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
  • 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
• • 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
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/12—Silica and alumina

Definitions

• This invention relates to novel hydrocarbon conversion catalysts and their supports, methods for their preparation, and use thereof in hydrocarbon conversion processes. More particularly, the present invention relates to a high activity, large-pore silica/alumina cogel suitable for the conversion of hydrocarbon feeds.
• the cogel may also advan- tageously incorporated into cracking and hydroproce ⁇ sing catalysts.
• Silica, alumina and their amorphous mixtures are well known as catalysts used in hydrocarbon conversion process.
• the method of preparation clearly controls the resultant activ- ity (such as cracking or i ⁇ omerization activity), and physical properties (such as pore structure and .volume, surface area, density and catalyst strength).
• Silica/- alumina catalysts such as in the present invention can be used "as is", particularly in reactions that require acidic catalysts, or can optionally be combined with zeolites, clays or other binders, and inorganic oxides for the cracking of liquid hydrocarbons in cracking reactors such as fluid catalytic crackers.
• silica/alumina catalyst composites Numerous silica/alumina catalyst composites and processes for their preparation are described in the patent litera- ture. Silica-alumina composites have been used commercially for a variety of hydrocarbon processing applications, such as cracking, desulfurization, demetalation, and denitrification.
• U.S. Patent No. 4,226,743 de ⁇ cribes a proces ⁇ for preparing a silica-alumina catalyst which is dense and attrition re ⁇ istant.
• the ⁇ ilica-alumina hydrogel is precipitated at high pH and ⁇ ub ⁇ equently reacted with sufficient acid alumi- num salt at a pH below 4 to obtain an acidic hydrogel slurry.
• Substantial quantities of clay and/or crystalline alumino- ⁇ ilicate zeolites may be included.
• U.S. Patent No. 4,310,441 describes large pore silica-alumina gels and a method for producing them.
• the ⁇ ilica-alumina gel is derived from a cationic aluminum ⁇ ource and also an anionic aluminum ⁇ ource.
• U.S. Patent No. 4,198,319, Alafandi discloses a process where catalyst is prepared by a method comprising mixing in a slurry a fauja ⁇ ite or ⁇ ilica-alumina gel containing 50-70 mole ⁇ ilica, and clay, and ⁇ pray-drying ⁇ lurry into a cata- ly ⁇ t.
• Alafandi also shows combinations of gel with clay and zeolite for u ⁇ e in an FCC unit.
• U.S. Patent No. 4,289,653 Jaffe teaches preparing an extruded catalyst by mixing aluminum sulfate and sulfuric acid with sodium silicate to form a ⁇ ilica ⁇ ol in an alumina salt solution at pH of 1-3, adding NH.OH under substantially constant pH of at least 4 to 6; adding more NH.OH to form a cogelled mas ⁇ to pH 7.5-8.5; wa ⁇ hing cogelled a ⁇ ; mulling the ma ⁇ with peptizing agent, a Group VI-B metal compound and a Group VIII metal compound to form extrudable dough; extruding; and drying and calcining.
• Thi ⁇ invention compri ⁇ e ⁇ catalytically-active ⁇ ilica/alumina cogel ⁇ capable of hydrocarbon conver ⁇ ion. Specifically, it compri ⁇ e ⁇ a cataly ⁇ t ba ⁇ e compri ⁇ ed of high ⁇ urface area silica/alumina cogel tailored to contribute to both the activity and octane-enhancing characteristic ⁇ of the cata- lyst.
• the invention also comprises a proces ⁇ for preparing the cataly ⁇ t and a proces ⁇ for converting hydrocarbonaceou ⁇ feedstock using the catalyst.
• the catalyst not only converts hydrocarbon feeds to high octane gasoline, but increa ⁇ e ⁇ the light cycle oil yield and decreases the heavy cycle oil yield also while improving the quality of both.
• the cataly ⁇ t co po ⁇ ition of thi ⁇ inven- tion comprises a cogelled, silica-alumina matrix prepared by the method which comprises:
• the catalyst also perform ⁇ well in combination with known "octane-enhancing" additive ⁇ , such as H-ZSM-5, to yield an increased octane rating of the gasoline fraction.
• octane-enhancing additive ⁇ such as H-ZSM-5
• FIGURE 1 is a graphic representation of the peak diameter of the pore size distribution versus the apparent bulk density (ABD) of a catalyst of the present invention.
• FIGURE 2 is a graphic representation of the pore volume versu ⁇ the apparent bulk density of a cataly ⁇ t of the present invention.
• FIGURE 3 is a graphic repre ⁇ entation of the the peak diameter of the pore ⁇ ize distribution versu ⁇ the apparent bulk density (ABD) of another, modified cogel of the present invention.
