate is dispersed into a hydrocarbon feed and the mixture is fed into mixing zone 1 wherein it contacts hot solids such as sand, which enter into mixing zone 1 through line 3.
  • hot solids such as sand
  • mixing zone 1 the hot solids and the relatively cold catalyst-oil mixture are equilibrated and enter into reactor 2 wherein the hydrocarbon oil is catalytically cracked into lower molecular weight products such as gas oil.
  • the catalyst oil mixture moves rapidly through the reactor at a rate faster than that of the heat carrier solids.
  • the products from reactor 2 pass to a separator 4 where a gas liquid product is separated.
  • This liquid product contains some of the micron or sub-micron size crystalline aluminosilicate zeolite, but the presence of these materials in the oil does not present any technical problems.
  • the remaining portion of the powdered material, together with the solids, passes through line 5 into an air calciner 6 to which air is introduced through line 7.
  • the powdered crystalline aluminosilicate zeolite passes through line 8 into filter 9 where it is recovered and either discarded or a portion recirculated back to reactor 3 through line 10.
  • the hot solids from the air calciner 6 are recirculated to the mixing zone 1 through line 3.
  • the reduced crude either neat or containing 400 to 2000 ppm of a dispersed acid cracking catalyst was charged into a fluidized bed reactor maintained at 510°C, at a rate of 1.13 gm/min.
  • the reactor contained 50 ml (19 grams) of y-alumina particles which served as the heat transfer solids.
  • the particles were fluidized by flowing 20 ml/min to 850 ml/min of helium depending on the activity of the dispersed catalyst and the oil residence time desired. Material balances were made at 10-minute intervals.
  • the oil was momentarily stopped and the reactor flushed with helium, after which the coke deposit on the heat transfer solids was burnt with a stream of 40% oxygen in nitrogen flowing at 400 ml/min and the combustion gas monitored with an IR detector for CO and CO 2 until all the coke was burnt.
  • the reactor was flushed with helium before restarting the crude oil/dispersed catalyst feed pump.
  • the reactor was filled with 19 gms of fluid particles of -alumina (60-120 mesh), a thermal background run was first made without any added dispersed catalyst. After the thermal run, the feed was changed to the one containing the dispersed catalyst.
  • a 40/1 Si0 2 /Al 2 O 3 ZSM-5 was steam activated according to U.S. Patent No. 4,326,994 to an alpha value of 1600.
  • the zeolite was in powdered form comprising submicron particles. It was dispersed in the oil at a concentration of 400 ppm.
  • the preparation was carried out contacting 52 grams of rare earth exchanged Y with 398.7 grams of 2.0 molar NH 4 N0 3 for 96°C for one hour.
  • the material was then steamed for one hour at 1000°F with saturated steam followed by treatment with ethylene diaminetetraacetic acid (neutralized with ammonium hydroxide to a pH of 6.7).
  • the treated material was then calcined at 1000°F for one hour followed by exchange with 2 molar hot NH 4 N0 3 .
  • the material was again calcined for one hour, exchanged with boiling NH 4 NO 3 for one hour and washed with boiling water.
  • the washed material was again exchanged with boiling NH 4 N0 3 (2 molar) for one hour, washed with boiling water and dried overnight at 130°F.
  • the zeolite was in the powdered form, comprising particles of 2 ⁇ m or smaller. It was dispersed in the oil at a concentration of 2000 ppm.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (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)
  • Catalysts (AREA)
EP83305769A 1982-09-28 1983-09-27 Katalytischer Krackprozess unter Verwendung gepulverter Zeolithkatalysatoren Expired EP0107375B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US42600182A 1982-09-28 1982-09-28
US426001 1982-09-28

Publications (2)

Publication Number Publication Date
EP0107375A1 true EP0107375A1 (de) 1984-05-02
EP0107375B1 EP0107375B1 (de) 1986-05-28

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EP83305769A Expired EP0107375B1 (de) 1982-09-28 1983-09-27 Katalytischer Krackprozess unter Verwendung gepulverter Zeolithkatalysatoren

Country Status (7)

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EP (1) EP0107375B1 (de)
JP (1) JPS5980489A (de)
AU (1) AU559911B2 (de)
BR (1) BR8305308A (de)
CA (1) CA1218619A (de)
DE (1) DE3363785D1 (de)
ZA (1) ZA837254B (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA859846B (en) * 1984-12-27 1987-08-26 Mobil Oil Corp Catalytic cracking with a mixture of faujasite type zeolites and zeolite beta

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1060749A (en) * 1964-04-13 1967-03-08 Mobil Oil Corp Catalytic conversion of hydrocarbons

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1060749A (en) * 1964-04-13 1967-03-08 Mobil Oil Corp Catalytic conversion of hydrocarbons

Also Published As

Publication number Publication date
BR8305308A (pt) 1984-05-08
AU559911B2 (en) 1987-03-26
CA1218619A (en) 1987-03-03
DE3363785D1 (en) 1986-07-03
JPS5980489A (ja) 1984-05-09
EP0107375B1 (de) 1986-05-28
AU1955483A (en) 1984-04-05
ZA837254B (en) 1985-05-29

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