• FIGURE 4 is a graphic representation of the pore volume versus the apparent bulk density of another, modified cataly ⁇ t of the present invention.
• the cogel comprising the present invention is preferably composed of ⁇ ilica, alumina and their amorphous mixtures.
• the method of preparation controls physical properties, such as pore structure and volume, surface area, density and catalyst strength, which in turn governs the resultant activity such as cracking or i ⁇ omerization. It u ⁇ t be noted that ⁇ eemingly very minor differences in the prepara- tion factors di ⁇ cu ⁇ ed below can make ⁇ ignificant differ- ence ⁇ in the make-up and effectivene ⁇ for a particular purpo ⁇ e of the matrix and a cataly ⁇ t of which it may be a component.
• the numerou ⁇ specific factor ⁇ that are involved in preparing material ⁇ containing ⁇ ilica-alumina mixture ⁇ include:
• the propertie ⁇ of the compo ⁇ ition are highly ⁇ en ⁇ itive to each of these factor ⁇ , and variations among these factors, especially in combination, will greatly influence the particular propertie ⁇ of the final cogel produced.
• This cogel is surprisingly active for the cracking of large molecule ⁇ , such a ⁇ in vacuum gas oils, to smaller molecule ⁇ , such as gasoline, and finds particular u ⁇ e as the active matrix for cataly ⁇ t ⁇ .
• the olefinicity of the products, a ⁇ indicated by the C. olefin to C . total ratio, is ⁇ urpri ⁇ - ingly high.
• Thi ⁇ i ⁇ indicative of ga ⁇ oline of high octane.
• the present invention also con- templates a proce ⁇ for preparing the amorphou ⁇ ⁇ ilica- alumina cogel, which can be formed into spheres via spray drying, and then ⁇ ub ⁇ equently dried to a water content of le ⁇ than 5 wt. percent. It i ⁇ al ⁇ o contemplated that the cogel may be incorporated into a multi-component cataly ⁇ t.
• the proce ⁇ for preparing the amorphous ⁇ ilica-alumina cogel yields a material which i ⁇ ⁇ urpri ⁇ ingly attrition-resistant in spray-dried sphere ⁇ , and surprisingly versatile with respect to the pore volumes, pore size distributions, and apparent bulk den ⁇ itie ⁇ , attainable.
• the cogels can be made in either a batch or a continuou ⁇ mode.
• high MAT conver ⁇ ions obtainable between about 55% and 80%;
• N_ pore volumes ranging from about 0.2 cc/gm to 1.2 cc/gm;
• N_ pore size di ⁇ tribution peak diameter ranging from about 3 ⁇ A to 260A, mo ⁇ t pore ⁇ occurring in the me ⁇ opore range of 20 to 500A.
• Micropore ⁇ are defined a ⁇ ⁇ 2 ⁇ A. Macropore ⁇ are defined a ⁇ >500A.
• the preferred cogel may be further defined a ⁇ one which, in it ⁇ equilibrium ⁇ tate, exhibit ⁇ a ⁇ pecified activity expre ⁇ ed a ⁇ a weight percentage derived from the micro- activity te ⁇ t (MAT). It may al ⁇ o be described a ⁇ one which exhibit ⁇ a ⁇ pecified ⁇ electivity expre ⁇ sed a ⁇ the ratio of C. olefin ⁇ to the total C . product a ⁇ derived by the MAT.
• the preferred MAT activity of the pre ⁇ ent catalyst i ⁇ measured by a modified ASTM D-3907.
• the ASTM D-3907 proce- dure provides relative MAT activity for conversion of a standard feed at standard conditions.
• the foregoing weight percentage and ratio of C, olefins to the total C . product are the values obtained on a standard feed at 496°C (925°F), 15 to 16 (weight hourly space velo- city), 3 C/O (catalyst to oil weight ratio), and calculated on the basi ⁇ of a pre-equilibrated (a ⁇ de ⁇ cribed above) cataly ⁇ t dried at 593°C (1100°F) in air.
• the preferred cogel can al ⁇ o be categorized as one which, in the course of extended operation, maintains a level of conversion of at least 40% by weight or volume and, more preferably, of at least 50% by weight, particularly on a Feedstock such as Feedstock A in the Examples.
• the silica-alumina cogelled catalyst i ⁇ prepared by the steps comprising:
• the mixing ⁇ tep ⁇ to make the cogelled ⁇ lurry can be prepared in either a batch or a continuou ⁇ ma ⁇ .
• the ⁇ ilica ⁇ ol de ⁇ cribed in Step 1 i ⁇ preferably defined a ⁇ a colloidal di ⁇ per ⁇ ion or ⁇ u ⁇ pen ⁇ ion of the metal oxide in a liquid.
• cogelled slurry or hydrogel may be de ⁇ cribed a ⁇ a coagulated colloid with an imbibed liquid phase.
• “synere ⁇ i ⁇ ” refer ⁇ to molecular rearrangements which occur in hydrogel ⁇ , in particular, ⁇ ilica and ⁇ ilica-alumina hydrogel ⁇ .
• the ⁇ e rearrangement ⁇ consist of condensation reactions among the units present in the hydrogel ⁇ . Any factor ⁇ which promote or disrupt these reactions affect the ⁇ tructure of the hydrogel and al ⁇ o the structure of the final dried cogel.
• a process parameter critical to the ⁇ ucce ⁇ ful creation of the de ⁇ ired cataly ⁇ t is the ⁇ yneresi ⁇ of the cogelled mass.
• Synere ⁇ i ⁇ may be best defined or analogized to an aging proce ⁇ s in which a compo ⁇ ition, particularly a hydrogel, contracts and gives up a liquid, usually water, in the process.
• This syneresis in the pre ⁇ ent invention materially alter ⁇ the nature of the cogelled may and therefore the re ⁇ ulting ⁇ pray-dried cogel cataly ⁇ t, rendering it uniquely ⁇ uitable for the purposes discussed above.
• °f synere ⁇ i ⁇ in ⁇ ilica-alumina gels ⁇ ee C. J. Plank, et al., J. Colloid. Sci., 2 (1947) 399, and C. J. Plank, J • Colloid. Sci., 2 (1947) 413, incorporated herein by reference.
• step 5 helps to control the physical and chemical characteri ⁇ tic ⁇ of the ⁇ pray-dried co-gel, e.g., pore volume and pore size distribution.
• Fir ⁇ t, the ⁇ ilica ⁇ ol de ⁇ cribed in Step 1 i ⁇ preferably defined a ⁇ a colloidal di ⁇ per ⁇ ion or ⁇ u ⁇ pen ⁇ ion of the metal oxide in a liquid.
• hydrogel refer ⁇ to molecular rearrangement ⁇ which occur in hydrogel ⁇ , in par- ticular, ⁇ ilica and ⁇ ilica-alumina hydrogel ⁇ . These rearrangements consist of condensation reactions among the units present in the hydrogel ⁇ . Any factor ⁇ which promote or di ⁇ rupt the ⁇ e reaction affect the structure of the hydrogel and the ⁇ tructure of the final dried cogel. Aging at temperature ⁇ of about 25-105°C, preferably 60-90°C, in ⁇ tep 3 affect ⁇ the rate of filtration in step 4 and the physical characteri ⁇ tic ⁇ of the spray-dried product of ⁇ tep 6. In a le ⁇ preferred embodiment, step 5 may be eliminated.
• Step 7 washing the cogelled mass or the spray- dried particles, may be accomplished at ambient or elevated temperature ⁇ , i.e. ⁇ 100°C, with ba ⁇ e exchange medium ⁇ uch a ⁇ ammonium acetate, or Al containing ⁇ olution to reduce the Na concentration to less that about 0.5 weight percent. Ammonium acetate at elevated washing temperatures is par- ticularly effective. Step 7 may be done at various point ⁇ in the procedure after ⁇ tep 2. Generally, the cogelled ma ⁇ s washed prior to mixing with the zeolite. The gellation, encompa ⁇ ed by ⁇ tep 1 and 2, may be done in a batch or continuou ⁇ manner.
• Thi ⁇ amorphou ⁇ ⁇ ilica-alumina cogel cataly ⁇ t shows high MAT conversion both a ⁇ prepared and after ⁇ teaming.
• the MAT conver ⁇ ion ⁇ of the fre ⁇ h cogelled cataly ⁇ t a ⁇ prepared range ⁇ from 45 to 80 weight percent conversion, preferably >65%, mo ⁇ t preferably > 70 weight %.
• the MAT conver ⁇ ion of the ⁇ teamed material ⁇ range from about 40 to -65 weight percent, more preferably >50 weight percent.
• the cogelled product i ⁇ spray-dried after homogenizing the slurry may al ⁇ o be exchanged with polyvalent ions sub ⁇ equent to ⁇ pray-drying, more preferably exchanged with rare earth ions subsequent to spray-drying.
• component ⁇ can be combined with the cogel, for example zeolite ⁇ (large, intermediate, and/or small pore), sieve ⁇ , ⁇ uch as Beta, SAPO' ⁇ , AlPO's etc., clays, modified clays, inorganic oxides, and oxide precursors, metals, carbon, organic ⁇ ub ⁇ tances, etc. These may be added in ⁇ tep ⁇ 1,2,5, and/or 7, above.
• other metal ⁇ may be used to exchange residual Na 2 0.
• the cogel ⁇ have been found to be excellent matrice ⁇ for FCC applica- tion ⁇ , a ⁇ well a ⁇ excellent supports for hydrocracking applications. See U.S.S.N. 252,236, filed September 30, 1988, incorporated herein by reference.
• the spray-dried cogel may be used as a cracking cataly ⁇ t, particularly when u ⁇ ed in combination with clay ⁇ or other binder ⁇ , and/or with a zeolite.
• a cracking cataly ⁇ t which ⁇ how ⁇ high level ⁇ of activity in a commercial FCC operation
• the weight percent conversion represent ⁇ 100 minu ⁇ the weight percent of fre ⁇ h feed boiling above the temperature of 221°C (430°F).
• the weight percent conver ⁇ ion includes the weight percent coke and the weight percent fre ⁇ h feed boiling below the temperature of 221°C (430°F).
• the conver ⁇ ion capabilitie ⁇ may be expre ⁇ ed in terms of the conversion produced during actual operation of the FCC proce ⁇ or in term ⁇ of the conversion produced in ⁇ tandard cataly ⁇ t activity te ⁇ t ⁇ . It i ⁇ al ⁇ o within the contemplation of the invention to include the use of the cogel for the in a proce ⁇ for the catalytic cracking of hydrocarbonaceou ⁇ feed ⁇ tock ⁇ . It find ⁇ particular u ⁇ e for proce ⁇ ing residuum or incremental residuum, more particularly re ⁇ iduum ⁇ containing catalyst-contaminating metals.
• Example ⁇ 1-5 are ⁇ hown in Table I.
• the filter cake was washed with a solution of 1.18 lbs. of NH.HCO, dis ⁇ olved in 30 liters of water (DI). This wash wa ⁇ repeated three more times. It was then washed once with 30 liters of water (DI).
• Batch A 600 ml ⁇ . of water (DI) wa ⁇ added to 4100 grams of cogelled mass. The mixture was homogenized. Its pH wa ⁇ about 8.1. The mixture was then spray dried.
• DI water
• Batch B,C,D 62 grams of acetic acid wa ⁇ added to 8,679.04 gram ⁇ of the cogelled ma ⁇ (LOI-90 wt. %) to reduce the pH to about 5.42 and induce ⁇ yneresis. 22 additional grams of acetic acid were added to reduce further the pH to 4.83. The mixture was then homogenized, after which ammonium hydroxide was added to raise the pH to 5.59.
• Batch B was aged at ambient temperature for 1 hour.
• Batch C wa ⁇ aged at ambient temperature for 4 hour ⁇ .
• Batch E 50 gram ⁇ of acetic acid wa ⁇ added to 4544 gram ⁇ of the cogelled ma ⁇ (LOI-90) to adjust the pH to 5.58.
• An additional 28 gram ⁇ of acid wa ⁇ added to reduce the pH further to 5.21, and finally 19 gram ⁇ more wa ⁇ added to reduce the pH to 4.85.
• the mixture wa ⁇ constantly homogenized.
• the pH wa ⁇ then raised to 5.58 by adding ammonium hydroxide.
• the material wa ⁇ again homogenized, ⁇ creened, and aged at ambient condition ⁇ for 24 hour ⁇ .
• the ⁇ e material ⁇ were all ⁇ pray dried to form an attrition re ⁇ i ⁇ tant ⁇ olid cogel cataly ⁇ t.
• Example 2 Material was prepared as in Example 1, except the after titrating with NH.OH, to a pH of 8, the ⁇ lurry wa ⁇ heated to 52°C for a total heating time of about 30 minute ⁇ , and filtered.
• the synere ⁇ i ⁇ ⁇ tep was accomplished by adding acetic acid to reduce the pH to 4.96.
• NH.OH wa ⁇ added to raise the pH to 5.63.
• the material wa ⁇ homogenized, aged overnight to a pH of ⁇ 5.57, rehomogenized, and spray dried.
• Example 3 Material was prepared as in Example 3, except that it wa ⁇ titrated with NH 4 OH to a pH of 5.6, heated to 80°C over a 30 minute period and held at 80°C for 10 minutes.

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• 1989
  • 1989-11-22 BR BR898907200A patent/BR8907200A/pt not_active Application Discontinuation
  • 1989-11-22 JP JP2500876A patent/JPH03503742A/ja active Pending
  • 1989-11-22 WO PCT/US1989/005298 patent/WO1990005702A1/en not_active Ceased
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